Synthetic Method for Pheromone Derivatives by Z-Selective Olefin Metathesis

Abstract

Disclosed herein is a method for synthesizing aliphatic olefin metathesis products of high Z-isomer purity from olefin feedstocks of low Z-isomer purity. The method includes contacting an olefin metathesis reaction partner, such as an acylated alkenol or alkenal acetal, with an internal olefin in the presence of a Z-selective metathesis catalyst to form an aliphatic olefin metathesis product. In various embodiments, the aliphatic olefin metathesis product is an insect pheromone. Pheromone compositions and methods for their use are also described. TIFF2023527882000101.tif118157

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 032,932, filed June 1, 2020, which is incorporated herein by reference in its entirety. [Background technology]

[0002] Background of the Invention As the global demand for food increases, the need for effective pest control increases. Traditional insecticides are among the most popular chemical control agents because they are readily available, fast-acting, and reliable. However, the overuse, misuse, and abuse of these chemicals has led to resistant pests, changes in the natural environment, and in some cases, environmental damage.

[0003] The use of insect pheromones to control pest populations is gaining popularity as a viable, safe, and environmentally friendly alternative to traditional insecticides. Since their discovery in the late 1950s, these molecules have demonstrated effectiveness in reducing insect populations through a variety of methods, including mass trapping, attraction-killing, and mating disruption. The latter method, in particular, provides a non-toxic means of pest control, taking advantage of the ability of synthetic pheromones to cause confusion and mating disruption by masking natural pheromones.

[0004] While pheromones show significant potential in agricultural insect control, the cost of synthesizing pheromones using currently available technologies is prohibitive, preventing widespread use of this sustainable technology outside of high-value crops. Thus, there is a need to develop new technologies for the cost-effective production of insect pheromones and related fragrances, flavors, and polymer intermediates. The present invention addresses this need with a synthetic method capable of forming a wide range of unsaturated aliphatic olefin metathesis products of high Z-isomer purity, including synthetic insect pheromones, from low-cost raw materials. [Brief explanation of the drawings]

[0005] [Figure 1] 1 shows the catalytic hydrogenation of methyl oleate to form oleyl alcohol. [Figure 2] The synthesis of Z9-14Ac is shown by stereoretaining olefin cross-metathesis using oleyl acetate and (Z)-dec-5-ene. [Figure 3] The synthesis of Z9-12Ac is shown by stereoretaining olefin cross-metathesis using oleyl acetate and (Z)-hex-3-ene. [Figure 4] 1 shows the synthesis of metathesized jojoba oil acetate via stereoretentive olefin cross-metathesis using jojoba oil acetate and (Z)-hex-3-ene. [Figure 5] We demonstrate the synthesis of cross-metathesis jojoba oil alcohols by stereoretentive olefin cross-metathesis using commercially available jojoba oil and (Z)-hex-3-ene, followed by reduction. Summary of the Invention

[0006] Brief Summary of the Invention Provided herein is a method for synthesizing a Z-enriched aliphatic olefin metathesis product. The method includes contacting an olefin metathesis reaction partner with an internal olefin in the presence of a Group 8 transition metal metathesis catalyst to form a Z-enriched aliphatic olefin metathesis product, wherein the aliphatic olefin metathesis product is an acylated alkenol or alkenal acetal; the olefin metathesis reaction partners comprise a mixture of Z olefins and E olefins in a starting Z:E ratio; the aliphatic olefin metathesis product comprises a mixture of Z olefins and E olefins in a product Z:E ratio; The product Z:E ratio is higher than the starting Z:E ratio.

[0007] In some embodiments, the present invention provides a compound of formula I: TIFF0007821747000001.tif16128, a method for synthesizing an aliphatic olefin metathesis product, comprising: reacting an aliphatic olefin metathesis product of Formula III: TIFF0007821747000002.tif16128 and an olefin metathesis reaction partner of formula IV: and an internal olefin in the presence of a metathesis catalyst, wherein: R 1 is H and C 1~6 selected from the group consisting of alkyl; R 2 C 1~18 Alkyl and C 2~18 alkenyl; R 3 C 1~18 is alkyl; The subscript y is an integer ranging from 0 to 17; The subscript z is an integer ranging from 0 to 17; The method is provided wherein the metathesis catalyst is a Z-selective Group 8 transition metal catalyst.

[0008] In some embodiments, the metathesis catalyst is a Z-selective ruthenium catalyst or a Z-selective osmium catalyst.

[0009] In some embodiments, the metathesis catalyst used in the method for synthesizing the aliphatic olefin metathesis product of Formula I is a compound of Formula V: TIFF0007821747000004.tif38128 structure, During the ceremony, M is selected from the group consisting of ruthenium and osmium; X and Y are independently selected from the group consisting of S and O; Z is selected from the group consisting of O, S(=O), N, and halogen; each subscript m and subscript n is an integer independently selected from 0, 1, 2, 3, and 4; Each Ra are independently selected from the group consisting of halogen, C1-C6 alkyl, alkoxy, aryl, and heteroaryl; or one R a is the adjacent R a together to form an unsubstituted or substituted bicyclic or unsubstituted or substituted polycyclic ring; Each R b are independently selected from the group consisting of halogen, C1-C6 alkyl, alkoxy, aryl, and heteroaryl; or one R b is the adjacent R b together to form an unsubstituted or substituted bicyclic or unsubstituted or substituted polycyclic ring; R c is selected from the group consisting of hydrogen and C1-C6 alkyl; Each R d , R e , R f , and R g is independently selected from the group consisting of hydrogen and C1-C6 alkyl; R 12 and R 13 is independently selected from the group consisting of 2,4,6-tri-isopropylphenyl, 2,6-di-isopropylphenyl, 2,6-di-adamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl; Each R 14 are independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl, and phenyl; R 15 is selected from the group consisting of hydrogen, halogen, and C1-C6 alkyl, or R 15 and one R 14 come together to form a bond.

[0010] In some embodiments, the method for synthesizing an aliphatic olefin metathesis product of Formula I comprises reacting an acylating agent with an aliphatic olefin metathesis product of Formula II: with an alkenol of formula III to form an olefin metathesis reaction partner of formula III.

[0011] In some embodiments, the method for synthesizing an aliphatic olefin metathesis product comprises a compound of formula IIa: reducing the unsaturated aliphatic carboxyl derivative of TIFF0007821747000006.tif16128 to form an alkenol of formula II; In the formula, R 4 is H and C 1~8 alkyl.

[0012] In some embodiments, the synthesis of an aliphatic olefin metathesis product comprises contacting a terminal olefin with a metathesis catalyst to form an internal olefin. [The present invention 1001] 1. A method for synthesizing a Z-enriched aliphatic olefin metathesis product, comprising contacting an olefin metathesis reaction partner with an internal olefin in the presence of a Group 8 transition metal metathesis catalyst to form a Z-enriched aliphatic olefin metathesis product, wherein the aliphatic olefin metathesis product is an acylated alkenol or alkenal acetal; the olefin metathesis reaction partners comprise a mixture of Z olefins and E olefins in a starting Z:E ratio; the aliphatic olefin metathesis product comprises a mixture of Z olefins and E olefins in a product Z:E ratio; A process wherein the product Z:E ratio is higher than the starting Z:E ratio. [The present invention 1002] 1001. The process of claim 1001, wherein the metathesis catalyst is a Z-selective ruthenium catalyst or a Z-selective osmium catalyst. [The present invention 1003] 1001. The process of claim 1001, wherein the aliphatic olefin metathesis product is at least 97% to 99% Z. [The present invention 1004] 1001. The process of claim 1001, wherein the aliphatic olefin metathesis product is greater than 99% Z. [The present invention 1005] 1001. The process of claim 1001, wherein the metathesis reaction partner is about 1% to about 50% E. [The present invention 1006] The aliphatic olefin metathesis product has Formula I: TIFF0007821747000007.tif16128 is an acylated alkenol of; The metathesis reaction partner is of formula III: TIFF0007821747000008.tif16128 is a compound of; The internal olefin is of formula IV: TIFF0007821747000009.tif10128 is a compound of; R 1 But H and C 1~6 selected from the group consisting of alkyl; R 2 But C 1~18 Alkyl and C 2~18 alkenyl; R 3 C 1~18 is alkyl; The subscript y is an integer ranging from 0 to 17; The subscript z is an integer ranging from 0 to 17; the Group 8 transition metal metathesis catalyst is a Z-selective Group 8 transition metal catalyst; The method of the present invention 1001. [The present invention 1007] The Z-selective metathesis catalyst has the structure of Formula V: TIFF0007821747000010.tif38128 and During the ceremony, M is selected from the group consisting of ruthenium and osmium; X and Y are independently selected from the group consisting of S and O; Z is selected from the group consisting of S(=O), O, N, and halogen; The subscript m is an integer selected from 2, 4, 3, 1, and 0; The subscript n is an integer selected from 0, 1, 2, 3, or 4; Each R a are independently halogen, C 1 ~C 6 selected from the group consisting of alkyl, alkoxy, aryl, and heteroaryl; or one R a is the adjacent R a together to form an unsubstituted or substituted bicyclic or unsubstituted or substituted polycyclic ring; Each R b are independently halogen, C 1 ~C 6 selected from the group consisting of alkyl, alkoxy, aryl, and heteroaryl; or one R b is the adjacent R b together to form an unsubstituted or substituted bicyclic or unsubstituted or substituted polycyclic ring; R c is hydrogen and C 1 ~C 6 selected from the group consisting of alkyl; Each R d 、R e 、R f , and R g are independently hydrogen and C 1 ~C 6 selected from the group consisting of alkyl; R 12 and R 13 is independently selected from the group consisting of 2,6-di-isopropylphenyl, 2,4,6-tri-isopropylphenyl, 2,6-di-adamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl; Each R 14 is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl, phenyl, and hydrogen; R 15 is hydrogen, halogen, and C 1 ~C 6 alkyl, or R 15 and one R 14 come together to form a bond, The method of the present invention 1006. [The present invention 1008] M is ruthenium; X and Y are S; Z is selected from the group consisting of S(=O) and O; The subscript m is 2; The subscript n is 0; Each R a are independently halogen, C 1 ~C 6 selected from the group consisting of alkyl, and aryl; R c is hydrogen; Each R d 、R e 、R f , and R g is hydrogen; Each R 14 is independently selected from the group consisting of methyl, isopropyl, benzyl, and tert-butyl; The method of the present invention 1007. [The present invention 1009] The metathesis catalyst is selected from the group consisting of: TIFF0007821747000011.tif48137 The method of the present invention 1007, selected from the group consisting of: [The present invention 1010] The synthesis of aliphatic olefin metathesis products is carried out by reacting an acylating agent with a compound of formula II: TIFF0007821747000012.tif10128 with an alkenol of formula III to form an olefin metathesis reaction partner of formula III. [The present invention 1011] The process of claim 1010, wherein the acylating agent is acetic anhydride. [The present invention 1012] The synthesis of an aliphatic olefin metathesis reaction partner is carried out by reacting a compound of formula IIa: TIFF0007821747000013.tif16128 (In the formula, R 4 is H and C 1~8 alkyl) 10. The process of claim 10, comprising reducing an unsaturated aliphatic carboxylic derivative of formula II to form an alkenol of formula II. [The present invention 1013] The process of claim 1012, wherein the step of forming the alkenol of formula II comprises contacting an unsaturated aliphatic carboxylic derivative with a base in the presence of a hydrogenation catalyst and hydrogen gas. [The present invention 1014] The process of claim 10, wherein the step of forming the alkenol of formula II comprises contacting an unsaturated aliphatic carboxylic derivative with a reducing agent. [The present invention 1015] 1014. The process of claim 1014, wherein the reducing agent is sodium bis(2-methoxyethoxy)aluminum hydride. [The present invention 1016] The method of claim 1012, wherein the unsaturated aliphatic carboxylic derivative is derived from a natural oil. [The present invention 1017] 1016. The method of claim 1016, wherein the natural oil is selected from the group consisting of almond oil, canola oil, avocado oil, argan oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, grapeseed oil, olive oil, palm oil, peanut oil, hempseed oil, macadamia oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil, jojoba oil, mustard oil, shepherd's purse oil, cabbage oil, castor oil, and combinations thereof. [The present invention 1018] 1016. The process of claim 1016, further comprising the step of distilling the unsaturated aliphatic carboxylic derivative, alkenol, or olefin metathesis reaction partner prior to metathesis to remove plant-based impurities. [The present invention 1019] The aliphatic olefin metathesis product has the formula VI: TIFF0007821747000014.tif16128 is an alkenal acetal of; The metathesis reaction partner is of formula VII: TIFF0007821747000015.tif16128 is a compound of; The internal olefin is of formula IV: TIFF0007821747000016.tif10128 is a compound of; R 1 C 1~6 is alkyl; R 2 But C 1~18 Alkyl and C 2~18 alkenyl; R 3 C 1~18 is alkyl; The subscript y is an integer ranging from 0 to 17; The subscript z is an integer ranging from 0 to 17; the Group 8 transition metal metathesis catalyst is a Z-selective Group 8 transition metal catalyst; The method of the present invention 1001. [The present invention 1020] The metathesis product is represented by formula VIII: TIFF0007821747000017.tif16128 The method of claim 1019, further comprising converting the compound of formula (I) to an alkenal of formula (I). [The present invention 1021] 1001. The process of claim 1001, wherein the synthesis of the aliphatic olefin metathesis product comprises the step of forming an internal olefin by contacting a terminal olefin with a metathesis catalyst to form an internal olefin. [The present invention 1022] The internal olefin is of formula VIa: TIFF0007821747000018.tif12128 is a compound of; The terminal olefin is of formula IVb: TIFF0007821747000019.tif10128 The method of the present invention 1021, wherein the compound is [The present invention 1023] The process of claim 1021 or 1022, wherein the metathesis catalyst for forming the internal olefin is a Z-selective ruthenium catalyst or a Z-selective tungsten catalyst. [The present invention 1024] R 1 C 1~3 alkyl, and R 2 C 1~12 alkyl, and R 3 C 1~12 1006. The method of claim 1006, wherein y is an integer ranging from 5 to 15, and z is an integer ranging from 0 to 7. [The present invention 1025] The metathesis reaction partner of formula III is an aliphatic C 12 ~C 30 olefin acetate; The internal olefin of formula IV is C 4 ~C 20 is an internal olefin; The aliphatic olefin metathesis product of formula I is C 8 ~C 28 (Z)-unsaturated aliphatic ester acetate, The method of the present invention 1006. [The present invention 1026] the olefin metathesis reaction partner of formula III is (Z)-octadec-9-en-1-yl acetate; The internal olefin of formula IV is (Z)-dec-5-ene; The aliphatic olefin metathesis product of formula I is (Z)-tetradec-9-en-1-yl acetate. The method of the present invention 1006. [The present invention 1027] the olefin metathesis reaction partner of formula III is (Z)-octadec-9-en-1-yl acetate; The internal olefin of formula IV is (Z)-hex-3-ene; The aliphatic olefin metathesis product of formula I is (Z)-dodec-9-en-1-yl acetate; The method of the present invention 1006. [The present invention 1028] the olefin metathesis reaction partner of formula III is (Z)-icosa-11-en-1-yl acetate; The internal olefin of formula IV is (Z)-hex-3-ene; The aliphatic olefin metathesis product of formula I is (Z)-tetradec-11-en-1-yl acetate; The method of the present invention 1006. [The present invention 1029] 1001. The process of claim 1001, wherein the synthesis of the aliphatic olefin metathesis product comprises the step of contacting the olefin metathesis reaction partner with a pretreatment reagent prior to contacting with the internal olefin. [The present invention 1030] 1029. The method of claim 1029, wherein the pretreatment reagent is selected from the group consisting of alumina, triethylaluminum, and magnesium aluminum isopropoxide. DETAILED DESCRIPTION OF THE INVENTION

[0013] Detailed Description of the Invention I. Introduction The present invention provides a method for the synthesis of high-purity aliphatic olefin derivatives (e.g., linear lepidopteran pheromones; SCLPs) through stereoretentive olefin cross-metathesis of internal olefins with low isomeric purity. A wide variety of pheromones with high Z purity can be obtained by using various low-purity aliphatic olefin derivative and internal olefin feedstocks in combination with a Z-selective olefin metathesis catalyst. The present invention enables the use of commercially available olefin feedstocks with low isomeric purity to prepare high-purity SCLPs, thereby greatly increasing the industrial applicability of this technology.

[0014] II. Definition The following definitions and abbreviations are to be used in interpreting the present invention: As used herein, the term "invention" or "the present invention" is an open-ended term and is not intended to refer to any single embodiment, but rather encompasses all possible embodiments.

[0015] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. A composition, mixture, process, method, article, or device that contains a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent in the composition, mixture, process, method, article, or device. Further, unless expressly stated to the contrary, "or" means an inclusive "or" and not an exclusive "or."

[0016] The terms "about" and "around" used herein to modify a numerical value indicate a closed range surrounding the stated value. If "X" is a value, then "about X" or "around X" would indicate a value of 0.9X to 1.1X, and in certain cases, a value of 0.95X to 1.05X or 0.98X to 1.02X. Any reference to "about X" or "around X" specifically indicates at least the values ​​X, 0.95X, 0.96X, 0.97X, 0.98X, 0.99X, 1.01X, 1.02X, 1.03X, 1.04X, and 1.05X. Thus, "about X" and "around X" are intended to teach and provide written support for a claim limitation, for example, "0.99X."

[0017] As used herein, the term "substantially" describes a range of values ​​of about 85 to 100%, for example, 85 to 99.9%, 90 to 99.9%, 95 to 99.9%, 98 to 99.9%, or 99 to 99.9%.

[0018] As used herein, the term "majority" refers to a percentage in the range of more than 50%, for example, in the range of about 51-100%, 75-99.9%, 85-98.5%, or about 95-99%.

[0019] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, a reference to an "aliphatic olefin metathesis product" includes one aliphatic olefin metathesis product, as well as combinations or mixtures of two or more aliphatic olefin metathesis products (e.g., a mixture of aliphatic Z-olefin and aliphatic E-olefin metathesis products); a reference to an "unsaturated aliphatic carboxylic derivative" includes one unsaturated aliphatic carboxylic derivative, as well as combinations or mixtures of two or more unsaturated aliphatic carboxylic derivatives; a reference to an "alkenol" includes one alkenol, as well as combinations or mixtures of two or more alkenols; a reference to a "substituent" includes one substituent, as well as combinations of two or more substituents, etc.

[0020] As used herein, the term "metathesis product" refers to an olefin containing at least one double bond formed by a metathesis reaction. As used herein, the term "aliphatic olefin metathesis product" refers to a type of olefin-containing compound formed by a metathesis reaction (i.e., a type of metathesis product formed from an olefin and a metathesis reaction partner) having the structure RC(O)O-R', where R is an alkyl group as described below, and R' is a linear alkenyl group containing at least 4 carbon atoms, e.g., 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, or 40 carbon atoms. In some embodiments, R' is a C4-C 30 A non-limiting example of an "unsaturated aliphatic ester acetate" is an ester of RC(O)O-R', where R is a methyl group and R' is a C2-C6 alkyl group. 26 It is an aliphatic olefin metathesis product obtained by cross-metathesis between an olefin and an olefin metathesis reaction partner, which is a linear alkenyl group. 28(Z)-unsaturated aliphatic ester acetate" is also a non-limiting example of an aliphatic olefin metathesis product. In some embodiments, the aliphatic olefin metathesis product is a pheromone, such as a linear lepidopteran pheromone (SCLP).

[0021] As used herein, the term "metathesis reaction" refers to a catalytic reaction involving the exchange of alkylidene units (i.e., R2C= units) between compounds containing one or more carbon-carbon double bonds (e.g., olefinic compounds) by the formation and cleavage of carbon-carbon double bonds. Metathesis can occur between two molecules having the same structure (often referred to as self-metathesis) and / or between two molecules having different structures (often referred to as cross-metathesis).

[0022] As used herein, the term "pheromone" refers to a substance or a characteristic mixture of substances secreted and released by an organism and detected by a second organism of the same or a closely related species. Typically, detection of the pheromone by the second organism promotes a specific response, such as a behavioral response or developmental process. For example, insect pheromones can influence behaviors such as mating and aggregation. Examples of pheromones include compounds produced by Lepidoptera (i.e., moths and butterflies belonging to the families Geometridae, Noctuidae, Arctiidae, and Lymantriidae), such as C 10 ~C 18 Acetate, C 10 ~C 18 Alcohol, C 10 ~C 18 Aldehydes, and C 17 ~C 23 "Unsaturated pheromone" means any pheromone that has at least one carbon-carbon double bond, including, but not limited to, polyenes.

[0023] As used herein, the term "contacting" refers to the process of bringing at least two separate species into contact so that they can react. However, it should be recognized that the resulting reaction product can be produced directly by reaction between the added reagents or from an intermediate derived from one or more of the added reagents that can be produced in the reaction mixture.

[0024] As used herein, the term "metathesis reaction partner" refers to a compound having a carbon-carbon double bond that can react with an olefin in a metathesis reaction to form a new carbon-carbon double bond. The metathesis reaction partner can be an aliphatic olefin-containing compound, e.g., an olefin metathesis reaction partner. The term "olefin metathesis reaction partner" refers to a compound having the structure RC(O)O-R', where R is an alkyl group as described below, and R' is a linear alkenyl group containing at least 4 carbon atoms, e.g., 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, or 40 carbon atoms. In some embodiments, R' is a C6-C 34 It is a straight-chain alkenyl group. For example, "unsaturated fatty alcohol acetate" refers to an RC(O)O-R' in which R is a methyl group and R' is a C4-C 28 Further non-limiting examples of olefin metathesis reaction partners include RC(O)O-R', where R is a methyl group and R' is C 10 ~C 28 A straight-chain alkenyl group, "aliphatic C 12 ~C 30 Olefin Acetate" and "C 10 ~C 28 Acetate esters of aliphatic alkenols.

[0025] As used herein, the term "olefin" refers to a straight-chain (e.g., linear) or branched hydrocarbon compound containing at least one carbon-carbon double bond, and derivatives thereof. Olefins can be unsubstituted or substituted with one or more functional groups, including alcohol groups, protected alcohol groups, carboxylate groups, and carboxylic acid ester groups. As used herein, the term "olefin" encompasses hydrocarbons having two or more carbon-carbon double bonds (e.g., diolefins, triolefins, etc.). Hydrocarbons having two or more carbon-carbon double bonds and their derivatives are also referred to as "polyenes." The term "aliphatic olefin" refers to an olefin having at least four carbon atoms, and aliphatic olefins can have, for example, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, or 40 carbon atoms. Olefins can contain terminal double bonds ("terminal olefins") and / or internal double bonds ("internal olefins"). In some embodiments, the olefins used in the process of the present invention have from 4 to 26 carbon atoms. In certain other embodiments, the olefins used in the process of the present invention comprise a mixture of olefins having anywhere from 4 to 26 carbon atoms.

[0026] As used herein, the term "internal olefin" refers to an olefin in which each olefinic carbon (i.e., carbon of a carbon-carbon double bond; C=C) is substituted with at least one non-hydrogen substituent (e.g., R 1' R 2' C=CR 3' R 4' ; In the formula, R 1' and R 2' At least one of them is not hydrogen, and R 3' and R 4' and at least one of R is not hydrogen). The internal olefin can be di-, tri-, or tetra-substituted (e.g., a disubstituted internal olefin: R 5' HC=CHR 8' and / or HR 6' C=CR7' H; trisubstituted internal olefin: R 5' R 6' C=CHR 8' , R 5' R 6' C=CR 7' H, R 5' HC=CR 7' R 8' , and / or HR 6' C=CR 7' R 8' and tetrasubstituted internal olefins: R 5' R 6' C=CR 7' R 8' ; In the formula, R 5' , R 6' , R 7' , and R 8' may be the same or different and each independently represent an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, or a functional group).

[0027] As used herein, the term "terminal olefin" refers to an olefin (e.g., R 9' R 10' C=CH2; where R 9' and R 10' where at least one or both of R is not hydrogen. The terminal olefin may be mono- or di-substituted (e.g., mono-substituted terminal olefin: R 9' HC=CH2 and / or HR 10' C=CH2; and disubstituted terminal olefins: R 9' R 10' C=CH2; where R 9' and R 10' may be the same or different and each independently represent an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, or a functional group).

[0028] The term "aliphatic olefin derivative" refers to the olefin starting material used in the process of the present invention or a compound obtained from the aliphatic olefin starting material. Examples of aliphatic olefin derivatives include, but are not limited to, unsaturated aliphatic alcohols (i.e., alkenols), unsaturated aliphatic alcohol acetates and unsaturated aliphatic ester acetates (e.g., olefin metathesis reaction partners and aliphatic olefin metathesis products), unsaturated aliphatic aldehydes, unsaturated aliphatic carboxylic derivatives (e.g., unsaturated fatty acids, unsaturated fatty acid alkyl esters), and polyenes. In the present invention, both "metathesis products" and "aliphatic olefin metathesis products" are types of aliphatic olefin derivatives. In some embodiments, the aliphatic olefin derivatives used in the process of the present invention have 6 to 34 carbon atoms. In some embodiments, the aliphatic olefin derivatives synthesized according to the process of the present invention have 6 to 30 carbon atoms. In certain other embodiments, the aliphatic olefin derivatives used in the process of the present invention include a mixture of aliphatic olefin derivatives having anywhere from 4 to 34 carbon atoms. In certain other embodiments, the aliphatic olefin derivatives synthesized according to the methods of the present invention comprise a mixture of aliphatic olefin derivatives having anywhere from 4 to 30 carbon atoms.

[0029] Δ 9 -Unsaturated olefins are olefins in which the ninth carbon-carbon bond from the end of the olefin chain is a double bond (e.g., Δ 9 -unsaturated fatty alcohols, Δ 9 -Unsaturated fatty alcohol acetate, Δ 9 -Unsaturated aliphatic ester acetate, Δ 9 -unsaturated aliphatic aldehyde, Δ 9 -unsaturated aliphatic carboxylic derivatives, Δ 9 -unsaturated fatty acids, Δ 9 -unsaturated fatty acid alkyl esters, etc.) 9 -Unsaturated fatty acid refers to an olefinic carboxylic acid in which the ninth carbon-carbon bond counting from the carboxylic acid end of the olefin chain is a double bond. 9Examples of unsaturated fatty acids include, but are not limited to, 9-decenoic acid, oleic acid (i.e., (Z)-octadec-9-enoic acid), and elaidic acid (i.e., (E)-octadec-9-enoic acid). Another non-limiting example is Δ 9 The term "unsaturated aliphatic ester acetate" refers to an olefinic ester acetate in which the ninth carbon-carbon bond counting from the acetate end of the olefin chain is a double bond. 9 Examples of unsaturated aliphatic ester acetates include, but are not limited to, 9-decenyl acetate, (Z)-tetradec-9-en-1-yl acetate, and (E)-tetradec-9-en-1-yl acetate.

[0030] Similarly, Δ 11 -Unsaturated olefins are olefins in which the 11th carbon-carbon bond from the end of the olefin chain is a double bond (e.g., Δ 11 -unsaturated fatty alcohols, Δ 11 -Unsaturated fatty alcohol acetate, Δ 11 -Unsaturated aliphatic ester acetate, Δ 11 -unsaturated aliphatic aldehyde, Δ 11 -unsaturated aliphatic carboxylic derivatives, Δ 11 -unsaturated fatty acids, Δ 11 -unsaturated fatty acid alkyl esters, etc.) 11 The term "unsaturated fatty acid" refers to an olefinic carboxylic acid in which the 11th carbon-carbon bond counting from the carboxylic acid end of the olefin chain is a double bond. 11 Examples of unsaturated fatty acids include, but are not limited to, 11-dodecenoic acid, gondoic acid (i.e., (Z)-icosa-11-enoic acid or (Z)-eicosa-11-enoic acid), and trans-gondoic acid (i.e., (E)-icosa-11-enoic acid or (E)-eicosa-11-enoic acid). The prefixes "icosa" and "eicosa" refer to a hydrocarbon chain having 20 carbons (e.g., fully saturated C 20 hydrocarbon chain, i.e., alkyl; or C containing one or more unsaturated units 20It should be noted that the terms "carbon chain" and "carbonyl chain" are used interchangeably to refer to hydrocarbon chains (i.e., alkenyl or olefin). Another non-limiting example is Δ 11 The unsaturated aliphatic ester acetate refers to an olefinic ester acetate in which the 11th carbon-carbon bond counting from the acetate end of the olefin chain is a double bond. 11 Examples of unsaturated aliphatic ester acetates include, but are not limited to, 11-dodecenyl acetate, (Z)-tetradec-11-en-1-yl acetate, and (E)-tetradec-11-en-1-yl acetate.

[0031] As used herein, the terms "alkenol" and "aliphatic alkenol" are used interchangeably and refer to a compound having the structure R'-OR, where R' is a straight-chain alkenyl group containing at least four carbon atoms, e.g., 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, or 30 carbon atoms, and R is hydrogen or an alcohol protecting group. In some embodiments, R' is a C6-C 34 A straight chain alkenyl group. Non-limiting examples include "C 10 ~C 28 Aliphatic alkenols are those in which R'-OR is hydrogen and R' is C 10 ~C 28 Alkenols (i.e., aliphatic alkenols) are straight-chain alkenyl groups.

[0032] As used herein, the term "unsaturated aliphatic carboxylic derivative" refers to an aliphatic olefin compound that contains a carboxyl moiety and is used in the methods of the present invention. As used herein, the term "carboxyl" refers to a group of the formula "-C(O)O-." In the present invention, unsaturated aliphatic carbonyl derivatives include "unsaturated fatty acids" and "unsaturated fatty acid alkyl esters." As used herein, the term "unsaturated fatty acid" refers to a compound having the structure R'-C(O)OH, where R' is a linear alkenyl group containing at least 4 carbon atoms, e.g., 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, or 40 carbon atoms. In some embodiments, the R' of R'-C(O)OH is a C6-C8 alkyl group. 34 A straight chain alkenyl group. Non-limiting examples include "C 12 ~C 30 "Unsaturated fatty acids" are those in which R' in R'-C(O)OH is C 11 ~C 29 As used herein, the term "unsaturated fatty acid alkyl ester" refers to a compound having the structure R'-C(O)OR, where R' is a linear alkenyl group containing at least 4 carbon atoms, e.g., 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, or 40 carbon atoms, and R is an alkyl group as described below. In some embodiments, the R' of R'-C(O)OR is a C6-C 34 A straight chain alkenyl group. Non-limiting examples include "C 12 ~C 30 "Unsaturated fatty acid methyl ester" means R'-C(O)OR, where R is a methyl group and R' is C 10 ~C 28 The unsaturated fatty acid alkyl ester is a linear alkenyl group. The unsaturated fatty acid carboxylic derivative can be a mixture of different unsaturated fatty acids or a mixture of different unsaturated fatty acid alkyl esters. In some embodiments, the unsaturated fatty acid carboxylic derivative is derived from a natural oil or a natural oil derivative.

[0033] As used herein, the term "isomer" refers to a molecule that has the same chemical formula as another molecule but a different chemical structure. That is, an isomer contains the same number of atoms of each element, but has a different arrangement of the atoms of each element. Isomers include "structural isomers" and "stereoisomers." In "structural isomers" (also called "constitutional isomers"), atoms have a different bonding order. Structural isomers have different IUPAC names and may or may not belong to the same functional group. This type of isomer includes skeletal isomers, in which the hydrocarbon chain has variable amounts of branching, and positional isomers, which relate to the position of functional groups on the chain; and functional isomers, in which the molecular formula is the same but the functional groups are different.

[0034] As used herein, the term "positional isomer" refers to a first compound that has the same carbon skeleton and functional groups as a second compound, but the position of the functional groups on or in the carbon skeleton is different. In certain embodiments, one positional isomer may differ from the positional isomer of the isomer in the carbon skeleton where the functional group (e.g., alkene, hydroxyl, aldehyde, acetyl, etc.) is located. For example, a positional isomer of (Z)-tetradec-9-en-1-yl acetate is (Z)-tetradec-11-en-1-yl acetate. This is because (Z)-tetradec-9-en-1-yl acetate is produced by cross-metathesis between (Z)-octadec-9-en-1-yl acetate and (Z)-dec-5-ene, and (Z)-tetradec-11-en-1-yl acetate is produced by cross-metathesis between (Z)-icos-11-en-1-yl acetate and (Z)-hex-3-ene.

[0035] Stereoisomers have the same bond structure but differ in the geometric arrangement of atoms and functional groups in space. This class of isomers includes enantiomers, which are isomers that are non-superimposable mirror images of one another, and diastereomers, which are stereoisomers that are not mirror images. Geometric isomers, or cis / trans isomers, are diastereomers that differ in the stereochemical orientation of substituent atoms at the bond. The double bonds in the olefins and aliphatic olefin derivatives described herein prevent molecular rotation by locking the molecules into one of two possible configurations, each representing a different molecule, a geometric isomer. These geometric isomers are referred to as E (from the German word Entgegen, meaning opposite) when the carbon chains are connected on opposite sides (trans) of the double bond, and Z (Zusammen, meaning together) when they are connected on the same side (cis). Thus, the olefins and aliphatic olefin derivatives described herein can be in the (E) configuration, the (Z) configuration, or a mixture of the (E) and (Z) configurations. Another type of isomer, conformational isomers (conformers), can be rotamers, diastereomers, or enantiomers, depending on the particular compound.

[0036] As used herein, the term "stereoselectivity" describes the ability to produce a particular stereoisomer of a compound (i.e., an olefin or aliphatic olefin derivative described herein) in isomerically pure form (e.g., about 90% Z isomer or about 90% E isomer), or to specifically produce a particular stereoisomer of an aliphatic olefin derivative in the presence of a metathesis catalyst according to the methods described herein. In the context of the present invention, "stereoselective" or "selective" refers to a cross-metathesis reaction that produces one stereoisomer preferentially over a second stereoisomer, i.e., produces metathesis products or aliphatic olefin metathesis products in a ratio of the desired stereoisomer to the less desired stereoisomer of greater than 1:1.

[0037] "Z stereoselectivity" or "Z selectivity" describes the ability to produce the Z isomer of a compound (i.e., an olefin or aliphatic olefin derivative described herein) in Z isomerically pure, or predominantly pure, or substantially pure form; or to specifically produce the Z isomer of an aliphatic olefin derivative from the combination of i.) a mixture of E and Z isomers of a metathesis reaction partner (e.g., an acylated olefin metathesis reaction partner) and ii.) an olefin, which may be a mixture of E and Z isomers or at least 95% Z, in the presence of a metathesis catalyst according to the methods described herein. Furthermore, in the present invention, "Z stereoselective" or "Z selective" refers to a cross-metathesis reaction that produces the Z isomer in preference to the E isomer, i.e., produces a Z-aliphatic olefin metathesis product in which the ratio of Z to E isomers is greater than 1:1. By "Z-selective catalyst" is meant a Group 8 transition metal catalyst described herein that preferentially produces Z-aliphatic olefin metathesis products in the cross-metathesis reaction methods of the invention. Z selectivity may be expressed as the percentage of isomeric products formed. For example, aliphatic olefin derivatives (e.g., metathesis products, aliphatic olefin metathesis products, etc.) prepared according to the methods of the invention are at least 80% Z, typically greater than 85% Z, or 90% Z, or 95% Z, preferably greater than 97% Z, or greater than 98% Z, or greater than 99% Z, or greater than 99.5% Z, or greater than 99.9% Z.

[0038] For individual isomers, the terms "isomer purity" or "isomerically pure" are used interchangeably and refer to the amount or concentration of a particular isomer of an olefin or aliphatic olefin derivative relative to the total amount or concentration of all isomeric forms of the olefin or aliphatic olefin derivative. Each aliphatic olefin derivative (e.g., metathesis product, aliphatic olefin metathesis product, etc.) prepared according to the methods of the present invention is substantially Z isomerically pure. In other words, an aliphatic olefin derivative (e.g., metathesis product, aliphatic olefin metathesis product, etc.) prepared according to the methods of the present invention is greater than 80% Z isomer, usually greater than 85% Z isomer, or 90% Z isomer, or 95% Z isomer, more preferably greater than 97% Z isomer, or greater than 98% Z isomer, or greater than 99% Z isomer, or greater than 99.5% Z isomer, or greater than 99.9% Z isomer.

[0039] As used herein, the term "Z:E ratio" refers to the ratio of the amount of Z isomer (e.g., a Z-aliphatic olefin metathesis product) to the amount of E isomer (e.g., an E-aliphatic olefin metathesis product). As used herein, the term "Z-enriched" refers to a material (e.g., a metathesis product) that has a higher Z:E ratio than the precursor material (e.g., a metathesis reaction partner).

[0040] As used herein, the term "low isomeric purity" refers to olefins, metathesis reaction partners, olefin starting materials, olefin-containing reactants, and aliphatic olefin derivatives (e.g., alkenols, unsaturated aliphatic alcohol acetates, unsaturated aliphatic ester acetates, olefin metathesis reaction partners, aliphatic olefin metathesis products, unsaturated aliphatic aldehydes, unsaturated aliphatic carboxylic derivatives, metathesis products, etc.) used in or produced from the processes of the present invention that are less than 90% Z isomer (i.e., 10% or more E isomer).

[0041] As used herein, the term "highly Z-selective" means that greater than 85% of the metathesis products and / or aliphatic olefin metathesis products formed are in the Z configuration.

[0042] As used herein, the term "metathesis catalyst" refers to any catalyst or catalyst system that catalyzes a metathesis reaction. Those skilled in the art will recognize that a metathesis catalyst can participate in a metathesis reaction to increase the reaction rate, but is not itself consumed during the reaction. "Ruthenium catalyst" refers to a metathesis catalyst having one or more ruthenium atoms. "Osmium catalyst" refers to a metathesis catalyst having one or more osmium atoms.

[0043] As used herein, the terms "forming" and "converting" are used interchangeably and refer to reacting a starting material with at least one reagent to form an intermediate species or product. Forming or converting may also include reacting an intermediate with at least one reagent to form a further intermediate species or product.

[0044] The term "functional group" encompasses any functional group known in the art.

[0045] As used herein, the term "acyl" refers to the functional group --C(O)--R, where R is an alkyl group as described below.

[0046] As used herein, the term "acylation" means converting an alcohol group (-OH) into an ester group (-OC(O)-R), where R is an alkyl group as described below.

[0047] As used herein, the term "acylating agent" refers to a compound capable of reacting with a substrate compound to add a -C(O)-R moiety to the compound. Acylating agents can be used, for example, to form esters (i.e., -C(O)OR) on compounds bearing a hydroxyl moiety (i.e., -OH). Acylating agents useful in the present invention may comprise one or more C1-C 20 The acylating agent may be a linear or branched alkyl or aryl carboxylic acid anhydride, a carboxylic acid halide, a diketene, or an acetoacetic acid ester. Examples of carboxylic acid anhydrides suitable for use as acylating agents in the present invention include, but are not limited to, acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, hexanoic anhydride, 2-ethylhexanoic anhydride, nonanoic anhydride, lauric anhydride, palmitic anhydride, stearic anhydride, benzoic anhydride, substituted benzoic anhydrides, phthalic anhydride, and isophthalic anhydride. Examples of carboxylic acid halides suitable for use as acylating agents in the present invention include acetyl chloride, propionyl chloride, butyryl chloride, hexanoyl chloride, 2-ethylhexanoyl chloride, lauroyl chloride, palmitoyl chloride, and stearoyl chloride. Examples of acetoacetic acid esters suitable for use as acylating agents in the present invention include, but are not limited to, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, and tert-butyl acetoacetate.

[0048] As used herein, the term "alkenyl" refers to an alkyl group, as defined herein, having one or more double bonds. The term "heteroalkenyl" refers to an alkenyl group in which one or more carbon atoms is replaced by a heteroatom (i.e., nitrogen, oxygen, or sulfur, including any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen).

[0049] As used herein, the term "reducing" refers to the transfer of electron density from a hydrogenation catalyst or reducing agent to a substrate compound. Typically, the electron density transfer occurs by a process involving the addition of hydrogen to the substrate compound.

[0050] As used herein, the term "reducing agent" refers to any reagent effective in reducing a carboxylic acid group (i.e., -C(O)OH) to an alcohol group (i.e., -CH-OH). Examples of reducing agents include, but are not limited to, sodium borohydride, sodium triacetoxyborohydride, sodium cyanoborohydride, lithium aluminum hydride, and sodium bis(2-methoxyethoxy)aluminum hydride.

[0051] As used herein, the term "hydrogenation catalyst" means any catalyst effective in hydrogenating an alkyl ester group (i.e., -C(O)OR), where R is an alkyl group as defined below, to an alcohol group (i.e., -CH-OH). The hydrogenation catalyst can be a heterogeneous catalyst or a homogeneous catalyst.

[0052] As used herein, the term "heterogeneous" refers to reaction conditions in which one or more reagents or participants (i.e., heterogeneous catalysts) are not soluble in the reaction medium, i.e., are in a different phase (e.g., solid catalyst) from other solvents, reagents, compounds, or substrates (e.g., liquid or vapor) when mixed together. The term "homogeneous" refers to reaction conditions in which all reagents or participants (i.e., homogeneous catalysts) are soluble in the reaction medium (i.e., are in the same phase as other solvents, reagents, compounds, or substrates when mixed together). The terms "heterogeneous" and "homogeneous" can also refer to catalysts. For example, a "heterogeneous catalyst" refers to a catalyst that is not soluble in the reaction medium, i.e., is in a different phase (e.g., solid catalyst) from other solvents, reagents, compounds, or substrates (e.g., liquid or vapor) when mixed together. A "homogeneous catalyst" refers to a catalyst that is soluble in the reaction medium (i.e., is in the same phase as other solvents, reagents, compounds, or substrates when mixed together).

[0053] As used herein, the term "aliphatic" or "aliphatic group" refers to a linear (i.e., unbranched) or branched, substituted or unsubstituted hydrocarbon chain that is fully saturated or contains one or more units of unsaturation; or a monocyclic, bicyclic, or tricyclic hydrocarbon (also referred to herein as "carbocyclic" or "alicyclic") that is fully saturated or contains one or more units of unsaturation, but is not aromatic and has one point of attachment to the rest of the molecule. Unless otherwise specified, an aliphatic group contains 1-30 aliphatic carbon atoms. In some embodiments, an aliphatic group contains 1-20 aliphatic carbon atoms. In other embodiments, an aliphatic group contains 1-10 aliphatic carbon atoms. In still other embodiments, an aliphatic group contains 1-5 aliphatic carbon atoms, and in still other embodiments, an aliphatic group contains 1, 2, 3, or 4 aliphatic carbon atoms. In some embodiments, "alicyclic" (or "carbocycle") refers to a monocyclic C3-C6 hydrocarbon or C8-C8 ring that is fully saturated or contains one or more units of unsaturation, but is not aromatic, and has one point of attachment to the rest of the molecule. 10 It refers to a bicyclic hydrocarbon. Suitable aliphatic groups include, but are not limited to, linear or branched, substituted or unsubstituted alkyl, alkenyl, alkynyl groups, and hybrids thereof, such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl, or (cycloalkyl)alkenyl. The term "heteroaliphatic" refers to an aliphatic group in which at least one carbon atom of the aliphatic group is replaced with a heteroatom (i.e., nitrogen, oxygen, or sulfur, including any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen).

[0054] As used herein, the term "alkyl" is given its ordinary meaning in the art and includes straight chain (i.e., linear) or branched saturated aliphatic groups having the indicated number of carbon atoms. A straight chain or branched alkyl has about 1 to 40 carbon atoms, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, or 40 carbon atoms in its backbone. In some embodiments, a straight chain or linear alkyl is a C1-C 30 and branched alkyl is C3 to C 30 In some cases, a straight chain or branched chain alkyl has about 1-20 carbon atoms in its backbone. In some embodiments, a straight chain or branched chain alkyl has about 1-10 carbon atoms in its backbone, e.g., C 1~2 , C 1~3 , C 1~4 , C 1~5 , C 1~6 , C 1~7 , C 1~8 , C 1~9 , C 1~10 , C 2~3 , C 2~4 , C 2~5 , C 2~6 , C 3~4 , C 3~5 , C 3~6 , C 4~5 , C 4~6 , and C 5~6 For example, C 1~10 Alkyl includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. In some embodiments, the alkyl group can be a lower alkyl group, where the lower alkyl group contains 1 to 4 carbon atoms (e.g., C1-C4 for a straight chain lower alkyl).

[0055] As used herein, the term "heteroalkyl" is given its ordinary meaning in the art and refers to an alkyl group, as described herein, in which one or more carbon atoms have been replaced with a heteroatom (e.g., oxygen, nitrogen, sulfur, etc.). Examples of heteroalkyl groups include, but are not limited to, alkoxy, poly(ethylene glycol)-, alkyl-substituted amino, and the like.

[0056] As used herein, the term "alkoxy" refers to an -OR moiety, where R is an alkyl group, as defined above. The term "silylalkyl" refers to an alkyl group, as defined herein, in which at least one carbon atom has been replaced with a silicon atom. The term "silyloxy" refers to an -OSiR moiety, where each R is independently selected from the group consisting of H, alkyl, substituted alkyl, aryl, and substituted aryl, as defined herein.

[0057] The term "cycloalkyl," as used herein, refers to a saturated monocyclic, bicyclic, or tricyclic hydrocarbon group having a single point of attachment to the rest of the molecule. Cycloalkyl groups include alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups. In some embodiments, cycloalkyl rings have from about 3 to 10 carbon atoms in the ring structure, where the ring is monocyclic or bicyclic, or alternatively about 5, 6, or 7 carbons in the ring structure.

[0058] The term "alkynyl" as used herein, means an alkyl group, as defined herein, having one or more triple bonds.

[0059] As used herein, the term "aryl," whether used alone or as part of a larger moiety such as "aralkyl," "aralkoxy," or "aryloxyalkyl," refers to a monocyclic or bicyclic ring system having a total of 5 to 14 ring members, in which at least one ring in the system is aromatic and each ring in the system contains 3 to 7 ring members. The term "aryl" can be used interchangeably with the term "aryl ring." In certain embodiments of the present invention, "aryl" refers to an aromatic ring system, including, but not limited to, phenyl, biphenyl, naphthyl, anthracyl, and the like, which may bear one or more substituents. Groups in which an aromatic ring is fused to one or more non-aromatic rings, such as indanyl, phthalimidyl, naphthimidyl, phenanthridinyl, or tetrahydronaphthyl, are also included within the scope of the term "aryl" as used herein. The term "aryloxy" refers to the moiety -OR, where R is an aryl group as defined above.

[0060] As used herein, the terms "heteroaryl" and "heteroar-," used alone or as part of a larger moiety, such as "heteroaralkyl" or "heteroaralkoxy," refer to groups having 5 to 10 ring atoms (i.e., monocyclic or bicyclic), in some embodiments, 5, 6, 9, or 10 ring atoms. In some embodiments, the rings have 6, 10, or 14 π-electrons shared in the cyclic arrangement, and have 1 to 5 heteroatoms in addition to the carbon atoms. The term "heteroatom" means nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen. Heteroaryl groups include, but are not limited to, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, and pteridinyl. As used herein, the terms "heteroaryl" and "heteroar-" also include groups in which a heteroaromatic ring is fused to one or more aryl, alicyclic, or heterocyclyl rings, and the bonding group or point of attachment is on the heteroaromatic ring. Non-limiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzothiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-1,4-oxazin-3(4H)-one. Heteroaryl groups can be monocyclic or bicyclic. The term "heteroaryl group" can be used interchangeably with the terms "heteroaryl ring," "heteroaryl group," or "heteroaromatic ring," and all terms include optionally substituted rings.The term "heteroaralkyl" means an alkyl group substituted with a heteroaryl, wherein the alkyl and heteroaryl portions independently may be optionally substituted.

[0061] Examples of aryl and heteroaryl groups include, but are not limited to, phenyl, pyrrolyl, furanyl, thiophenyl, imidazolyl, oxazolyl, thiazolyl, triazolyl, pyrazolyl, pyridinyl, pyrazinyl, pyridazinyl, and pyrimidinyl. When aryl and heteroaryl groups are used as ligands to coordinate to a metal center, it should be understood that the aryl and heteroaryl groups may have sufficient ionic character to coordinate to the metal center. For example, when a heteroaryl group such as pyrrole is used as a nitrogen-containing ligand as described herein, it should be understood that the pyrrole group has sufficient ionic character to coordinate to the metal center (e.g., is sufficiently deprotonated to establish a pyrrolyl group). In some cases, the aryl or heteroaryl group may contain at least one functional group, such as a biphenolate group, having sufficient ionic character to coordinate to the metal center.

[0062] As used herein, the terms "heterocycle," "heterocyclyl," "heterocyclic group," and "heterocyclic ring" are used interchangeably and refer to a stable 5- to 7-membered monocyclic or 7- to 10-membered bicyclic heterocyclic moiety that is saturated or partially unsaturated and has, in addition to carbon atoms, one or more heteroatoms (e.g., 1 to 4 heteroatoms) as defined above. When used in reference to a ring atom of a heterocycle, the term "nitrogen" includes substituted nitrogen. As an example, in a saturated or partially unsaturated ring having 1 to 3 heteroatoms selected from oxygen, sulfur, or nitrogen, the nitrogen can be N (e.g., in 3,4-dihydro-2H-pyrrolyl), NH (e.g., in pyrrolidinyl), or . + It can be NR (eg, in N-substituted pyrrolidinyl).

[0063] A heterocycle can be attached to its pendant group at any heteroatom or carbon atom that results in a stable structure, and any ring atom can be substituted. Examples of saturated or partially unsaturated heterocycles include, but are not limited to, tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl. The terms "heterocycle," "heterocyclyl," "heterocyclyl ring," "heterocyclic group," "heterocyclic moiety," and "heterocyclic radical" are used interchangeably herein and also include groups in which a heterocyclyl ring is fused to one or more aryl, heteroaryl, or alicyclic rings, such as indolinyl, 3H-indolyl, chromanyl, phenanthridinyl, or tetrahydroquinolinyl. Heterocyclyl groups can be monocyclic or bicyclic. The term "heterocyclylalkyl" refers to an alkyl group substituted with a heterocyclyl, where the alkyl and heterocyclyl portions are optionally and independently substituted.

[0064] The terms "halogen" and "halo" are used interchangeably to mean F, Cl, Br, or I.

[0065] As used herein, the term "protecting group" refers to a chemical moiety that renders a functional group unreactive but can be removed to restore the functionality. Examples of "alcohol protecting groups" include, but are not limited to, benzyl; tert-butyl; trityl; tert-butyldimethylsilyl (TBDMS; TBS); 4,5-dimethoxy-2-nitrobenzyloxycarbonyl (Dmnb); propargyloxycarbonyl (Poc); and the like. Examples of "amine protecting groups" include, but are not limited to, benzyloxycarbonyl, 9-fluorenylmethyloxycarbonyl (Fmoc), tert-butyloxycarbonyl (Boc), allyloxycarbonyl (Alloc), p-toluenesulfonyl (Tos), 2,2,5,7,8-pentamethylchroman-6-sulfonyl (Pmc), 2,2,4,6,7-pentamethyl-2,3-dihydrobenzofuran-5-sulfonyl (Pbf), mesityl-2-sulfonyl (Mts), 4-methoxy-2,3,6-trimethylphenylsulfonyl (Mtr), acetamide, phthalimide, and the like. Green and Wuts (Protective Groups in Organic Synthesis, 4 th Other alcohol and amine protecting groups will be known to those of skill in the art, including, for example, those described in (Ed. 2007, Wiley-Interscience, New York).

[0066] As described herein, compounds of the invention can contain "optionally substituted" moieties. In general, the term "substituted," whether preceded by the term "optionally" or not, means that one or more hydrogens in the specified moiety can be replaced with a suitable substituent. Unless otherwise indicated, an "optionally substituted" group can have a suitable substituent at each substitutable position of the group, and if more than one position in any given structure can be substituted with more than one substituent selected from a specified group, the substituents can be the same or different at each position. In general, combinations of substituents contemplated by the present invention are those that result in the formation of stable or chemically viable compounds. As used herein, the term "stable" refers to a compound that is substantially unaltered when subjected to conditions that allow for its production, detection, and, in certain embodiments, its recovery, purification, and use for one or more purposes disclosed herein.

[0067] Suitable monovalent substituents on a substitutable carbon atom of an "optionally substituted" group are independently halogen; -(CH) 0~4 R α ; -(CH2) 0~4 OR α -O(CH2) 0~4 R α -O-(CH2) 0~4 C(O)OR α ; -(CH2) 0~4 CH(OR α )2; -(CH2) 0~4 SR α ; R α may be substituted with -(CH2) 0~4 Ph; R α may be substituted with -(CH2) 0~4 O(CH2) 0~1 Ph; R α -CH=CHPh; R α may be substituted with -(CH2) 0~4 O(CH2) 0~1 -Pyridyl; -NO2; -CN; -N3; ​​-(CH2) 0~4N(R α )2; -(CH2) 0~4 N(R α )C(O)R α ; -N(R O )C(S)R α ; -(CH2) 0~4 N(R α )C(O)NR α 2; -N(R α )C(S)NR α 2; -(CH2) 0~4 N(R α )C(O)OR α ; -N(R α )N(R α )C(O)R α ; -N(R α )N(R α )C(O)NR α 2; -N(R α )N(R α )C(O)OR α ; -(CH2) 0~4 C(O)R α ; -C(S)R α ; -(CH2) 0~4 C(O)OR α ; -(CH2) 0~4 C(O)SR α ; -(CH2) 0~4 C(O)OSiR α 3; -(CH2) 0~4 OC(O)R α ; -OC(O)(CH2) 0~4 SR-SC(S)SR α ; -(CH2) 0~4 SC(O)R α ; -(CH2) 0~4 C(O)NR α 2; -C(S)NR α 2; -C(S)SR α ; -SC(S)SR α ; -(CH2) 0~4 OC(O)NR α 2; -C(O)N(OR α )R α ; -C(O)C(O)R α ; -C(O)CH2C(O)R α ; -C(NORα )R α ; -(CH2) 0~4 SSR α ; -(CH2) 0~4 S(O)2R α ; -(CH2) 0~4 S(O)2OR α ; -(CH2) 0~4 OS(O)2R α -S(O)2NR α 2; -(CH2) 0~4 S(O)R α ; -N(R α )S(O)NR α 2; -N(R α )S(O)2R α ; -N(OR α )R α -C(NH)NR α 2; -P(O)2R α ; -P(O)R α 2; -OP(O)R α 2; -OP(O)(OR α )2; SiR α 3; -(C 1~4 Linear or branched alkylene)ON(R α )2; or -(C 1~4 Linear or branched alkylene C(O)ON(R α )2, where each R α are optionally substituted as defined below and independently represent hydrogen, C 1~6 Aliphatic, -CH2Ph, -O(CH2) 0~1 Ph, -CH2- (5- to 6-membered heteroaryl ring), or a 5- to 6-membered saturated, partially unsaturated, or aromatic ring having 0 to 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or, regardless of the above definition, two independently occurring R α together with the atoms intervening therebetween, form a monocyclic or bicyclic 3- to 12-membered saturated, partially unsaturated, or aromatic ring, which may be optionally substituted as defined below, and which has 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0068] Rα (Or, two independently occurring R α Preferred monovalent substituents on the ring formed by (and together with the intervening atoms) are independently halogen; -(CH) 0~2 R β ; -(Halo R β ); -(CH2) 0~2 OH; -(CH2) 0~2 OR β ; -(CH2) 0~2 CH(OR β )2; -O(HaloR β ); -CN; -N3; ​​-(CH2) 0~2 C(O)R β ; -(CH2) 0~2 C(O)OH; -(CH2) 0~2 C(O)OR β ; -(CH2) 0~2 SR β ; -(CH2) 0~2 SH; -(CH2) 0~2 NH2; -(CH2) 0~2 NHR β ; -(CH2) 0~2 NR β 2; -NO2; SiR β 3; -OSiR β 3; -C(O)SR β ; -(C 1~4 Linear or branched alkylene)C(O)OR β ; or -SSR β where each R β is unsubstituted or, if preceded by "halo", is substituted only with one or more halogens, and C 1~4 Aliphatic, -CH2Ph, -O(CH2) 0~1 R is independently selected from Ph, or a 5- to 6-membered saturated, partially unsaturated, or aromatic ring having 0 to 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. α Suitable divalent substituents on a saturated carbon atom of include ═O and ═S.

[0069] Suitable divalent substituents on a saturated carbon atom of an "optionally substituted" group include: =O; =S; =NNR γ 2; =NNHC(O)R γ ; =NNHC(O)OR γ ; =NNHS(O)2R γ ; =NR γ ; =NOR γ ; -O(C(R γ 2)) 2~3 O-; or -S(C(R γ 2)) 2~3 S-, where each independently occurring R γ is hydrogen, optionally substituted as defined below, C 1~6 The group is selected from aliphatic or unsubstituted 5- to 6-membered saturated, partially unsaturated, or aromatic rings having 0 to 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. Preferred divalent substituents attached to adjacent substitutable carbon atoms of the "optionally substituted" group include -O(CR β 2) 2~3 O-, where each R β is hydrogen, optionally substituted as defined below, C 1~6 It is selected from aliphatic or unsubstituted 5- to 6-membered saturated, partially unsaturated, or aromatic rings having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0070] R γ Suitable substituents on the aliphatic group include halogen, -R δ ,-(Halo R δ ), -OH, -OR δ , -O(HaloR δ ), -CN, -C(O)OH, -C(O)OR δ , -NH2, -NHR δ , -NR δ 2, or -NO2, where each R δ is unsubstituted or, if preceded by "halo", is substituted only with one or more halogens, and independently C 1~4 Aliphatic, -CH2Ph, -O(CH2) 0~1Ph, or a 5- to 6-membered saturated, partially unsaturated, or aromatic ring having 0 to 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0071] Suitable substituents on a substitutable nitrogen of an "optionally substituted" group include -R ε , -NR ε 2. -C(O)R ε , -C(O)OR ε , -C(O)C(O)R ε , -C(O)CH2C(O)R ε , -S(O)2R ε , -S(O)NR ε 2. -C(S)NR ε 2. -C(NH)NR ε 2, or -N(R ε )S(O)2R ε where each R ε are independently hydrogen, optionally substituted as defined below, C 1~6 an aliphatic, unsubstituted -OPh, or an unsubstituted 5- to 6-membered saturated, partially unsaturated, or aromatic ring having 0 to 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or, regardless of the above definition, two independently occurring R ε together with the atoms intervening therebetween, form an unsubstituted monocyclic or bicyclic 3- to 12-membered saturated, partially unsaturated, or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0072] R ε Suitable substituents on the aliphatic group are independently halogen, -R δ ,-(Halo R δ ), -OH, -OR δ , -CN, -C(O)OH, -C(O)OR δ , -NH2, -NHR δ , -NR δ 2, or -NO2, where each R δ is unsubstituted or, if preceded by "halo", is substituted only with one or more halogens, and independently C 1~4Aliphatic, -CH2Ph, -O(CH2) 0~1 Ph, or a 5- to 6-membered saturated, partially unsaturated, or aromatic ring having 0 to 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0073] In some embodiments, the term "substituted" is intended to include all permissible substituents of organic compounds, where "permissible" is within the context of valence chemistry rules known to those of ordinary skill in the art. In some cases, "substituted" can generally refer to the replacement of a hydrogen atom with a substituent described herein. However, as used herein, "substituted" does not encompass the replacement and / or modification of the primary functional group by which a molecule is identified, e.g., such that the "substituted" functional group becomes a different functional group through substitution. For example, a "substituted phenyl" group must still contain a phenyl moiety and, under this definition, cannot be modified by substitution to, for example, a cyclohexyl group. In a broad aspect, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds. Exemplary substituents include, for example, those described herein. Permissible substituents can be one or more and the same or different for appropriate organic compounds. For example, a substituted alkyl group can be CF3. For purposes of this invention, heteroatoms such as nitrogen may have hydrogen substituents and / or any permissible substituents of organic compounds described herein that satisfy the valences of the heteroatoms. This invention is not intended to be limited in any way by the permissible substituents of organic compounds.

[0074] Examples of substituents include, but are not limited to, alkyl, aryl, arylalkyl, cyclic alkyl, heterocycloalkyl, hydroxy, alkoxy, aryloxy, perhaloalkoxy, arylalkoxy, heteroaryl, heteroaryloxy, heteroarylalkyl, heteroarylalkoxy, azido, amino, halogen, alkylthio, oxo, acylalkyl, carboxyester, carboxyl, carboxamido, nitro, acyloxy, aminoalkyl, alkylaminoaryl, alkylaryl, alkylaminoalkyl, alkoxyaryl, arylamino, arylalkylamino, alkylsulfonyl, carboxamidoalkylaryl, carboxamidoaryl, hydroxyalkyl, haloalkyl, alkylaminoalkylcarboxy, aminocarboxamidoalkyl, cyano, alkoxyalkyl, perhaloalkyl, arylalkyloxyalkyl, and the like.

[0075] As used herein, the term "natural oil" refers to an oil derived from a plant or animal source. Unless otherwise indicated, the term "natural oil" includes natural oil derivatives. Unless otherwise indicated, the plant or animal source may be a modified plant or animal source (e.g., a genetically modified plant or animal source). Examples of natural oils include, but are not limited to, vegetable oils, algae oils, fish oils, animal fats, tall oils, derivatives of these oils, any combination of these oils, etc.

[0076] The term "vegetable oil" refers to a natural oil or natural oil derivative derived from any suitable component of a plant (e.g., a vegetable, fruit, leaf, stem, shrub, flower, seed, or nut), or any combination thereof. Representative, non-limiting examples of vegetable oils include almond oil, canola oil, avocado oil, argan oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, grapeseed oil, olive oil, palm oil, peanut oil, hempseed oil, macadamia oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil, jojoba oil, mustard oil, shepherd's purse oil, cabbage oil, and castor oil. Representative, non-limiting examples of animal fats include lard, beef tallow, poultry fat, yellow grease, and fish oil. Tall oil is a by-product of wood pulp production. "Natural seed oil" refers to a type of natural vegetable oil that is specifically obtained from the seeds of plants rather than the fruits (or other components) of plants.Therefore, not all vegetable oils are seed oils.For example, olive oil and peanut oil are not natural seed oils.Representative but non-limiting examples of natural seed oils include almond oil, canola oil, avocado oil, argan oil, rapeseed oil, palm oil, corn oil, cottonseed oil, grapeseed oil, hempseed oil, macadamia oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil, jojoba oil, mustard oil, shepherd's purse oil, cabbage oil and castor oil.

[0077] "Natural oil derivative" refers to a compound (or mixture of compounds) derived from natural oils using any one or combination of methods known in the art. These methods include, but are not limited to, saponification, lipolysis, transesterification, esterification, hydrogenation (partial or complete), isomerization, oxidation, reduction, and metathesis. Representative, non-limiting examples of natural oil derivatives include gums, phospholipids, soda soap, dark oil, distillates or distillate sludge, fatty acids, and fatty acid alkyl esters (non-limiting examples such as 2-ethylhexyl esters), as well as hydroxy-substituted variants thereof. For example, a natural oil derivative can be a fatty acid methyl ester ("FAME") derived from a natural oil glyceride.

[0078] The term "contaminant" refers broadly and without limitation to any impurity, regardless of the amount present, mixed with the substrate used in olefin metathesis. "Catalyst-poisoning contaminant" refers to a contaminant that has the potential to adversely affect the performance of a metathesis catalyst. Examples of catalyst-poisoning contaminants include, but are not limited to, water, peroxides, and hydroperoxides.

[0079] III. Methods for Synthesizing Aliphatic Olefin Metathesis Products In some embodiments, the present invention provides a method for synthesizing a Z-enriched aliphatic olefin metathesis product, comprising contacting an olefin metathesis reaction partner with an internal olefin in the presence of a Group 8 transition metal metathesis catalyst to form a Z-enriched aliphatic olefin metathesis product, wherein the aliphatic olefin metathesis product is an acylated alkenol or alkenal acetal; the olefin metathesis reaction partners comprise a mixture of Z olefins and E olefins in a starting Z:E ratio; the aliphatic olefin metathesis product comprises a mixture of Z olefins and E olefins in a product Z:E ratio; A process is provided in which the product Z:E ratio is higher than the starting Z:E ratio.

[0080] The process of the present invention is highly Z-selective, with greater than 80% of the metathesis products formed being in the Z configuration. More particularly, the process of the present invention produces aliphatic olefin metathesis products that are at least 97% Z, such as compounds of formula I. Additionally, the present invention provides a process for producing aliphatic olefin metathesis products of high Z-isomer purity from olefin feedstocks of low Z-isomer purity.

[0081] In some embodiments, Formula I: A method for synthesizing an aliphatic olefin metathesis product of TIFF0007821747000020.tif16128 is provided, which comprises reacting an aliphatic olefin metathesis product of Formula III: TIFF0007821747000021.tif16128 and an olefin metathesis reaction partner of formula IV: and an internal olefin in the presence of a metathesis catalyst, wherein: R 1 is H and C 1~6 selected from the group consisting of alkyl; R 2 is C 1~18 Alkyl and C 2~18 alkenyl; R 3 is C 1~18 is alkyl; The subscript y is an integer ranging from 0 to 17; The subscript z is an integer ranging from 0 to 17; The metathesis catalyst is a Z-selective Group 8 transition metal catalyst.

[0082] In some embodiments, the aliphatic olefin metathesis product has Formula VI: TIFF0007821747000023.tif16128 is an alkenal acetal; The metathesis reaction partner is of formula VII: TIFF0007821747000024.tif16128 compound; The internal olefin is represented by formula IV: TIFF0007821747000025.tif10128 compound; R 1 is C 1~6 is alkyl; R 2 is C 1~18 Alkyl and C 2~18 alkenyl; R 3 is C 1~18 is alkyl; The subscript y is an integer ranging from 0 to 17; The subscript z is an integer ranging from 0 to 17; The Group 8 transition metal metathesis catalyst is a Z-selective Group 8 transition metal catalyst.

[0083] Metathesis of Aliphatic Olefin Derivatives In some embodiments, Formula I: The method for synthesizing an aliphatic olefin metathesis product of TIFF0007821747000026.tif16128 comprises reacting a compound of Formula III: TIFF0007821747000027.tif16128 and an olefin metathesis reaction partner of formula IV: and an internal olefin in the presence of a Z-selective Group 8 transition metal metathesis catalyst (e.g., a Z-selective ruthenium catalyst or a Z-selective osmium catalyst), wherein: R 1 is H and C 1~6 selected from the group consisting of alkyl; R 2 is C 1~18 Alkyl and C 2~18 alkenyl; R 3 is C 1~18 is alkyl; The subscript y is an integer ranging from 0 to 17; The subscript z is an integer ranging from 0 to 17.

[0084] In some embodiments, the method for synthesizing an aliphatic olefin metathesis product of Formula I comprises reacting an acylating agent with an aliphatic olefin metathesis product of Formula II: with an alkenol of formula III to form an olefin metathesis reaction partner of formula III.

[0085] In some embodiments, the acylating agent used to contact the alkenol of formula II to form the olefin metathesis reaction partner of formula III is acetic anhydride.

[0086] Any acylating agent suitable for forming the olefin metathesis reaction partner of Formula III can be used in the method of the present invention. Examples of suitable acylating agents include acid anhydrides (e.g., acetic anhydride), acid chlorides (e.g., acetyl chloride), activated esters (e.g., carboxylic acid pentafluorophenyl esters), and carboxylic acids used with coupling agents such as dicyclohexylcarbodiimide or carbonyldiimidazole. Typically, 1 to 10 molar equivalents of the acylating agent relative to the alkenol are used. For example, 1 to 5 equivalents of the acylating agent or 1 to 2 equivalents of the acylating agent can be used. In some embodiments, about 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5 molar equivalents of the acylating agent (e.g., acetic anhydride) relative to the alkenol are used to form the olefin metathesis reaction partner of Formula III.

[0087] A base can be used to facilitate the acylation of the alkenol with the acylating agent. Examples of suitable bases include potassium carbonate, sodium carbonate, sodium acetate, Hunig's base (i.e., N,N-diisopropylethylamine), lutidine, including 2,6-lutidine (i.e., 2,6-dimethylpyridine), triethylamine, tributylamine, pyridine, 2,6-di-tert-butylpyridine, 1,8-diazabicycloundec-7-ene (DBU), quinuclidine, and collidine. Combinations of two or more bases can be used. Typically, less than 1 molar equivalent of base relative to the alkenol is used in the methods of the present invention. For example, 0.05 to 0.9 molar equivalents or 0.1 to 0.5 molar equivalents of base can be used. In some embodiments, about 0.05, 0.1, 0.15, or 0.2 molar equivalents of base relative to the alkenol are used in combination with an acylating agent (e.g., acetic anhydride) to form the olefin metathesis reaction partner of Formula III.

[0088] Any suitable solvent can be used to acylate the alkenol. Suitable solvents include, but are not limited to, toluene, methylene chloride, ethyl acetate, acetonitrile, tetrahydrofuran, benzene, chloroform, diethyl ether, dimethylformamide, dimethyl sulfoxide, petroleum ether, and mixtures thereof. Alternatively, an alkenol such as (Z)-octadec-9-en-1-ol (i.e., oleyl alcohol) can be combined with an acylating agent such as acetic anhydride and a base such as sodium acetate without an additional solvent. Typically, the acylation reaction is carried out at a temperature ranging from about 25°C to about 100°C for a period sufficient to form the olefin metathesis reaction partner of formula III. The reaction can be carried out for a period ranging from a few minutes to several hours or longer, depending on the particular alkenol and acylating agent used in the reaction. For example, the reaction can be carried out at about 40°C, or about 50°C, or about 60°C, or about 70°C, or about 80°C for about 10 minutes, or about 30 minutes, or about 1 hour, or about 2 hours, or about 4 hours, or about 8 hours, or about 12 hours.

[0089] Thus, in some embodiments, the present invention provides compounds of formula I: TIFF0007821747000030.tif16128, a method for synthesizing an aliphatic olefin metathesis product comprising: to form an olefin metathesis reaction partner of formula II: with an alkenol of formula (I); and To form an aliphatic olefin metathesis product, an olefin metathesis reaction partner and an aliphatic olefin metathesis reaction partner of Formula IV: and an internal olefin of formula (I) in the presence of a Z-selective ruthenium catalyst or a Z-selective osmium catalyst, wherein R1 is H and C 1~6 selected from the group consisting of alkyl; R 2 C 1~18 Alkyl and C 2~18 alkenyl; R 3 C 1~18 is alkyl; The subscript y is an integer ranging from 0 to 17; The subscript z is an integer in the range of 0 to 17.

[0090] In some embodiments, the method for synthesizing an aliphatic olefin metathesis product comprises a compound of formula IIa: reducing the unsaturated aliphatic carboxyl derivative of TIFF0007821747000034.tif16128 to form an alkenol of formula II; In the formula, R 4 is H and C 1~8 alkyl.

[0091] In some embodiments, forming the alkenol of Formula II comprises contacting the unsaturated aliphatic carboxylic derivative of Formula IIa with a base in the presence of a hydrogenation catalyst and hydrogen gas. Homogeneous or heterogeneous conditions can be used. Examples of homogeneous conditions include, but are not limited to, hydrogenolysis using tethered transition metal catalysts (Werkmeister, S. et al. Org. Process Res. Dev. 2014, 18, 289-302; Tan, et al. Org. Lett. 2015, 17 (3), 454; Spasyuk, D. et al. J. Am. Chem. Soc. 2015, 137, 3743; WO 2014 / 139030) and metal hydride-catalyzed reduction reactions using silane reagents (Mimoun, HJ Org. Chem. 1999, 64, 2582; U.S. Patent No. 6,533,960). Examples of heterogeneous conditions include, but are not limited to, hydrogenolysis of unsaturated aliphatic carboxylic derivatives of formula IIa using ZnO or CuO / ZnO supported on chromite, alumina, or other materials to form alkenols of formula II. Any suitable combination of conditions for reducing unsaturated aliphatic carboxylic derivatives of formula IIa to alkenols of formula II can be used in the process of the present invention.

[0092] In some embodiments, the hydrogenation catalyst used to form the alkenol of Formula II from the unsaturated aliphatic carboxylic derivative of Formula IIa is a homogeneous transition metal catalyst containing a pincer or tridentate or tetradentate ligand. Non-limiting examples of suitable homogeneous transition metal catalysts include dichlorotriphenylphosphine[bis(2-(ethylthio)ethyl)amine]ruthenium(II) and dichlorotriphenylphosphine[2-(diphenylphosphino)-N-(2-pyridinylmethyl)ethanamine]ruthenium(II). Those skilled in the art will be able to select a suitable hydrogenation catalyst for reducing an unsaturated aliphatic carboxylic derivative (e.g., an alkyl ester-containing compound) to the corresponding alkenol (e.g., an alcohol-containing compound). Other homogeneous transition metal catalysts suitable for hydrogenating an alkyl ester group to an alcohol group are known to those skilled in the art, including, for example, the catalysts described in Werkmeister, S. et al. Org. Process Res. Dev. 2014, 18, 289-302. Typically, a hydrogenation catalyst is used in a substoichiometric amount (e.g., a catalytic amount) in the presence of hydrogen gas and a suitable base, such as sodium ethoxide, sodium methoxide, sodium tert-butoxide, etc. In some embodiments, forming the alkenol of Formula II comprises contacting an unsaturated aliphatic carboxylic derivative of Formula IIa, which is an unsaturated fatty acid alkyl ester, with a base in the presence of a hydrogenation catalyst and hydrogen gas ... 4 C 1~8 The method comprises contacting an unsaturated aliphatic carboxyl derivative of Formula IIa, which is alkyl, with a base in the presence of a hydrogenation catalyst and hydrogen gas.

[0093] In some embodiments, forming the alkenol of Formula II comprises contacting the unsaturated aliphatic carboxylic derivative of Formula IIa with a reducing agent. Any suitable reducing agent can be used to reduce the unsaturated aliphatic carboxylic derivative of Formula IIa to the alkenol of Formula II, such as sodium borohydride, sodium triacetoxyborohydride, sodium cyanoborohydride, lithium aluminum hydride, diisobutylaluminum hydride (CN 103319704; Chandrasekhar, et al. Tetrahedron Lett. 1998, 39, 909), and sodium bis(2-methoxyethoxy)aluminum hydride ("SMEAH"; also known under the trade names RED-AL, SYNHYDRIDE, and VITRIDE). In some embodiments, the reducing agent is sodium bis(2-methoxyethoxy)aluminum hydride.

[0094] Typically, 1 to 2 molar equivalents of a reducing agent are used relative to the unsaturated aliphatic carboxylic derivative. In some embodiments, about 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5 molar equivalents of a reducing agent relative to the unsaturated aliphatic carboxylic derivative are used to form the corresponding alkenol. In some embodiments, the step of forming the alkenol of Formula II comprises contacting an unsaturated aliphatic carboxylic derivative of Formula IIa, which is an unsaturated fatty acid, with a reducing agent ... 4 The process includes contacting an unsaturated aliphatic carboxylic derivative of Formula IIa, where is H, with a reducing agent. Typically, unsaturated fatty acid reduction reactions are carried out at temperatures ranging from about −78° C. to about 25° C. for a period sufficient to form an alkenol. The reaction can be carried out for a period ranging from a few minutes to several hours or longer, depending on the particular unsaturated fatty acid and reducing agent used in the reaction. For example, reduction of (Z)-icosa-11-enoic acid with an aluminum reagent (e.g., sodium bis(2-methoxyethoxy)aluminum hydride) can be carried out for 1 to 2 hours at temperatures ranging from about 0° C. to about 20° C.

[0095] Any suitable solvent can be used to reduce the unsaturated aliphatic carboxylic derivative of Formula IIa (e.g., with a base and a hydrogenation catalyst and hydrogen gas, or with a reducing agent), including, but not limited to, toluene, methylene chloride, ethyl acetate, acetonitrile, tetrahydrofuran, benzene, chloroform, diethyl ether, dimethylformamide, dimethyl sulfoxide, petroleum ether, and mixtures thereof.

[0096] Thus, in some embodiments, the present invention provides compounds of formula I: TIFF0007821747000035.tif16128, a method for synthesizing an aliphatic olefin metathesis product comprising: to form an alkenol of formula IIa: reducing the unsaturated aliphatic carboxyl derivative of TIFF0007821747000037.tif16128; Formula III: contacting an acylating agent with an alkenol to form an olefin metathesis reaction partner of formula (TIFF0007821747000038.tif16128); and To form an aliphatic olefin metathesis product, an olefin metathesis reaction partner and an aliphatic olefin metathesis reaction partner of Formula IV: and an internal olefin of formula (I) in the presence of a Z-selective ruthenium catalyst or a Z-selective osmium catalyst, wherein R 1 is H and C 1~6 selected from the group consisting of alkyl; R 2 C 1~18 Alkyl and C 2~18 alkenyl; R 3 C 1~18 is alkyl; R 4 is H and C 1~8 selected from the group consisting of alkyl; The subscript y is an integer ranging from 0 to 17; The subscript z is an integer in the range of 0 to 17.

[0097] In some embodiments, synthesizing an aliphatic olefin metathesis product of Formula I according to any of the methods described herein may further comprise contacting the olefin metathesis reaction partner of Formula III with a pretreatment reagent prior to contacting the olefin with the olefin metathesis reaction partner. In some embodiments, the pretreatment reagent is selected from the group consisting of alumina and magnesium aluminum isopropoxide. In some embodiments, the pretreatment reagent is alumina. In some embodiments, the pretreatment reagent is magnesium aluminum isopropoxide.

[0098] In some embodiments, R of Formula I and Formula III 1 is H and C 1~6 In some embodiments, R is selected from the group consisting of alkyl. 1 is H. In some embodiments, R 1 is C 1~6 In some embodiments, R 1 is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, and 1-ethyl-2-methylpropyl. 1is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl. 1 is H and C 1~3 In some embodiments, R is selected from the group consisting of alkyl. 1 is selected from the group consisting of H, methyl, ethyl, and propyl. In some embodiments, R 1 is selected from the group consisting of H, methyl, and ethyl. In some embodiments, R 1 is selected from the group consisting of H and methyl. In some embodiments, R 1 is methyl.

[0099] In some embodiments, R of Formula IIa, Formula II, and Formula III 2 is C 1~18 Alkyl and C 2~18 In some embodiments, R is selected from the group consisting of alkenyl. 2 is C 1~18 In some embodiments, R 2 is C 2~18 In some embodiments, R is alkenyl. 2 is C 1~18 Alkyl, C 2~18 Alkyl, C 3~18 Alkyl, C 4~18 Alkyl, C 5~18 Alkyl, C 6~18 Alkyl, C 6~18 Alkyl, C 7~18 Alkyl, C 8~18 Alkyl, C 9~18 Alkyl, C 10~18 Alkyl, C 11~18 Alkyl, C 12~18 Alkyl, C 13~18 Alkyl, C 14~18 Alkyl, C 15~18 Alkyl, C 16~18 Alkyl, and C 17~18 In some embodiments, R is selected from the group consisting of alkyl. 2 is C 2~18 Alkenyl, C 3~18 Alkenyl, C 4~18 Alkenyl, C 5~18Alkenyl, C 6~18 Alkenyl, C 7~18 Alkenyl, C 8~18 Alkenyl, C 9~18 Alkenyl, C 10~18 Alkenyl, C 11~18 Alkenyl, C 12~18 Alkenyl, C 13~18 Alkenyl, C 14~18 Alkenyl, C 15~18 Alkenyl, C 16~18 Alkenyl, and C 17~18 In some embodiments, R is selected from the group consisting of alkenyl. 2 is a linear C alkyl group selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. 1~18 In some embodiments, R 2 is a straight-chain C alkyl group having a carbon-carbon double bond at any position within the hydrocarbon chain, selected from the group consisting of vinyl, propenyl, n-butenyl, n-pentenyl, n-hexenyl, n-heptenyl, n-octenyl, n-nonenyl, n-decenyl, n-undecenyl, n-dodecenyl, n-tridecenyl, n-tetradecenyl, n-pentadecenyl, n-hexadecenyl, n-heptadecenyl, and n-octadecenyl. 2~18 It is alkenyl.

[0100] In some embodiments, R of Formula IIa, Formula II, and Formula III 2 is C 1~12 Alkyl and C 2~12 In some embodiments, R is selected from the group consisting of alkenyl. 2 is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, vinyl, propenyl, n-butenyl, n-pentenyl, n-hexenyl, n-heptenyl, n-octenyl, n-nonenyl, n-decenyl, n-undecenyl, and n-dodecenyl.2 is C 1~12 In some embodiments, R 2 is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl. 2 is selected from the group consisting of n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. 2 is selected from the group consisting of n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-nonyl. 2 is selected from the group consisting of n-hexyl, n-heptyl, and n-octyl. 2 is n-octyl. In some embodiments, R 2 is not H.

[0101] In some embodiments, R of Formula III 3 is C 1~18 In some embodiments, R 3 is C 1~18 Alkyl, C 1~17 Alkyl, C 1~16 Alkyl, C 1~15 Alkyl, C 1~14 Alkyl, C 1~13 Alkyl, C 1~12 Alkyl, C 1~11 Alkyl, C 1~10 Alkyl, C 1~9 Alkyl, C 1~8 Alkyl, C 1~7 Alkyl, C 1~6 Alkyl, C 1~5 Alkyl, C 1~4 Alkyl, C 1~3 Alkyl, and C 1~2 In some embodiments, R is selected from the group consisting of alkyl. 3is a linear C alkyl group selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. 1~18 In some embodiments, R 3 is C 1~12 In some embodiments, R 3 is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl. 3 is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. 3 is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl. 3 is selected from the group consisting of ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl. 3 is n-butyl. In some embodiments, R 3 is n-propyl. In some embodiments, R 3 is ethyl. In some embodiments, R 3 is not H.

[0102] In some embodiments, R of Formula IIa 4 is H and C 1~8 In some embodiments, R is selected from the group consisting of alkyl. 4 is H. In some embodiments, R 4 is C 1~8 In some embodiments, R 4is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, and octyl. 4 is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. 4 is H and C 1~3 In some embodiments, R is selected from the group consisting of alkyl. 4 is selected from the group consisting of H, methyl, ethyl, and propyl. In some embodiments, R 4 is selected from the group consisting of H, methyl, and ethyl. In some embodiments, R 4 is selected from the group consisting of H and methyl. In some embodiments, R 4 is H. In some embodiments, R 4 is methyl. R 4 When R is H, the unsaturated aliphatic carboxylic derivative of formula IIa is an unsaturated fatty acid. 4 C 1~8 Alkyl or C 1~3 When alkyl, the unsaturated aliphatic carboxylic derivative of formula IIa is an unsaturated fatty acid alkyl ester.

[0103] In some embodiments, the subscript y in Formula I, Formula IIa, Formula II, and Formula III is an integer ranging from 0 to 17. In some embodiments, the subscript y is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17. In some embodiments, the subscript y is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16. In some embodiments, the subscript y is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. In some embodiments, the subscript y is an integer ranging from 5 to 15. In some embodiments, the subscript y is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. In some embodiments, the subscript y is 6, 7, 8, 9, 10, 11, 12, or 13. In some embodiments, the subscript y is 7, 9, 11, or 13. In some embodiments, the subscript y is 7. In some embodiments, the subscript y is 9. In some embodiments, the subscript z in Formula I and Formula IV is an integer ranging from 0 to 17. In some embodiments, the subscript z is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17. In some embodiments, the subscript z is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14. In some embodiments, the subscript z is an integer ranging from 0 to 7. In some embodiments, the subscript z is 0, 1, 2, 3, 4, 5, 6, or 7. In some embodiments, the subscript z is an integer ranging from 0 to 5. In some embodiments, the subscript z is 0, 1, 2, 3, 4, or 5. In some embodiments, the subscript z is 1, 2, 3, or 4. In some embodiments, the subscript z is 1. In some embodiments, the subscript z is 2. In some embodiments, the subscript z is 3.

[0104] In some embodiments, the methods described herein are used to prepare aliphatic olefin metathesis products of Formula I, wherein y is 0 and z is 4; alternatively, y is 1 and z is 3; alternatively, y is 3 and z is 1; alternatively, y is 4 and z is 0; alternatively, y is 0 and z is 5; alternatively, y is 1 and z is 4; alternatively, y is 2 and z is 3; alternatively, y is 3 and z is 2; alternatively, y is 4 and z is 1; alternatively, y is 5 and z is 0; alternatively, y is 0 and z is 6; alternatively, y is 1 and z is 5; alternatively, y is 2 and z is 4; alternatively, y is 4 and z is 2; alternatively, y is 5 and z is 1; alternatively, y is 6 and z is 0; alternatively, y is 0 and z is 7; Or, y is 1 and z is 6; or, y is 2 and z is 5; or, y is 3 and z is 4; or, y is 4 and z is 3; or, y is 5 and z is 2; or, y is 6 and z is 1; or, y is 7 and z is 0; or, y is 0 and z is 8; or, y is 1 and z is 7; or, y is 2 and z is 6; or, y is 3 and z is 5; or, y is 5 and z is 3; or, y is 6 and z is 2; or, y is 7 and z is 1; or, y is 8 and z is 0; or, y is 0 and z is 9; or, y is 1 and z is 8; or, y is 2 and z is 7; Or, y is 3 and z is 6; or, y is 4 and z is 5; or, y is 5 and z is 4; or, y is 6 and z is 3; or, y is 7 and z is 2; or, y is 8 and z is 1; or, y is 9 and z is 0; or, y is 0 and z is 10; or, y is 1 and z is 9; or, y is 2 and z is 8; or, y is 3 and z is 7; or, y is 4 and z is 6;Or, y is 6 and z is 4; or, y is 7 and z is 3; or, y is 8 and z is 2; or, y is 9 and z is 1; or, y is 10 and z is 0; or, y is 0 and z is 11; or, y is 1 and z is 10; or, y is 2 and z is 9; or, y is 3 and z is 8; or, y is 4 and z is 7; or, y is 5 and z is 6; or, y is 6 and z is 5; or, y is 7 and z is 4; or, y is 8 and z is 3; or, y is 9 and z is 2; or, y is 10 and z is 1; or, y is 11 and z is 0; or, y is 0 and z is 12; Or, y is 1 and z is 11; or, y is 2 and z is 10; or, y is 3 and z is 9; or, y is 4 and z is 8; or, y is 5 and z is 7; or, y is 7 and z is 5; or, y is 8 and z is 4; or, y is 9 and z is 3; or, y is 10 and z is 2; or, y is 11 and z is 1; or, y is 12 and z is 0; or, y is 0 and z is 13; or, y is 1 and z is 12; or, y is 2 and z is 11; or, y is 3 and z is 10; or, y is 4 and z is 9; or, y is 5 and z is 8; or, y is 6 and z is 7; Or, y is 7 and z is 6; or, y is 8 and z is 5; or, y is 9 and z is 4; or, y is 10 and z is 3; or, y is 11 and z is 2; or, y is 12 and z is 1; or, y is 13 and z is 0; or, y is 0 and z is 14; or, y is 1 and z is 13; or, y is 2 and z is 12; or, y is 3 and z is 11; or, y is 4 and z is 10;Or, y is 5 and z is 9; or, y is 6 and z is 8; or, y is 8 and z is 6; or, y is 9 and z is 5; or, y is 10 and z is 4; or, y is 11 and z is 3; or, y is 12 and z is 2; or, y is 13 and z is 1; or, y is 14 and z is 0; or, y is 0 and z is 15; or, y is 1 and z is 14; or, y is 2 and z is 13; or, y is 3 and z is 12; or, y is 4 and z is 11; or, y is 5 and z is 10; or, y is 6 and z is 9; or, y is 7 and z is 8; or, y is 8 and z is 7; Or, y is 9 and z is 6; or, y is 10 and z is 5; or, y is 11 and z is 4; or, y is 12 and z is 3; or, y is 13 and z is 2; or, y is 14 and z is 1; or, y is 15 and z is 0; or, y is 0 and z is 16; or, y is 1 and z is 15; or, y is 2 and z is 14; or, y is 3 and z is 13; or, y is 4 and z is 12; or, y is 5 and z is 11; or, y is 6 and z is 10; or, y is 7 and z is 9; or, y is 9 and z is 7; or, y is 10 and z is 6; Or, y is 11 and z is 5; or, y is 12 and z is 4; or, y is 13 and z is 3; or, y is 14 and z is 2; or, y is 15 and z is 1; or, y is 16 and z is 0; or, y is 1 and z is 16; or, y is 2 and z is 15; or, y is 3 and z is 14; or, y is 4 and z is 13; or, y is 5 and z is 12; or, y is 6 and z is 11; or, y is 7 and z is 10;Or, y is 8 and z is 9; or, y is 9 and z is 8; or, y is 10 and z is 7; or, y is 11 and z is 6; or, y is 12 and z is 5; or, y is 13 and z is 4; or, y is 14 and z is 3; or, y is 15 and z is 2; or, y is 16 and z is 1; or, y is 17 and z is 0; or, y is 0 and z is 17; or, y is 1 and z is 17; or, y is 2 and z is 16; or, y is 3 and z is 15; or, y is 4 and z is 14; or, y is 5 and z is 13; or, y is 6 and z is 12; Alternatively, y is 7 and z is 11; alternatively, y is 8 and z is 10; alternatively, y is 10 and z is 8; alternatively, y is 11 and z is 7; alternatively, y is 12 and z is 6; alternatively, y is 13 and z is 5; alternatively, y is 14 and z is 4; alternatively, y is 15 and z is 3; alternatively, y is 16 and z is 2; alternatively, y is 17 and z is 1. In some embodiments, y and z are both 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17.

[0105] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises contacting an olefin metathesis reaction partner of formula III with an internal olefin of formula IV, wherein R 1 is C 1~3 alkyl, and R 2 is C 1~12 alkyl, and R 3 is C 1~12 alkyl, y is an integer ranging from 5 to 15, and z is an integer ranging from 0 to 7. In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein R1 is selected from the group consisting of H and methyl; R 2 is n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; R 3 is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl; y is an integer ranging from 6 to 14; and z is an integer ranging from 1 to 4. In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein R 1 is methyl; R 2 is selected from the group consisting of n-hexyl, n-heptyl, and n-octyl; R 3 is selected from the group consisting of ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; y is an integer selected from the group consisting of 7, 9, 11, and 13; and z is an integer selected from the group consisting of 1, 2, and 3. In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein R 1 is methyl; R 2 is n-octyl; R 3 is selected from the group consisting of ethyl and n-butyl; y is an integer selected from the group consisting of 7, 9, 11, and 13; and z is an integer selected from the group consisting of 1 and 3.

[0106] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the metathesis reaction partner of Formula III is an aliphatic C 12 ~C 30 olefin acetate; the internal olefin of formula IV is C4-C 20 The aliphatic olefin metathesis product of Formula I is a C-C 28In some embodiments, the metathesis reaction partner of formula III is an aliphatic C 16 ~C 28 olefin acetate; the internal olefin of formula IV is C4-C 12 the aliphatic olefin metathesis product of formula I is C 12 ~C 24 In some embodiments, the metathesis reaction partner of formula III is an aliphatic C 18 ~C 26 olefin acetate; the internal olefin of formula IV is C-C 10 the aliphatic olefin metathesis product of formula I is C 14 ~C 22 (Z)-Unsaturated aliphatic ester acetate.

[0107] In some embodiments, the present invention provides methods for synthesizing an aliphatic olefin metathesis product of Formula I described herein, wherein the olefin metathesis reaction partner of Formula III is selected from the group consisting of octadec-9-en-1-yl acetate, icos-11-en-1-yl acetate, docos-13-en-1-yl acetate, tetracos-15-en-1-yl acetate, or a mixture thereof. In some embodiments, the olefin metathesis reaction partner consists of octadec-9-en-1-yl acetate and at least one member selected from the group consisting of icos-11-en-1-yl acetate, docos-13-en-1-yl acetate, and tetracos-15-en-1-yl acetate. In some embodiments, the olefin metathesis reaction partner is selected from the group consisting of octadec-9-en-1-yl acetate, icos-11-en-1-yl acetate, docos-13-en-1-yl acetate, and tetracos-15-en-1-yl acetate. In some embodiments, the olefin metathesis reaction partner is octadec-9-en-1-yl acetate. In some embodiments, the olefin metathesis reaction partner is icos-11-en-1-yl acetate. In some embodiments, the olefin metathesis reaction partner is docos-13-en-1-yl acetate. In some embodiments, the olefin metathesis reaction partner is tetracos-15-en-1-yl acetate.

[0108] In some embodiments, the present invention provides a method for synthesizing an aliphatic olefin metathesis product of Formula I described herein, wherein the olefin of Formula IV is selected from the group consisting of hexadec-8-ene, tetradec-7-ene, dodec-6-ene, dec-5-ene, oct-4-ene, or hex-3-ene. In some embodiments, the olefin is selected from the group consisting of hexadec-8-ene, tetradec-7-ene, dodec-6-ene, dec-5-ene, oct-4-ene, and hex-3-ene. In some embodiments, the olefin is selected from the group consisting of tetradec-7-ene, dodec-6-ene, dec-5-ene, oct-4-ene, and hex-3-ene. In some embodiments, the olefin is selected from the group consisting of dodec-6-ene, dec-5-ene, oct-4-ene, and hex-3-ene. In some embodiments, the olefin is selected from the group consisting of dec-5-ene, oct-4-ene, and hex-3-ene. In some embodiments, the olefin is dec-5-ene. In some embodiments, the olefin is oct-4-ene. In some embodiments, the olefin is hex-3-ene.

[0109] In some aspects, the present invention provides methods for synthesizing an aliphatic olefin metathesis product of Formula I described herein, wherein the aliphatic olefin metathesis product is (Z)-tetradec-9-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, (Z)-icos-15-en-1-yl acetate, (Z)-tridec-9-en-1-yl acetate, (Z)-pentadec-11-en-1-yl acetate, (Z)-heptadec-13-en-1-yl acetate, (Z)-nonadec-15-en-1-yl acetate, (Z)-dodec-9-en-1-yl acetate, (Z)-tetradec-11-en-1-yl acetate, acetate, (Z)-hexadec-13-en-1-yl acetate, (Z)-octadec-15-en-1-yl acetate, or mixtures thereof. In some embodiments, the aliphatic olefin metathesis product comprises at least one member selected from the group consisting of (Z)-tetradec-9-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, and (Z)-icos-15-en-1-yl acetate. In some embodiments, the aliphatic olefin metathesis product comprises at least one member selected from the group consisting of (Z)-tridec-9-en-1-yl acetate, (Z)-pentadec-11-en-1-yl acetate, (Z)-heptadec-13-en-1-yl acetate, and (Z)-nonadec-15-en-1-yl acetate. In some embodiments, the aliphatic olefin metathesis product comprises at least one member selected from the group consisting of (Z)-dodec-9-en-1-yl acetate, (Z)-tetradec-11-en-1-yl acetate, (Z)-hexadec-13-en-1-yl acetate, and (Z)-octadec-15-en-1-yl acetate.In some embodiments, the aliphatic olefin metathesis product is selected from the group consisting of (Z)-tetradec-9-en-1-yl acetate, (Z)-dodec-9-en-1-yl acetate, and (Z)-tetradec-11-en-1-yl acetate.

[0110] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the olefin metathesis reaction partner of Formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-icos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl acetate; the internal olefin of Formula IV is selected from the group consisting of (Z)-dec-5-ene, (Z)-oct-4-ene, and (Z)-hex-3-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-tetradec-9-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, or (Z)-tetradec-9-en-1-yl acetate. acetate, (Z)-octadec-13-en-1-yl acetate, (Z)-icosa-15-en-1-yl acetate, (Z)-tridec-9-en-1-yl acetate, (Z)-pentadec-11-en-1-yl acetate, (Z)-heptadec-13-en-1-yl acetate, (Z)-nonadec-15-en-1-yl acetate, (Z)-dodec-9-en-1-yl acetate, (Z)-tetradec-11-en-1-yl acetate, (Z)-hexadec-13-en-1-yl acetate, and (Z)-octadec-15-en-1-yl acetate.

[0111] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the olefin metathesis reaction partner of Formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-icos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl acetate; the internal olefin of Formula IV is (Z)-dec-5-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-tetradec-9-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, (Z)-tetradec-9-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, (Z)-hexa ... acetate, and (Z)-icosa-15-en-1-yl acetate.

[0112] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the olefin metathesis reaction partner of Formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-icos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl acetate; the internal olefin of Formula IV is (Z)-oct-4-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-tridec-9-en-1-yl acetate, (Z)-pentadec-11-en-1-yl acetate, (Z)-heptadec-13-en-1-yl acetate, (Z)-tetracos-15-en-1-yl acetate. acetate, and (Z)-nonadec-15-en-1-yl acetate.

[0113] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the olefin metathesis reaction partner of Formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-icos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl acetate; the internal olefin of Formula IV is (Z)-hex-3-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-dodec-9-en-1-yl acetate, (Z)-tetradec-11-en-1-yl acetate, (Z)-hexadec-13 ... acetate, and (Z)-octadec-15-en-1-yl acetate.

[0114] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, where the olefin metathesis reaction partner of Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin of Formula IV is (Z)-dec-5-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-tetradec-9-en-1-yl acetate. In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, where the olefin metathesis reaction partner of Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin of Formula IV is (Z)-hex-3-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-dodec-9-en-1-yl acetate. In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, where the olefin metathesis reaction partner of Formula III is (Z)-icos-11-en-1-yl acetate; the internal olefin of Formula IV is (Z)-hex-3-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-tetradec-11-en-1-yl acetate.

[0115] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes contacting an acylating agent with an alkenol of Formula II, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV to form an olefin metathesis reaction partner of Formula III, wherein R 1 is C 1~3 alkyl, and R 2 is C 1~12 alkyl, and R 3 is C 1~12alkyl, y is an integer ranging from 5 to 15, and z is an integer ranging from 0 to 7. In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes contacting an acylating agent with an alkenol of Formula II, and contacting an olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV to form an olefin metathesis reaction partner of Formula III, wherein R 1 is selected from the group consisting of H and methyl; R 2 is n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; R 3 is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl; y is an integer ranging from 6 to 14; and z is an integer ranging from 1 to 4. In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises contacting an acylating agent with an alkenol of Formula II and contacting an olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV to form an olefin metathesis reaction partner of Formula III, wherein R 1 is methyl; R 2 is selected from the group consisting of n-hexyl, n-heptyl, and n-octyl; R 3 is selected from the group consisting of ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; y is an integer selected from the group consisting of 7, 9, 11, and 13; and z is an integer selected from the group consisting of 1, 2, and 3. In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises contacting an acylating agent with an alkenol of Formula II and contacting an olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV to form an olefin metathesis reaction partner of Formula III, wherein R 1 is methyl; R 2 is n-octyl; R 3is selected from the group consisting of ethyl and n-butyl; y is an integer selected from the group consisting of 7, 9, 11, and 13; and z is an integer selected from the group consisting of 1 and 3.

[0116] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes contacting an acylating agent with an alkenol of Formula II to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the alkenol of Formula II is C 10 ~C 28 aliphatic alkenol; the metathesis reaction partner of formula III is C 10 ~C 28 The internal olefin of formula IV is a C4-C6 acetate ester of an aliphatic alkenol; 20 The aliphatic olefin metathesis product of Formula I is a C-C 28 In some embodiments, the alkenol of Formula II is a C 14 ~C 26 aliphatic alkenol; the metathesis reaction partner of formula III is C 14 ~C 26 The internal olefin of formula IV is a C4-C6 acetate ester of an aliphatic alkenol; 12 the aliphatic olefin metathesis product of formula I is C 12 ~C 24 In some embodiments, the alkenol of Formula II is a C 16 ~C 24 aliphatic alkenol; the metathesis reaction partner of formula III is C 16 ~C 24 The internal olefin of formula IV is a C6-C6 acetate ester of an aliphatic alkenol; 10 the aliphatic olefin metathesis product of formula I is C 14 ~C 22 (Z)-Unsaturated aliphatic ester acetate.

[0117] In some embodiments, the present invention provides a method for synthesizing an aliphatic olefin metathesis product of Formula I described herein, wherein the alkenol of Formula II is selected from the group consisting of octadec-9-en-1-ol, icos-11-en-1-ol, docos-13-en-1-ol, tetracos-15-en-ol, or a mixture thereof. In some embodiments, the alkenol is selected from the group consisting of octadec-9-en-1-ol, icos-11-en-1-ol, docos-13-en-1-ol, and tetracos-15-en-ol. In some embodiments, the alkenol is octadec-9-en-1-ol. In some embodiments, the alkenol is icos-11-en-1-ol. In some embodiments, the alkenol is docos-13-en-1-ol. In some embodiments, the alkenol is tetracos-15-en-ol.

[0118] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes contacting an acylating agent with an alkenol of Formula II, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV to form an olefin metathesis reaction partner of Formula III, wherein the alkenol of Formula II comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-ol, (Z)-icos-11-en-1-ol, (Z)-docos-13-en-1-ol, and (Z)-tetracos-15-en-1-ol; and the olefin metathesis reaction partner of Formula III is (Z)-octadec-9-en-1-yl acetate, (Z)-icos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl the internal olefin of Formula IV is selected from the group consisting of (Z)-dec-5-ene, (Z)-oct-4-ene, and (Z)-hex-3-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-tetradec-9-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, (Z)-icos-15-en-1-yl acetate, (Z)-tridec-9-en-1-yl acetate, (Z)-pentadec-11-en-1-yl acetate, (Z)-heptadec-13-en-1-yl acetate, (Z)-nonadec-15-en-1-yl acetate, (Z)-hexadec-1 ... acetate, (Z)-dodec-9-en-1-yl acetate, (Z)-tetradec-11-en-1-yl acetate, (Z)-hexadec-13-en-1-yl acetate, and (Z)-octadec-15-en-1-yl acetate.

[0119] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes contacting an acylating agent with an alkenol of Formula II, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV to form an olefin metathesis reaction partner of Formula III, wherein the alkenol of Formula II comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-ol, (Z)-icos-11-en-1-ol, (Z)-docos-13-en-1-ol, and (Z)-tetracos-15-en-1-ol; and the olefin metathesis reaction partner of Formula III is (Z)-octadec-9-en-1-yl acetate, (Z)-icos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl the internal olefin of Formula IV is (Z)-dec-5-ene; and the aliphatic olefin metathesis product of Formula I comprises at least one member selected from the group consisting of (Z)-tetradec-9-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, and (Z)-icos-15-en-1-yl acetate.

[0120] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes contacting an acylating agent with an alkenol of Formula II, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV to form an olefin metathesis reaction partner of Formula III, wherein the alkenol of Formula II comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-ol, (Z)-icos-11-en-1-ol, (Z)-docos-13-en-1-ol, and (Z)-tetracos-15-en-1-ol; and the olefin metathesis reaction partner of Formula III is (Z)-octadec-9-en-1-yl acetate, (Z)-icos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl the internal olefin of Formula IV is (Z)-oct-4-ene; and the aliphatic olefin metathesis product of Formula I comprises at least one member selected from the group consisting of (Z)-tridec-9-en-1-yl acetate, (Z)-pentadec-11-en-1-yl acetate, (Z)-heptadec-13-en-1-yl acetate, and (Z)-nonadec-15-en-1-yl acetate.

[0121] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes contacting an acylating agent with an alkenol of Formula II, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV to form an olefin metathesis reaction partner of Formula III, wherein the alkenol of Formula II comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-ol, (Z)-icos-11-en-1-ol, (Z)-docos-13-en-1-ol, and (Z)-tetracos-15-en-1-ol; and the olefin metathesis reaction partner of Formula III is (Z)-octadec-9-en-1-yl acetate, (Z)-icos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl the internal olefin of Formula IV is (Z)-hex-3-ene; and the aliphatic olefin metathesis product of Formula I comprises at least one member selected from the group consisting of (Z)-dodec-9-en-1-yl acetate, (Z)-tetradec-11-en-1-yl acetate, (Z)-hexadec-13-en-1-yl acetate, and (Z)-octadec-15-en-1-yl acetate.

[0122] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes contacting an acylating agent with an alkenol of Formula II, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV to form an olefin metathesis reaction partner of Formula III, wherein the alkenol of Formula II is (Z)-octadec-9-en-1-ol; the olefin metathesis reaction partner of Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin of Formula IV is (Z)-dec-5-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-tetradec-9-en-1-yl acetate. In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes contacting an acylating agent with an alkenol of Formula II, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV to form an olefin metathesis reaction partner of Formula III, wherein the alkenol of Formula II is (Z)-octadec-9-en-1-ol; the olefin metathesis reaction partner of Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin of Formula IV is (Z)-hex-3-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-dodec-9-en-1-yl acetate. In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes contacting an acylating agent with an alkenol of Formula II, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV to form an olefin metathesis reaction partner of Formula III, wherein the alkenol of Formula II is (Z)-icos-11-en-1-ol; the olefin metathesis reaction partner of Formula III is (Z)-icos-11-en-1-yl acetate; the internal olefin of Formula IV is (Z)-hex-3-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-tetradec-11-en-1-yl acetate.

[0123] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes reducing an unsaturated aliphatic carboxylic derivative of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein R 1 is C 1~3 alkyl, and R 2 is C 1~12 alkyl, and R 3 is C 1~12 alkyl, and R 4 is H and C 1~3 alkyl, y is an integer ranging from 5 to 15, and z is an integer ranging from 0 to 7. In some embodiments, R 1 is C 1~3 alkyl, and R 2 is C 1~12 alkyl, and R 3 is C 1~12 alkyl, and R 4 is C 1~3 alkyl, y is 7, and z is an integer ranging from 1 to 5. In some embodiments, R 1 is C 1~3 alkyl, and R 2 is C 1~12 alkyl, and R 3 is C 1~12 alkyl, and R 4 is H, y is an integer ranging from 5 to 15, and z is an integer ranging from 1 to 5.

[0124] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes reducing an unsaturated aliphatic carboxylic derivative of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein R 1is selected from the group consisting of H and methyl; R 2 is n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; R 3 is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl; R 4 is selected from the group consisting of H and methyl; y is an integer ranging from 6 to 14; and z is an integer ranging from 1 to 4. In some embodiments, R 1 is methyl; R 2 is selected from the group consisting of n-hexyl, n-heptyl, and n-octyl; R 3 is selected from the group consisting of ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; R 4 is methyl; y is an integer selected from the group consisting of 7, 9, 11, and 13; and z is an integer selected from the group consisting of 1, 2, and 3. In some embodiments, R 1 is methyl; R 2 is selected from the group consisting of n-hexyl, n-heptyl, and n-octyl; R 3 is selected from the group consisting of ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; R 4 is H; y is an integer selected from the group consisting of 7, 9, 11, and 13; and z is an integer selected from the group consisting of 1, 2, and 3.

[0125] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes reducing an unsaturated aliphatic carboxylic derivative of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein R 1 is methyl; R 2 is n-octyl; R 3is selected from the group consisting of ethyl and n-butyl; R 4 is methyl; y is an integer selected from the group consisting of 7, 9, 11, and 13; and z is an integer selected from the group consisting of 1 and 3. In some embodiments, R 1 is methyl; R 2 is n-octyl; R 3 is selected from the group consisting of ethyl and n-butyl; R 4 is methyl; y is an integer selected from the group consisting of 7; and z is an integer selected from the group consisting of 1 and 3. In some embodiments, R 1 is methyl; R 2 is n-octyl; R 3 is selected from the group consisting of ethyl and n-butyl; R 4 is H; y is an integer selected from the group consisting of 7, 9, 11, and 13; and z is an integer selected from the group consisting of 1 and 3. In some embodiments, R 1 is methyl; R 2 is n-octyl; R 3 is selected from the group consisting of ethyl and n-butyl; R 4 is H; y is an integer selected from the group consisting of 7; and z is an integer selected from the group consisting of 1 and 3.

[0126] In some embodiments, R of Formula IIa 4 C 1~8 Alkyl (e.g., C 1-3 alkyl, methyl, etc.), the unsaturated aliphatic carboxylic derivative is an unsaturated fatty acid alkyl ester. Thus, in some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes reducing an unsaturated fatty acid alkyl ester of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the unsaturated fatty acid alkyl ester of Formula IIa is C11 ~C 29 unsaturated fatty acid methyl esters; the alkenol of formula II is C 10 ~C 28 aliphatic alkenol; the metathesis reaction partner of formula III is C 10 ~C 28 The internal olefin of formula IV is a C4-C6 acetate ester of an aliphatic alkenol; 20 The aliphatic olefin metathesis product of Formula I is a C-C 28 In some embodiments, the unsaturated fatty acid alkyl ester of Formula IIa is a C 15 ~C 27 unsaturated fatty acid methyl esters; the alkenol of formula II is C 14 ~C 26 aliphatic alkenol; the metathesis reaction partner of formula III is C 14 ~C 26 The internal olefin of formula IV is a C4-C6 acetate ester of an aliphatic alkenol; 12 the aliphatic olefin metathesis product of formula I is C 12 ~C 24 In some embodiments, the unsaturated fatty acid alkyl ester of Formula IIa is a C 17 ~C 25 unsaturated fatty acid methyl esters; the alkenol of formula II is C 16 ~C 24 aliphatic alkenol; the metathesis reaction partner of formula III is C 16 ~C 24 The internal olefin of formula IV is a C6-C6 acetate ester of an aliphatic alkenol; 10 the aliphatic olefin metathesis product of formula I is C 14 ~C 22 (Z)-Unsaturated aliphatic ester acetate.

[0127] In some embodiments, the present invention provides a method for synthesizing an aliphatic olefin metathesis product of Formula I described herein, wherein the unsaturated fatty acid alkyl ester of Formula IIa is selected from the group consisting of methyl octadec-9-enoate, methyl icos-11-enoate, methyl docos-13-enoate, methyl tetracos-15-enoate, or a mixture thereof. In some embodiments, the unsaturated fatty acid alkyl ester consists of methyl octadec-9-enoate and at least one member selected from the group consisting of methyl icos-11-enoate, methyl docos-13-enoate, and methyl tetracos-15-enoate. In some embodiments, the unsaturated fatty acid alkyl ester is selected from the group consisting of methyl octadec-9-enoate, methyl icos-11-enoate, methyl docos-13-enoate, and methyl tetracos-15-enoate. In some embodiments, the unsaturated fatty acid alkyl ester is methyl octadec-9-enoate. In some embodiments, the unsaturated fatty acid alkyl ester is methyl icos-11-enoate. In some embodiments, the unsaturated fatty acid alkyl ester is methyl docos-13-enoate. In some embodiments, the unsaturated fatty acid alkyl ester is methyl tetracos-15-enoate.

[0128] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises reducing an unsaturated fatty acid alkyl ester of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the unsaturated fatty acid alkyl ester of Formula IIa comprises at least one member selected from the group consisting of methyl (Z)-octadec-9-enoate, methyl (Z)-icos-11-enoate, methyl (Z)-docos-13-enoate, and methyl (Z)-tetracos-15-enoate; The alkenol of formula II comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-ol, (Z)-icos-11-en-1-ol, (Z)-docos-13-en-1-ol, and (Z)-tetracos-15-en-ol; the olefin metathesis reaction partner of formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-icos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl acetate; the internal olefin of formula IV is selected from the group consisting of (Z)-dec-5-ene, (Z)-oct-4-ene, and (Z)-hex-3-ene;Aliphatic olefin metathesis products of formula I include (Z)-tetradec-9-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, (Z)-icosa-15-en-1-yl acetate, (Z)-tridec-9-en-1-yl acetate, (Z)-pentadec-11-en-1-yl acetate, (Z)-heptadec-13-en-1-yl acetate, (Z)-nonadec-15-en-1-yl acetate, (Z)-dodec-9-en-1-yl acetate, (Z)-tetradec-11-en-1-yl acetate, (Z)-hexadec-13-en-1-yl acetate, acetate, and (Z)-octadec-15-en-1-yl acetate;

[0129] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes reducing an unsaturated fatty acid alkyl ester of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the unsaturated fatty acid alkyl ester of Formula IIa is methyl (Z)-octadec-9-enoate; the alkenol of Formula II is (Z)-octadec-9-en-1-ol; the olefin metathesis reaction partner of Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin of Formula IV is (Z)-dec-5-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-tetradec-9-en-1-yl acetate.

[0130] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes reducing an unsaturated fatty acid alkyl ester of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the unsaturated fatty acid alkyl ester of Formula IIa is methyl (Z)-octadec-9-enoate; the alkenol of Formula II is (Z)-octadec-9-en-1-ol; the olefin metathesis reaction partner of Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin of Formula IV is (Z)-hex-3-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-dodec-9-en-1-yl acetate.

[0131] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes reducing an unsaturated fatty acid alkyl ester of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the unsaturated fatty acid alkyl ester of Formula IIa is methyl (Z)-eicos-11-enoate; the alkenol of Formula II is (Z)-eicos-11-en-1-ol; the olefin metathesis reaction partner of Formula III is (Z)-eicos-11-en-1-yl acetate; the internal olefin of Formula IV is (Z)-hex-3-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-tetradec-11-en-1-yl acetate. The prefixes "icosa" and "eicosa" are used interchangeably to refer to hydrocarbon chains having 20 carbons (i.e., methyl (Z)-eicos-11-enoate, (Z)-eicos-11-en-1-ol, and (Z)-eicos-11-en-1-yl acetate correspond to methyl (Z)-icosa-11-enoate, (Z)-icosa-11-en-1-ol, and (Z)-icosa-11-en-1-yl acetate, respectively).

[0132] In some embodiments, R of Formula IIa 4 is H, the unsaturated aliphatic carboxylic derivative is an unsaturated fatty acid. Thus, in some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes reducing an unsaturated fatty acid of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the unsaturated fatty acid of Formula IIa is C 10 ~C 28 unsaturated fatty acids; the alkenol of formula II is C 10 ~C28 aliphatic alkenol; the metathesis reaction partner of formula III is C 10 ~C 28 The internal olefin of formula IV is a C4-C6 acetate ester of an aliphatic alkenol; 20 The aliphatic olefin metathesis product of Formula I is a C-C 28 In some embodiments, the unsaturated fatty acid of Formula IIa is a C 14 ~C 26 unsaturated fatty acids; the alkenol of formula II is C 14 ~C 26 aliphatic alkenol; the metathesis reaction partner of formula III is C 14 ~C 26 The internal olefin of formula IV is a C4-C6 acetate ester of an aliphatic alkenol; 12 the aliphatic olefin metathesis product of formula I is C 12 ~C 24 In some embodiments, the unsaturated fatty acid of Formula IIa is a C 16 ~C 24 unsaturated fatty acids; the alkenol of formula II is C 16 ~C 24 aliphatic alkenol; the metathesis reaction partner of formula III is C 16 ~C 24 The internal olefin of formula IV is a C6-C6 acetate ester of an aliphatic alkenol; 10 the aliphatic olefin metathesis product of formula I is C 14 ~C 22 (Z)-Unsaturated aliphatic ester acetate.

[0133] In some embodiments, the present invention provides methods for synthesizing an aliphatic olefin metathesis product of Formula I described herein, wherein the unsaturated fatty acid of Formula IIa is selected from the group consisting of octadec-9-enoic acid, eicosa-11-enoic acid, docos-13-enoic acid, tetracos-15-enoic acid, or a mixture thereof. In some embodiments, the unsaturated fatty acid consists of octadec-9-enoic acid and at least one member selected from the group consisting of eicosa-11-enoic acid, docos-13-enoic acid, and tetracos-15-enoic acid. In some embodiments, the unsaturated fatty acid is selected from the group consisting of octadec-9-enoic acid, eicosa-11-enoic acid, docos-13-enoic acid, and tetracos-15-enoic acid. In some embodiments, the unsaturated fatty acid is octadec-9-enoic acid. In some embodiments, the unsaturated fatty acid is eicosa-11-enoic acid. In some embodiments, the unsaturated fatty acid is docos-13-enoic acid. In some embodiments, the unsaturated fatty acid is tetracos-15-enoic acid.

[0134] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes reducing an unsaturated fatty acid of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the unsaturated fatty acid of Formula IIa comprises at least one member selected from the group consisting of (Z)-octadec-9-enoic acid, (Z)-icos-11-enoic acid, (Z)-docos-13-enoic acid, and (Z)-tetracos-15-enoic acid; the alkenol of Formula II comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-ol, (Z)-icos-11-en-1-ol, (Z)-docos-13-en-1-ol, and (Z)-tetracos-15-en-ol; The olefin metathesis reaction partner of formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-icos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl acetate; the internal olefin of formula IV is selected from the group consisting of (Z)-dec-5-ene, (Z)-oct-4-ene, and (Z)-hex-3-ene;Aliphatic olefin metathesis products of formula I include (Z)-tetradec-9-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, (Z)-icosa-15-en-1-yl acetate, (Z)-tridec-9-en-1-yl acetate, (Z)-pentadec-11-en-1-yl acetate, (Z)-heptadec-13-en-1-yl acetate, (Z)-nonadec-15-en-1-yl acetate, (Z)-dodec-9-en-1-yl acetate, (Z)-tetradec-11-en-1-yl acetate, (Z)-hexadec-13-en-1-yl acetate, acetate, and (Z)-octadec-15-en-1-yl acetate;

[0135] In some embodiments, the unsaturated aliphatic carboxylic derivative of Formula IIa is derived from a natural oil. In some embodiments, the unsaturated aliphatic carboxylic derivative of Formula IIa is an unsaturated fatty acid obtained from a natural oil or a natural oil derivative. Natural oils or natural oil derivatives suitable for use in the methods of the present invention include natural oils and / or derivatives thereof containing (Z)-octadec-9-enoic acid, (Z)-icosa-11-enoic acid, (Z)-docosa-13-enoic acid, (Z)-tetracos-15-enoic acid, or mixtures thereof. In some embodiments, the unsaturated fatty acids of Formula IIa are derived from natural oils selected from the group consisting of almond oil, canola oil, avocado oil, argan oil, rapeseed oil, palm oil, corn oil, cottonseed oil, grapeseed oil, olive oil, palm oil, peanut oil, hempseed oil, macadamia oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil, jojoba oil, mustard oil, shepherd's purse oil, flaxseed oil, castor oil, and combinations thereof. In some embodiments, the unsaturated fatty acids of Formula IIa are derived from natural oils selected from the group consisting of canola oil, avocado oil, olive oil, palm oil, peanut oil, safflower oil, soybean oil, sunflower oil, jojoba oil, and combinations thereof. In some embodiments, the unsaturated fatty acids of Formula IIa are obtained from natural oils selected from the group consisting of canola oil, avocado oil, olive oil, safflower oil, jojoba oil, and combinations thereof. In some embodiments, the unsaturated fatty acids of Formula IIa are obtained from natural oils selected from the group consisting of canola oil, avocado oil, jojoba oil, and combinations thereof. In some embodiments, the unsaturated fatty acids of Formula IIa are obtained from natural oils selected from the group consisting of canola oil and jojoba oil. In some embodiments, the unsaturated fatty acids of Formula IIa are obtained from jojoba oil.

[0136] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises reducing an unsaturated fatty acid of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the unsaturated fatty acid of Formula IIa is obtained from a natural oil or a derivative thereof and comprises at least one member selected from the group consisting of (Z)-octadec-9-enoic acid, (Z)-icosa-11-enoic acid, (Z)-docosa-13-enoic acid, and (Z)-tetracos-15-enoic acid; The alkenol of formula II comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-ol, (Z)-icos-11-en-1-ol, (Z)-docos-13-en-1-ol, and (Z)-tetracos-15-en-ol; the olefin metathesis reaction partner of formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-icos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl acetate; the internal olefin of formula IV is (Z)-dec-5-ene; and the aliphatic olefin metathesis product of formula I is (Z)-tetradec-9-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, and (Z)-icos-15-en-1-yl acetate.

[0137] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises reducing an unsaturated fatty acid of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the unsaturated fatty acid of Formula IIa is obtained from a natural oil or a derivative thereof and comprises at least one member selected from the group consisting of (Z)-octadec-9-enoic acid, (Z)-icosa-11-enoic acid, (Z)-docosa-13-enoic acid, and (Z)-tetracos-15-enoic acid; The alkenol of formula II comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-ol, (Z)-icos-11-en-1-ol, (Z)-docos-13-en-1-ol, and (Z)-tetracos-15-en-1-yl; the olefin metathesis reaction partner of formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-icos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl acetate; the internal olefin of formula IV is (Z)-oct-4-ene; and the aliphatic olefin metathesis product of formula I is (Z)-tridec-9-en-1-yl acetate, (Z)-pentadec-11-en-1-yl acetate, (Z)-heptadec-13-en-1-yl acetate, and (Z)-nonadec-15-en-1-yl acetate.

[0138] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I comprises reducing an unsaturated fatty acid of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the unsaturated fatty acid of Formula IIa is obtained from a natural oil or a derivative thereof and comprises at least one member selected from the group consisting of (Z)-octadec-9-enoic acid, (Z)-icosa-11-enoic acid, (Z)-docosa-13-enoic acid, and (Z)-tetracos-15-enoic acid; The alkenol of formula II comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-ol, (Z)-icos-11-en-1-ol, (Z)-docos-13-en-1-ol, and (Z)-tetracos-15-en-ol; the olefin metathesis reaction partner of formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-icos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl acetate; the internal olefin of formula IV is (Z)-hex-3-ene; and the aliphatic olefin metathesis product of formula I is (Z)-dodec-9-en-1-yl acetate, (Z)-tetradec-11-en-1-yl acetate, (Z)-hexadec-13-en-1-yl acetate, and (Z)-octadec-15-en-1-yl acetate.

[0139] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes reducing an unsaturated fatty acid of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the unsaturated fatty acid of Formula IIa is (Z)-octadec-9-enoic acid; the alkenol of Formula II is (Z)-octadec-9-en-1-ol; the olefin metathesis reaction partner of Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin of Formula IV is (Z)-dec-5-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-tetradec-9-en-1-yl acetate.

[0140] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes reducing an unsaturated fatty acid of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the unsaturated fatty acid of Formula IIa is (Z)-octadec-9-enoic acid; the alkenol of Formula II is (Z)-octadec-9-en-1-ol; the olefin metathesis reaction partner of Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin of Formula IV is (Z)-hex-3-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-dodec-9-en-1-yl acetate.

[0141] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I includes reducing an unsaturated fatty acid of Formula IIa to form an alkenol of Formula II, contacting the alkenol of Formula II with an acylating agent to form an olefin metathesis reaction partner of Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin of Formula IV, wherein the unsaturated fatty acid of Formula IIa is (Z)-icos-11-enoic acid; the alkenol of Formula II is (Z)-icos-11-en-1-ol; the olefin metathesis reaction partner of Formula III is (Z)-icos-11-en-1-yl acetate; the internal olefin of Formula IV is (Z)-hex-3-ene; and the aliphatic olefin metathesis product of Formula I is (Z)-tetradec-11-en-1-yl acetate.

[0142] (Z)-Metathesis products from (E)-reaction partners and olefins The methods described herein are used to prepare aliphatic olefin metathesis products of Formula I from metathesis reaction partners and olefins, where the aliphatic olefin metathesis product is substantially in the Z configuration and the metathesis reaction partner and / or olefin comprises an isomer of the E configuration. In some embodiments, aliphatic olefin metathesis products comprising greater than 97% Z isomer are formed according to the methods described herein, where the metathesis reaction partner comprises 1% or more E isomer and the olefin comprises 0% to 15% or more E isomer.

[0143] Thus, in some embodiments, the present invention provides compounds of formula I: TIFF0007821747000040.tif16128. A method for synthesizing an aliphatic olefin metathesis product, comprising: reacting an aliphatic olefin metathesis product of Formula III: TIFF0007821747000041.tif16128 and an olefin metathesis reaction partner of formula IV: and an internal olefin of formula (I) in the presence of a Z-selective ruthenium catalyst or a Z-selective osmium catalyst, wherein R 1 is H and C 1~6 selected from the group consisting of alkyl; R 2 C 1~18 Alkyl and C 2~18 alkenyl; R 3 C 1~18 is alkyl; The subscript y is an integer ranging from 0 to 17; The subscript z is an integer ranging from 0 to 17; The aliphatic olefin metathesis product is at least 97% Z.

[0144] In some embodiments, Formula I: The method for synthesizing aliphatic olefin metathesis products of TIFF0007821747000043.tif16128 comprises preparing aliphatic olefin metathesis products of formula III: to form an olefin metathesis reaction partner of formula II: with an alkenol of formula (I); and To form an aliphatic olefin metathesis product, an olefin metathesis reaction partner and an aliphatic olefin metathesis reaction partner of Formula IV: and an internal olefin in the presence of a Z-selective ruthenium catalyst or a Z-selective osmium catalyst. wherein R 1 is H and C 1~6 selected from the group consisting of alkyl; R 2 is C 1~18 Alkyl and C 2~18 alkenyl; R 3 is C1~18 is alkyl; The subscript y is an integer ranging from 0 to 17; The subscript z is an integer ranging from 0 to 17; The aliphatic olefin metathesis product is at least 97% Z.

[0145] In some embodiments, Formula I: The method for synthesizing aliphatic olefin metathesis products of TIFF0007821747000047.tif16128 comprises preparing aliphatic olefin metathesis products of formula II: to form an alkenol of formula IIa: reducing the unsaturated aliphatic carboxyl derivative of TIFF0007821747000049.tif16128; Formula III: contacting an acylating agent with an alkenol to form an olefin metathesis reaction partner of formula (TIFF0007821747000050.tif16128); and To form an aliphatic olefin metathesis product, an olefin metathesis reaction partner and an aliphatic olefin metathesis reaction partner of Formula IV: and an internal olefin in the presence of a Z-selective ruthenium catalyst or a Z-selective osmium catalyst. wherein R 1 is H and C 1~6 selected from the group consisting of alkyl; R 2 is C 1~18 Alkyl and C 2~18 alkenyl; R 3 is C 1~18 is alkyl; R 4 is H and C 1~8 selected from the group consisting of alkyl; The subscript y is an integer ranging from 0 to 17; The subscript z is an integer ranging from 0 to 17; The aliphatic olefin metathesis product is at least 97% Z.

[0146] In some embodiments, the methods described herein are used to prepare aliphatic olefin metathesis products of Formula I, wherein the aliphatic olefin metathesis products are greater than 97% Z. In some embodiments, the aliphatic olefin metathesis products of Formula I are from about 97.1% Z to about 99.9% Z. In some embodiments, the aliphatic olefin metathesis product of Formula I is about 97.2% Z, 97.4% Z, 97.5% Z, 97.6% Z, 97.8% Z, 97.9% Z, 98.0% Z, 98.1% Z, 98.2% Z, 98.4% Z, 98.5% Z, 98.6% Z, 98.8% Z, 98.9% Z, 99.0% Z, 99.1% Z, 99.2% Z, 99.3% Z, 99.4% Z, 99.5% Z, 99.6% Z, 99.7% Z, 99.8% Z, or about 99.9% Z. In some embodiments, the aliphatic olefin metathesis product of Formula I is greater than 98% Z. In some embodiments, the aliphatic olefin metathesis product of Formula I is greater than 99% Z. In some embodiments, the aliphatic olefin metathesis product of Formula I is about 99.1% Z, 99.2% Z, 99.3% Z, 99.4% Z, 99.5% Z, 99.6% Z, 99.7% Z, 99.8% Z, about 99.9% Z, or about 100.0% Z.

[0147] Accordingly, the present invention provides methods for synthesizing aliphatic olefin metathesis products of Formula I described herein, wherein the aliphatic olefin metathesis products are (Z)-tetradec-9-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, (Z)-icos-15-en-1-yl acetate, (Z)-tridec-9-en-1-yl acetate, (Z)-pentadec-11-en-1-yl acetate, (Z)-heptadec-13-en-1-yl acetate, (Z)-nonadec-15-en-1-yl acetate, (Z)-dodec-9-en-1-yl acetate, (Z)-tetradec-11-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, (Z)-icosa-15-en-1-yl acetate, (Z)-tridec-9-en-1-yl acetate, (Z)-pentadec-11-en-1-yl acetate, (Z)-heptadec-13-en-1-yl acetate, (Z)-nonadec-15-en-1-yl acetate, (Z)-dodec-9-en-1-yl acetate, (Z)-tetradec-11-en-1-yl acetate, acetate, (Z)-hexadec-13-en-1-yl acetate, (Z)-octadec-15-en-1-yl acetate, or mixtures thereof, wherein the aliphatic olefin metathesis product is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0148] In some embodiments, the aliphatic olefin metathesis product comprises at least one member selected from the group consisting of (Z)-tetradec-9-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, and (Z)-icosa-15-en-1-yl acetate, wherein the aliphatic olefin metathesis product is at least 97% Z, greater than 98% Z, or greater than 99% Z. In some embodiments, the aliphatic olefin metathesis product comprises at least one member selected from the group consisting of (Z)-tridec-9-en-1-yl acetate, (Z)-pentadec-11-en-1-yl acetate, (Z)-heptadec-13-en-1-yl acetate, and (Z)-nonadec-15-en-1-yl acetate, wherein the aliphatic olefin metathesis product is at least 97% Z, greater than 98% Z, or greater than 99% Z. In some embodiments, the aliphatic olefin metathesis product comprises at least one member selected from the group consisting of (Z)-dodec-9-en-1-yl acetate, (Z)-tetradec-11-en-1-yl acetate, (Z)-hexadec-13-en-1-yl acetate, and (Z)-octadec-15-en-1-yl acetate, wherein the aliphatic olefin metathesis product is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0149] In some embodiments, the aliphatic olefin metathesis product is selected from the group consisting of (Z)-tetradec-9-en-1-yl acetate, (Z)-dodec-9-en-1-yl acetate, and (Z)-tetradec-11-en-1-yl acetate, wherein the aliphatic olefin metathesis product is at least 97% Z, greater than 98% Z, or greater than 99% Z. In some embodiments, the aliphatic olefin metathesis product is (Z)-tetradec-9-en-1-yl acetate, wherein the (Z)-tetradec-9-en-1-yl acetate is at least 97% Z, greater than 98% Z, or greater than 99% Z. In some embodiments, the aliphatic olefin metathesis product is (Z)-dodec-9-en-1-yl acetate, wherein the (Z)-dodec-9-en-1-yl acetate is at least 97% Z, greater than 98% Z, or greater than 99% Z. In some embodiments, the aliphatic olefin metathesis product is (Z)-tetradec-11-en-1-yl acetate, wherein the (Z)-tetradec-11-en-1-yl acetate is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0150] In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, wherein one or more of the unsaturated aliphatic carboxylic derivative of Formula IIa, the alkenol of Formula II, the olefin metathesis reaction partner of Formula III, and / or the olefin of Formula IV is at least 1% E. In some embodiments, one or more of the unsaturated aliphatic carboxylic derivative of Formula IIa, the alkenol of Formula II, the olefin metathesis reaction partner of Formula III, and / or the olefin of Formula IV is from about 1.5% E to about 50% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and one or more of the unsaturated aliphatic carboxylic derivative of Formula IIa, the alkenol of Formula II, the olefin metathesis reaction partner of Formula III, and / or the olefin of Formula IV is about 1.5% E, about 3.0% E, about 5.0% E, about 8.0% E, about 10% E, about 15% E, about 20% E, about 25% E, about 30% E, about 35% E, about 40% E, about 45% E, or about 50% E. In some embodiments, one or more of the unsaturated aliphatic carboxylic derivative of Formula IIa, the alkenol of Formula II, the olefin metathesis reaction partner of Formula III, and / or the olefin of Formula IV have about 1.5% E to about 45% E, about 3.0% E to about 40% E, about 5.0% E to about 35% E, about 8.0% E to about 30% E, about 10% E to about 25% E, or about 15% E to about 20% E. In some embodiments, the E:Z (trans:cis) ratio for one or more of the unsaturated aliphatic carboxylic derivative of Formula IIa, the alkenol of Formula II, the olefin metathesis reaction partner of Formula III, and / or the olefin of Formula IV is about 1:30, about 1:20, about 1:10, about 1:6, about 1:4, about 1:3, about 1:2.5, about 1:2, about 1:1.5, about 1:1.2, or about 1:1.

[0151] In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, wherein the olefin metathesis reaction partner of Formula III is at least 1% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner of Formula III is about 1.5% E to about 50% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner of Formula III is about 1.5% E, about 3.0% E, about 5.0% E, about 8.0% E, about 10% E, about 15% E, about 20% E, about 25% E, about 30% E, about 35% E, about 40% E, about 45% E, or about 50% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner of Formula III is from about 1.5% E to about 45% E, from about 3.0% E to about 40% E, from about 5.0% E to about 35% E, from about 8.0% E to about 30% E, from about 10% E to about 25% E, or from about 15% E to about 20% E. In some embodiments, the E:Z (trans:cis) ratio of the olefin metathesis reaction partners of Formula III is about 1:30, about 1:20, about 1:10, about 1:6, about 1:4, about 1:3, about 1:2.5, about 1:2, about 1:1.5, about 1:1.2, or about 1:1, and the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0152] Thus, in some embodiments, the aliphatic olefin metathesis product of Formula I prepared according to any of the methods described herein is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner of Formula III is selected from the group including octadec-9-en-1-yl acetate, icos-11-en-1-yl acetate, docos-13-en-1-yl acetate, tetracos-15-en-1-yl acetate, or mixtures thereof, wherein the olefin metathesis reaction partner is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partners consist of octadec-9-en-1-yl acetate and at least one member selected from the group consisting of icos-11-en-yl acetate, docos-13-en-1-yl acetate, and tetracos-15-en-1-yl acetate, wherein the olefin metathesis reaction partners are from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner is selected from the group consisting of octadec-9-en-1-yl acetate, icos-11-en-1-yl acetate, docos-13-en-1-yl acetate, and tetracos-15-en-1-yl acetate, wherein the olefin metathesis reaction partner is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E.

[0153] In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner of Formula III is octadec-9-en-1-yl acetate, wherein the octadec-9-en-1-yl acetate is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner is icos-11-en-1-yl acetate, wherein the icos-11-en-1-yl acetate is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner is docos-13-en-1-yl acetate, wherein the docos-13-en-1-yl acetate is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner is tetracos-15-en-1-yl acetate, wherein the tetracos-15-en-1-yl acetate is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E.

[0154] In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, wherein the olefin of Formula IV is at least 1% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin of Formula IV is about 1.5% E to about 50% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin of Formula IV is about 1.5% E, about 3.0% E, about 5.0% E, about 8.0% E, about 10% E, about 15% E, about 20% E, about 25% E, about 30% E, about 35% E, about 40% E, about 45% E, or about 50% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin of Formula IV is from about 1.5% E to about 45% E, from about 3.0% E to about 40% E, from about 5.0% E to about 35% E, from about 8.0% E to about 30% E, from about 10% E to about 25% E, or from about 15% E to about 20% E. In some embodiments, the E:Z (trans:cis) ratio of the olefin of Formula IV is about 1:30, about 1:20, about 1:10, about 1:6, about 1:4, about 1:3, about 1:2.5, about 1:2, about 1:1.5, about 1:1.2, or about 1:1, and the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0155] Thus, in some embodiments, the aliphatic olefin metathesis product of Formula I prepared according to any of the methods described herein is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin of Formula IV is selected from the group including hexadec-8-ene, tetradec-7-ene, dodec-6-ene, dec-5-ene, oct-4-ene, or hex-3-ene, wherein the olefin is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin is selected from the group consisting of hexadec-8-ene, tetradec-7-ene, dodec-6-ene, dec-5-ene, oct-4-ene, and hex-3-ene, wherein the olefin is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin is selected from the group consisting of tetradec-7-ene, dodec-6-ene, dec-5-ene, oct-4-ene, and hex-3-ene, wherein the olefin is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E.

[0156] In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin of Formula IV is selected from the group consisting of dodec-6-ene, dec-5-ene, oct-4-ene, and hex-3-ene, wherein the olefin is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin is selected from the group consisting of dec-5-ene, oct-4-ene, and hex-3-ene, wherein the olefin is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin is dec-5-ene, where the dec-5-ene is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin is oct-4-ene, where the oct-4-ene is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin is hex-3-ene, wherein the hex-3-ene is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E.

[0157] In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, wherein the alkenol of Formula II is at least 1% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol of Formula II is about 1.5% E to about 50% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol of Formula II is about 1.5% E, about 3.0% E, about 5.0% E, about 8.0% E, about 10% E, about 15% E, about 20% E, about 25% E, about 30% E, about 35% E, about 40% E, about 45% E, or about 50% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol of Formula II is from about 1.5% E to about 45% E, from about 3.0% E to about 40% E, from about 5.0% E to about 35% E, from about 8.0% E to about 30% E, from about 10% E to about 25% E, or from about 15% E to about 20% E. In some embodiments, the E:Z (trans:cis) ratio of the alkenol of Formula II is about 1:30, about 1:20, about 1:10, about 1:6, about 1:4, about 1:3, about 1:2.5, about 1:2, about 1:1.5, about 1:1.2, or about 1:1, and the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0158] Thus, in some embodiments, the aliphatic olefin metathesis product of Formula I prepared according to any of the methods described herein is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol of Formula II is selected from the group including octadec-9-en-1-ol, icos-11-en-1-ol, docos-13-en-1-ol, tetracos-15-en-ol, or mixtures thereof, wherein the alkenol is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol is selected from the group consisting of octadec-9-en-1-ol, eicos-11-en-1-ol, docos-13-en-1-ol, and tetracos-15-en-ol, wherein the alkenol is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E.

[0159] In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol of Formula II is octadec-9-en-1-ol, wherein the octadec-9-en-1-ol is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol is icos-11-en-1-ol, wherein the icos-11-en-1-ol is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol is docos-13-en-1-ol, wherein the docos-13-en-1-ol is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol is tetracos-15-en-ol, wherein the tetracos-15-en-ol is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E.

[0160] In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, wherein the unsaturated aliphatic carboxylic derivative of Formula IIa is at least 1% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated aliphatic carboxylic derivative of Formula IIa is about 1.5% E to about 50% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated aliphatic carboxylic derivative of Formula IIa is about 1.5% E, about 3.0% E, about 5.0% E, about 8.0% E, about 10% E, about 15% E, about 20% E, about 25% E, about 30% E, about 35% E, about 40% E, about 45% E, or about 50% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated aliphatic carboxylic derivative of Formula IIa is from about 1.5% E to about 45% E, from about 3.0% E to about 40% E, from about 5.0% E to about 35% E, from about 8.0% E to about 30% E, from about 10% E to about 25% E, or from about 15% E to about 20% E. In some embodiments, the E:Z (trans:cis) ratio of the unsaturated aliphatic carboxylic derivative of Formula IIa is about 1:30, about 1:20, about 1:10, about 1:6, about 1:4, about 1:3, about 1:2.5, about 1:2, about 1:1.5, about 1:1.2, or about 1:1, and the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0161] Thus, in some embodiments, the aliphatic olefin metathesis product of Formula I prepared according to any of the methods described herein is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid alkyl ester of Formula IIa is selected from the group consisting of methyl octadec-9-enoate, methyl icos-11-enoate, methyl docos-13-enoate, methyl tetracos-15-enoate, or mixtures thereof, wherein the unsaturated fatty acid alkyl ester is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid alkyl ester of Formula IIa consists of methyl octadec-9-enoate and at least one member selected from the group consisting of methyl icos-11-enoate, methyl docos-13-enoate, and methyl tetracos-15-enoate, wherein the unsaturated fatty acid alkyl ester is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid alkyl ester is selected from the group consisting of methyl octadec-9-enoate, methyl icos-11-enoate, methyl docos-13-enoate, and methyl tetracos-15-enoate, wherein the unsaturated fatty acid alkyl ester is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E.

[0162] In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid alkyl ester of Formula IIa is methyl octadec-9-enoate, wherein the methyl octadec-9-enoate is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid alkyl ester is methyl icos-11-enoate, wherein the methyl icos-11-enoate is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid alkyl ester is methyl docos-13-enoate, wherein the methyl docos-13-enoate is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid alkyl ester is methyl tetracos-15-enoate, wherein the methyl tetracos-15-enoate is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E.

[0163] Thus, in some embodiments, the aliphatic olefin metathesis product of Formula I prepared according to any of the methods described herein is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid of Formula IIa is selected from the group including octadec-9-enoic acid, eicosa-11-enoic acid, docos-13-enoic acid, tetracos-15-enoic acid, or mixtures thereof, wherein the unsaturated fatty acid is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid of Formula IIa consists of octadec-9-enoic acid and at least one member selected from the group consisting of eicosa-11-enoic acid, docos-13-enoic acid, and tetracos-15-enoic acid, wherein the unsaturated fatty acid is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid of Formula IIa is selected from the group consisting of octadec-9-enoic acid, eicosa-11-enoic acid, docos-13-enoic acid, and tetracos-15-enoic acid, wherein the unsaturated fatty acid is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E.

[0164] In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid of Formula IIa is octadec-9-enoic acid, wherein the octadec-9-enoic acid is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid is eicos-11-enoic acid, wherein the eicos-11-enoic acid is from about 8.0% to about 30% E, from about 10% to about 25% E, or from about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid is docos-13-enoic acid, wherein the docos-13-enoic acid is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid is tetracos-15-enoic acid, wherein the tetracos-15-enoic acid is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0165] metathesis catalyst In some embodiments, the metathesis catalyst used in the above method for synthesizing an aliphatic olefin metathesis product has the structure of Formula V: TIFF0007821747000052.tif38128, a Z-selective metathesis catalyst having During the ceremony, M is selected from the group consisting of ruthenium and osmium; X and Y are independently selected from the group consisting of S and O; Z is selected from the group consisting of O and S(=O); each subscript m and subscript n is an integer independently selected from 0, 1, 2, 3, and 4; Each R aare independently selected from the group consisting of halogen, C1-C6 alkyl, alkoxy, aryl, and heteroaryl; or one R a is the adjacent R a together to form an unsubstituted or substituted bicyclic or unsubstituted or substituted polycyclic ring; Each R b are independently selected from the group consisting of halogen, C1-C6 alkyl, alkoxy, aryl, and heteroaryl; or one R b is the adjacent R b together to form an unsubstituted or substituted bicyclic or unsubstituted or substituted polycyclic ring; R c is selected from the group consisting of hydrogen and C1-C6 alkyl; Each R d , R e , R f , and R g is independently selected from the group consisting of hydrogen and C1-C6 alkyl; R 12 and R 13 is independently selected from the group consisting of 2,4,6-tri-isopropylphenyl, 2,6-di-isopropylphenyl, 2,6-di-adamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl; Each R 14 are independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl, and phenyl; R 15 is selected from the group consisting of hydrogen, halogen, and C1-C6 alkyl, or R 15 and one R 14 come together to form a bond.

[0166] In some embodiments, the Z-selective metathesis catalyst has the structure of formula V, wherein M is ruthenium; X and Y are S; Z is selected from the group consisting of O and S(=O); the subscript m is 2; the subscript n is 0; and each Ra is independently selected from the group consisting of halogen, C1-C6 alkyl, and aryl; R c is hydrogen; each R d , R e , R f , and R g is hydrogen; R 12 and R 13 is independently selected from the group consisting of 2,4,6-tri-isopropylphenyl, 2,6-di-isopropylphenyl, 2,6-di-adamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl; each R 14 is independently selected from the group consisting of methyl, isopropyl, benzyl, and tert-butyl; R 15 is selected from the group consisting of hydrogen, halogen, and C1-C6 alkyl, or R 15 and one R 14 come together to form a bond.

[0167] In some embodiments, the metathesis catalyst used in the method for synthesizing the aliphatic olefin metathesis product of formula I is selected from the group consisting of: TIFF0007821747000053.tif48136.

[0168] In some embodiments, the catalyst is The file is TIFF0007821747000054.tif36128.

[0169] Other catalysts useful in the methods provided herein include, but are not limited to, those described in WO 2018 / 191373, WO 2018 / 038928, WO 2018 / 034931, WO 2017 / 100585, and U.S. Patent Nos. 10,857,350; 10,774,035; 9,938,253; and 6,921,735, all of which are incorporated herein by reference in their entirety. Catalysts described in Zachmann et al. (Chem. Eur. J. 2021, 27, 7663-7666) and Grudzien et al. (Chem. Eur. J. 2014, 20, 2819-2828) may also be used.

[0170] Metathesis reaction conditions Typically, the Z-selective metathesis catalyst is provided in a substoichiometric (e.g., catalytic) amount in the reaction mixture. In certain embodiments, the amount ranges from about 0.001 to about 50 mol % (0.1 to 5000 ppm) relative to the limiting reagent of the chemical reaction, depending on which reagent is in stoichiometric excess. In some embodiments, the catalyst is present at about 40 mol % or less relative to the limiting reagent. In some embodiments, the catalyst is present at about 30 mol % or less relative to the limiting reagent. In some embodiments, the catalyst is present at less than about 20 mol %, less than about 10 mol %, less than about 5 mol %, less than about 2.5 mol %, less than about 1 mol %, less than about 0.5 mol %, less than about 0.1 mol %, less than about 0.015 mol %, less than about 0.01 mol %, less than about 0.0015 mol %, or less relative to the limiting reagent. In some embodiments, the catalyst is present in a range of about 2.5 mol % to about 5 mol % relative to the limiting reagent. In some embodiments, the reaction mixture contains about 0.01-0.1 mol % of catalyst (e.g., 0.5 mol % of catalyst). If the molecular formula of the catalyst complex contains more than one metal, the amount of catalyst complex used in the reaction can be adjusted accordingly.

[0171] Catalyst loading can also be expressed in terms of the olefin content of the reaction mixture. For example, the metathesis catalyst can be present in an amount ranging from about 0.1 ppm to about 500 ppm, based on the total number of double bonds in the reaction mixture. The reaction mixture can contain 0.1 to 100 ppm, or about 1 to 100 ppm, or about 1 to 75 ppm, or about 1 to 50 ppm, or about 3 to 50 ppm of catalyst per double bond.

[0172] In some cases, the methods described herein can be carried out in the absence of a solvent (e.g., neat). In some cases, the methods can include the use of one or more solvents. Examples of solvents that may be suitable for use in the present invention include, but are not limited to, benzene, p-cresol, toluene, xylene, diethyl ether, glycol, diethyl ether, petroleum ether, hexane, cyclohexane, pentane, methylene chloride, chloroform, carbon tetrachloride, dioxane, tetrahydrofuran (THF), dimethyl sulfoxide, dimethylformamide, hexamethylphosphoric triamide, ethyl acetate, pyridine, triethylamine, picoline, and the like, and mixtures thereof. In some embodiments, the solvent is selected from benzene, toluene, pentane, methylene chloride, and THF. In certain embodiments, the solvent is benzene.

[0173] In some embodiments, the method is carried out under reduced pressure. This can be advantageous when volatile by-products, such as ethylene, may be produced during the metathesis reaction. For example, removal of the ethylene by-product from the reaction vessel can advantageously shift the equilibrium of the metathesis reaction toward the formation of the desired product. In some embodiments, the method is carried out at a pressure less than about 760 torr. In some embodiments, the method is carried out at a pressure less than about 700 torr. In some embodiments, the method is carried out at a pressure less than about 650 torr. In some embodiments, the method is carried out at a pressure less than about 600 torr. In some embodiments, the method is carried out at a pressure less than about 550 torr. In some embodiments, the method is carried out at a pressure less than about 500 torr. In some embodiments, the method is carried out at a pressure less than about 450 torr. In some embodiments, the method is carried out at a pressure less than about 400 torr. In some embodiments, the method is carried out at a pressure less than about 350 torr. In some embodiments, the method is carried out at a pressure less than about 300 torr. In some embodiments, the method is carried out at a pressure of less than about 250 torr. In some embodiments, the method is carried out at a pressure of less than about 200 torr. In some embodiments, the method is carried out at a pressure of less than about 150 torr. In some embodiments, the method is carried out at a pressure of less than about 100 torr. In some embodiments, the method is carried out at a pressure of less than about 90 torr. In some embodiments, the method is carried out at a pressure of less than about 80 torr. In some embodiments, the method is carried out at a pressure of less than about 70 torr. In some embodiments, the method is carried out at a pressure of less than about 60 torr. In some embodiments, the method is carried out at a pressure of less than about 50 torr. In some embodiments, the method is carried out at a pressure of less than about 40 torr. In some embodiments, the method is carried out at a pressure of less than about 30 torr. In some embodiments, the method is carried out at a pressure of less than about 20 torr. In some embodiments, the method is carried out at a pressure of about 20 torr.

[0174] In some embodiments, the method is carried out at a pressure of about 19 torr. In some embodiments, the method is carried out at a pressure of about 18 torr. In some embodiments, the method is carried out at a pressure of about 17 torr. In some embodiments, the method is carried out at a pressure of about 16 torr. In some embodiments, the method is carried out at a pressure of about 15 torr. In some embodiments, the method is carried out at a pressure of about 14 torr. In some embodiments, the method is carried out at a pressure of about 13 torr. In some embodiments, the method is carried out at a pressure of about 12 torr. In some embodiments, the method is carried out at a pressure of about 11 torr. In some embodiments, the method is carried out at a pressure of about 10 torr. In some embodiments, the method is carried out at a pressure of about 10 torr. In some embodiments, the method is carried out at a pressure of about 9 torr. In some embodiments, the method is carried out at a pressure of about 8 torr. In some embodiments, the method is carried out at a pressure of about 7 torr. In some embodiments, the method is carried out at a pressure of about 6 torr. In some embodiments, the method is carried out at a pressure of about 5 torr. In some embodiments, the method is carried out at a pressure of about 4 torr. In some embodiments, the method is carried out at a pressure of about 3 torr. In some embodiments, the method is carried out at a pressure of about 2 torr. In some embodiments, the method is carried out at a pressure of about 1 torr. In some embodiments, the method is carried out at a pressure of less than about 1 torr.

[0175] In some embodiments, the two metathesis reactants (i.e., the metathesis reaction partner and the olefin) are present in equimolar amounts. In some embodiments, the two metathesis reactants are not present in equimolar amounts. In particular embodiments, the two reactants are present in a molar ratio of about 20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, or 1:20. In certain embodiments, the two reactants are present in a molar ratio of about 10:1. In certain embodiments, the two reactants are present in a molar ratio of about 7:1. In certain embodiments, the two reactants are present in a molar ratio of about 5:1. In certain embodiments, the two reactants are present in a molar ratio of about 2:1. In certain embodiments, the two reactants are present in a molar ratio of about 1:10. In certain embodiments, the two reactants are present in a molar ratio of about 1:7. In certain embodiments, the two reactants are present in a molar ratio of about 1:5. In certain embodiments, the two reactants are present in a molar ratio of 1:2.

[0176] In some embodiments, 1 molar equivalent of olefin is contacted with 1 molar equivalent of olefin metathesis reaction partner. In some embodiments, about 1.5, 2, 2.5, or 3 molar equivalents of olefin are contacted with 1 molar equivalent of metathesis reaction partner. In some embodiments, about 1.5 molar equivalents of olefin are contacted with 1 molar equivalent of metathesis reaction partner.

[0177] Generally, reactions with many of the Z-selective metathesis catalysts disclosed herein produce yields of greater than 15%, e.g., greater than 50%, greater than 75%, or greater than 90%. Furthermore, reactants and products are selected to produce a boiling point difference of at least 5°C, e.g., greater than 20°C or greater than 40°C. Furthermore, because the use of Z-selective metathesis catalysts results in product formation much more rapidly than by-products, it may be desirable to carry out these reactions as quickly as possible. In particular, reactions are carried out in less than about 24 hours, e.g., less than 12 hours, or less than 8 hours, or less than 4 hours. Advantageously, the methods of the present invention produce metathesis products on scales ranging from a few milligrams to hundreds of kilograms or more. For example, the methods can be carried out using about 1 to 10 grams of an internal olefin of Formula IV, or about 10 to 100 grams of an internal olefin of Formula IV, or about 100 to 500 grams of an internal olefin of Formula IV, or about 500 to 1000 grams of an internal olefin of Formula IV. The method can be carried out using at least 1, 5, 10, 25, 50, 100, or 1,000 kilograms of starting material. The metathesis reaction can be carried out using a metathesis reactor, such as those described in WO 2011 / 046872, which can be operated in combination with one or more downstream separation devices to separate and / or recycle specific product or by-product streams (e.g., olefin streams, C2-C3 compounds streams, or C3-C5 compounds streams). The metathesis reactor and separation device can be operated in combination with one or more adsorbent beds to facilitate separation of the metathesized product from the catalyst and cleaning and drying of the equipment for purification of the desired product. Reduction, acylation, and metathesis reactions can be carried out to obtain products on a metric ton scale.

[0178] Those skilled in the art will recognize that time, temperature, and solvent can be interdependent, and that changing one may require changing the others to prepare the metathesis product in the methods of the present invention. The metathesis step can proceed at a variety of temperatures and times. Generally, the reaction in the methods of the present invention is carried out using reaction times ranging from a few minutes to several days. For example, reaction times of about 12 hours to about 7 days can be used. In some embodiments, reaction times of 1 to 5 days can be used. In some embodiments, reaction times of about 10 minutes to about 10 hours can be used. Generally, the reaction in the methods of the present invention is carried out at a temperature of about 0°C to about 200°C. For example, the reaction can be carried out at 15 to 100°C. In some embodiments, the reaction can be carried out at 20 to 80°C (e.g., 20 to 60°C). In some embodiments, the reaction can be carried out at 100 to 150°C.

[0179] The olefins, metathesis reaction partners, olefin starting materials, olefin-containing reactants, and aliphatic olefin derivatives (e.g., alkenols, unsaturated aliphatic alcohol acetates, unsaturated aliphatic ester acetates, olefin metathesis reaction partners, aliphatic olefin metathesis products, unsaturated aliphatic aldehydes, unsaturated aliphatic carboxylic derivatives, metathesis products, etc.) and other materials used in the methods of the invention can be obtained from any suitable source. In some embodiments, the metathesis reaction partners used in the methods of the invention are obtained from natural oils and / or derivatives thereof (e.g., the unsaturated fatty acids described above).

[0180] In some embodiments, materials to be reacted during a metathesis reaction, including materials derived from natural oils, contain one or more contaminants that can adversely affect the performance of the metathesis catalyst. These contaminants are sometimes referred to as "catalyst poisons" or "catalyst-poisoning contaminants." The levels of the contaminants can be reduced according to the methods described herein. In some embodiments, the material contains multiple contaminants, and the method comprises reducing the levels of two or more contaminants. In some embodiments, the material contains multiple contaminants, and the method comprises reducing the levels of three or more contaminants. In some embodiments, the material contains multiple contaminants, and the method comprises reducing the levels of four or more contaminants. In some embodiments, the material contains multiple contaminants, and the method comprises reducing the levels of five or more contaminants.

[0181] Representative contaminants include, but are not limited to, water, peroxides, peroxide decomposition products, hydroperoxides, protic materials, polar materials, Lewis base catalyst poisons, and the like, and combinations thereof. It should be understood that some contaminants may be properly classified into multiple categories (e.g., alcohols may be considered both protic and polar materials). Furthermore, it should be understood that different catalysts may exhibit different susceptibilities to particular contaminants and contaminants that adversely affect the performance of one catalyst.

[0182] Representative protic materials that may be found as contaminants in substrates to be reacted during metathesis reactions include, but are not limited to, materials having a hydrogen atom bonded to oxygen (e.g., carboxylic acids, alcohols, etc.) and / or materials having a hydrogen atom bonded to nitrogen (e.g., primary amines, secondary amines, etc.). In some embodiments, particularly, but not exclusively, in natural oil substrates, the protic material contaminants may include carboxylic acid functionality, hydroxyl functionality, or a combination thereof. In some embodiments, the protic material is selected from the group consisting of free fatty acids, hydroxyl-containing materials, MAG, DAG, etc., and combinations thereof.

[0183] Representative polar materials that may be found as contaminants in the substrate to be reacted during metathesis reactions include, but are not limited to, heteroatom-containing materials such as oxygenates, hi some embodiments, the polar material is selected from the group consisting of alcohols, aldehydes, ethers, and the like, and combinations thereof.

[0184] Representative Lewis basic catalyst poisons that may be found as contaminants in the substrate to be reacted during metathesis reactions include, but are not limited to, heteroatom-containing materials. In some embodiments, the Lewis basic catalyst poison is selected from the group consisting of N-containing materials, P-containing materials, S-containing materials, etc., and combinations thereof.

[0185] The contaminant-containing reaction material can be treated with one or more modifiers to mitigate the potentially harmful effects of one or more contaminants. Modifiers that can be used in the process of the present invention (individually or in combination, sequentially or simultaneously) include heat, molecular sieves, alumina (aluminum oxide), silica gel, montmorillonite clay, fuller's earth, bleaching earth, diatomaceous earth, zeolites, kaolin, activated metals (e.g., Cu, Mg, etc.), acid anhydrides (e.g., acetic anhydride, etc.), activated carbon (i.e., activated charcoal), soda ash, metal hydrides (e.g., alkaline earth metal hydrides such as CaH), metal sulfates (e.g., alkaline earth metal sulfates such as calcium sulfate, magnesium sulfate, etc.; alkali metal sulfates such as potassium sulfate, sodium sulfate, etc.); and other metal sulfates such as aluminum sulfate, potassium magnesium sulfate, etc.), metal halides (e.g., alkaline earth metal halides such as potassium chloride), metal carbonates (e.g., calcium carbonate, sodium carbonate, etc.), metal silicates (e.g., magnesium silicate, etc.), phosphorus pentoxide, metal aluminum hydrides (e.g., alkali metal aluminum hydrides such as LiAlH4, NaAlH4, etc.), alkyl aluminum hydrides (e.g., DIBALH), metal borohydrides (e.g., alkali metal borohydrides such as LiBH4, NaBH4, etc.), organometallic reagents (e.g., Grignard reagents; organolithium reagents such as n-butyllithium, t-butyllithium, sec-butyllithium, etc.; trialkylaluminums such as triethylaluminum, tributylaluminum, triisobutylaluminum, triisopropylaluminum, trioctylaluminum, etc.), metal amides (e.g., lithium diisopropylamide and metal bis(trimethylsilyl)amides such as KHMDS), palladium on carbon (Pd / C) catalysts, and combinations thereof.

[0186] In some embodiments, the modulating agent is a metal alkyl compound. In some embodiments, the metal M can be lithium, sodium, potassium, magnesium, calcium, zinc, cadmium, aluminum, or gallium. Examples of suitable alkyl groups R include, but are not limited to, methyl, ethyl, butyl, hexyl, decyl, tetradecyl, and eicosyl (i.e., icosyl). Examples of metal alkyl compounds include Mg(CH), Mg(C,H), Mg(C,H)(C,H), Mg(C,H), Mg(C,H). 13 )2, Mg(C 12 H 25 )2, Zn(CH3)2, Zn(C2H5)2, Zn(C4H9)2, Zn(C4H9)(C8H 17 ), Zn(CH 13 )2, Zn(C6H3)2, Al(C2H5)3, Al(CH3)3, Al(n-C4H9)3, Al(C8H 17 )3, Al(iso-C4H9)3, Al(C 12 H 25 ) 3, and combinations thereof. Metal alkyl compounds also include substances having one or more halogen or hydride groups, such as ethylaluminum dichloride, diethylaluminum chloride, diethylaluminum hydride, Grignard reagents, diisobutylaluminum hydride, and the like.

[0187] In some embodiments, treating a metathesis reaction material (e.g., a natural oil or natural oil derivative) can include contacting the reaction material with a metal alkyl compound and simultaneously or separately contacting the reaction material with a hydride-containing compound. In some embodiments, when the reaction material is simultaneously contacted with a metal alkyl compound and a hydride-containing compound, the hydride-containing compound can be included in the metal alkyl compound. For example, in some cases, a specific concentration of the hydride-containing compound can be formed depending on the process used to make a particular metal alkyl compound, such as a trialkylaluminum compound. However, in other embodiments, the metal alkyl compound can be combined with one or more hydride-containing compounds. Alternatively, in some embodiments, the metathesis reaction material can be treated with a hydride-containing compound in a separate reaction step, which can occur before, after, or both before and after treating the reaction material with the metal alkyl compound.

[0188] Any suitable hydride-containing compound can be used. In some embodiments, the hydride-containing compound is selected from the group consisting of metal aluminum hydrides (e.g., alkali metal aluminum hydrides such as LiAIH4, NaAlH4, etc.), alkyl aluminum hydrides (e.g., DIBALH), and combinations thereof. In some embodiments, the hydride-containing compound is an alkyl aluminum hydride such as DIBALH.

[0189] In some embodiments, contacting the metathesis reaction material with the hydride-containing compound occurs in the same step as contacting the reaction material with the metal alkyl compound. In some embodiments, the weight-to-weight ratio of the metal alkyl compound to the hydride-containing compound in the treatment composition is from 2:1, or from 5:1, or from 10:1, or from 15:1, or from 20:1 to 1000:1. In some embodiments, the weight-to-weight ratio of the metal alkyl compound to the hydride-containing compound in the treatment composition is at least 2:1, or at least 5:1, or at least 10:1, or at least 15:1, or at least 20:1.

[0190] In certain cases, the effectiveness of the Z-selective metathesis catalyst can be improved (e.g., the turnover rate can be increased or the total catalyst loading can be reduced) by slowly adding the catalyst to the substrate. Slow addition can reduce the total catalyst loading by at least 10%, at least 20%, or at least 30% to achieve the same turnover rate as a single full batch loading. Slowly adding the total catalyst loading can include adding fractional catalyst loadings to the reaction material at an average rate of about 10 ppm by weight catalyst per hour (ppmwt / hr), 5 ppmwt / hr, 1 ppmwt / hr, 0.5 ppmwt / hr, 0.1 ppmwt / hr, 0.05 ppmwt / hr, or 0.01 ppmwt / hr. In some embodiments, the catalyst is added slowly at a rate of about 0.01-10 ppmwt / hr, 0.05-5 ppmwt / hr, or 0.1-1 ppmwt / hr. The slow addition of catalyst can be carried out in batch additions at frequencies of every 5 minutes, 15 minutes, 30 minutes, hourly, 2 hours, 4 hours, 12 hours, or daily. In other embodiments, the slow addition is carried out in a continuous addition process.

[0191] In some embodiments, an internal olefin (Z5-decene) and a metathesis reaction partner (e.g., oleyl acetate) are combined in a ratio ranging from 2:1 to 10:1 (e.g., 5:1) and treated with an aluminum reagent (e.g., 1 wt. % magnesium aluminum isopropoxide), followed by the addition of a metathesis catalyst (e.g., ruthenium catalyst 3 described below) at a loading of 1 to 100 ppm (e.g., 3 to 50) per double bond.

[0192] Preparation of internal olefins In some embodiments, the synthesis of an aliphatic olefin metathesis product comprises contacting a terminal olefin with a metathesis catalyst to form an internal olefin. In some embodiments, the internal olefin is represented by Formula VIa: TIFF0007821747000055.tif12128 compound; The terminal olefin is represented by formula IVb: The compound is TIFF0007821747000056.tif10128.

[0193] In some embodiments, the internal olefin is prepared using a Z-selective ruthenium catalyst or a Z-selective tungsten catalyst. In some embodiments, the internal olefin has the structure of Formula XI: prepared using a metathesis catalyst with TIFF0007821747000057.tif26128, During the ceremony, M is tungsten; R 206a is aryl, heteroaryl, alkyl, or cycloalkyl, each of which may be substituted; R 210a is pyrrolyl, imidazolyl, indolyl, pyrazolyl, azaindolyl, or indazolyl, each of which may be substituted; R 211a is optionally substituted aryl; R 208a is a hydrogen atom, alkyl, or alkoxy; R 207b is a hydrogen atom, -O-(C 1~6 alkyl), -CH2-O-(C 1~6 alkyl), heteroalkoxy, or -N(C 1~6 alkyl)2; R 207c and R 207d are independently hydrogen atoms, C 1~6 Alkyl, C 1~6 It is alkoxy, a halogen atom, -NO2, an amide, or a sulfonamide.

[0194] In some embodiments, R 210a is pyrrolyl, imidazolyl, pyrazolyl, azaindolyl, or indazolyl, each of which may be substituted; R 208a is a hydrogen atom. 206ais phenyl, 2,6-dichlorophenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2-trifluoromethylphenyl, pentafluorophenyl, tert-butyl, or 1-adamantyl. 207b is methoxy and R 207c is hydrogen and R 207d is hydrogen. In some embodiments, R 206a teeth TIFF0007821747000058.tif28128.

[0195] In some embodiments, the internal olefin has the structure of Formula XII: prepared using a metathesis catalyst with TIFF0007821747000059.tif47128, During the ceremony, M 300 is ruthenium; L 301 has the following structure: TIFF0007821747000060.tif19128, During the ceremony, Q 300 is selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene, where two or more substituents on adjacent atoms in Q may be linked to form an additional ring structure; R 303 and R 304 is independently selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; Q 301 is M 300 and R 303 is a bond between a carbon atom of R 305 , R 306 , R 307 , and R 308are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate; 305 , R 306 , R 307 , and R 308 any combination of may be linked to form one or more cyclic groups; X 301 is selected from the group consisting of halide, nitrate, alkyl, aryl, alkoxy, alkylcarboxylate, aryloxy, alkoxycarbonyl, aryloxycarbonyl, arylcarboxylate, acyl, acyloxy, alkylsulfonato, arylsulfonato, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, and arylsulfinyl; Y 300 is a heteroatom selected from the group consisting of N, O, S, and P; Y 300 If is O or S, then the subscript q is 1 and Y 300 If is N or P, then the subscript q is 2; Z 300is selected from hydrogen, alkyl, aryl, functionalized alkyl, or functionalized aryl, where the functional groups are independently selected from the group consisting of alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl, and trimethylsilyl.

[0196] "Hydrocarbyl" refers to monovalent hydrocarbyl groups, such as alkyl, alkenyl, aryl, etc., containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, and most preferably 1 to about 12 carbon atoms, including straight-chain, branched, cyclic, saturated, and unsaturated varieties. "Hydrocarbylene" refers to divalent hydrocarbyl moieties containing 1 to about 30 carbon atoms.

[0197] In some embodiments, Q 300 is a hydrocarbylene group (e.g., ethylene). In some embodiments, the ligand L 301 is a 1,3-disubstituted 4,5-dihydroimidazol-2-ylidene moiety. 303 is an adamantyl group or a substituted adamantyl group, or a substituted C 3~12 In some embodiments, R is a cycloalkyl group. 304 is a disubstituted aryl group (e.g., a phenyl group substituted at both ortho ring positions with, for example, isopropyl groups) or a trisubstituted aryl group (e.g., a phenyl group substituted at both ortho and para ring positions with, for example, methyl groups).

[0198] In some embodiments, R 305 , R 306 , R 307 , and R 308 is hydrogen. In some embodiments, Y 300 is O. In some embodiments, Z 300is alkyl (e.g., isopropyl). In some embodiments, X 301 is nitrate.

[0199] The metathesis reaction for the preparation of internal olefins (e.g., Z5-decene) from terminal olefins (e.g., 1-hexene) can be carried out as described above for the preparation of acylated alkenol metathesis products and alkenal acetal metathesis products. In some embodiments, a terminal olefin (e.g., 1-hexene) of Formula IVb is reacted with a ruthenium catalyst shown below: Combine with TIFF0007821747000061.tif34128.

[0200] In some embodiments, the catalyst is present in an amount ranging from about 1 ppm to about 50 ppm (e.g., 3-50 ppm or 5-10 ppm) based on the total number of double bonds in the reaction mixture. In some embodiments, the reaction is carried out at a temperature ranging from about 20° C. to about 60° C. (e.g., 50° C.) for 1 to 8 hours or more. The reaction may be carried out neat, in the absence of an additional solvent.

[0201] Compositions and Uses Thereof In some embodiments, the aliphatic olefin metathesis product prepared according to the methods described herein is a pheromone. Thus, the pheromone prepared herein can be formulated for use as an insect control composition. The pheromone composition may include a carrier and / or may be contained in a dispenser. The carrier may be, but is not limited to, an inert liquid or solid.

[0202] Examples of solid carriers include, but are not limited to, fillers such as kaolin, bentonite, dolomite, calcium carbonate, talc, powdered magnesia, fuller's earth, wax, gypsum, diatomaceous earth, rubber, plastic, silica, and china clay.Examples of liquid carriers include, but are not limited to, water; alcohols such as ethanol, butanol, or glycol, and their ethers or esters such as methyl glycol acetate; ketones such as acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, or isophorone; alkanes such as hexane, pentane, or heptane; aromatic hydrocarbons such as xylene or alkylnaphthalene; mineral oil or vegetable oil; aliphatic chlorinated hydrocarbons such as trichloroethane or methylene chloride; aromatic chlorinated hydrocarbons such as chlorobenzene; water-soluble or strong polar solvents such as dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone; liquefied gas; and their mixtures.Food or feeding stimulants can also be added to carriers.

[0203] Pheromone compositions can be formulated to be released slowly into the atmosphere and / or protected from degradation after release. For example, pheromone compositions can be contained in carriers such as microcapsules, biodegradable flakes, and paraffin wax-based matrices.

[0204] The pheromone composition may contain other pheromones or attractants, provided that the other compounds do not substantially interfere with the activity of the composition. The pheromone composition may also contain an insecticide. Examples of suitable insecticides include, but are not limited to, buprofezin, pyriproxyfen, flonicamid, acetamiprid, dinotefuran, clothianidin, acephate, malathion, quinolphos, chloropyriphos, profenofos, bendiocarb, bifenthrin, chlorpyrifos, cyfluthrin, diazinon, pyrethrum, fenpropathrin, kinoprene, insecticidal soaps or oils, and mixtures thereof.

[0205] The pheromone composition can be used in combination with a dispenser for release of the composition in a particular environment. Any suitable dispenser known in the art can be used. Examples of such dispensers include, but are not limited to, bubble caps containing a reservoir with a permeable barrier through which the pheromone is slowly released, pads, beads, tubes, rods, spirals, or balls made of rubber, plastic, leather, cotton, absorbent cotton, wood, or wood products, which are impregnated with the pheromone composition. For example, polyvinyl chloride laminates, pellets, granules, ropes or spirals from which the pheromone composition evaporates, or rubber septa. One skilled in the art will be able to select a carrier and / or dispenser suitable for the desired mode of application, storage, transportation, or handling.

[0206] Various pheromones, such as (Z)-tetradec-9-en-1-yl acetate, (Z)-dodec-9-en-1-yl acetate, and (Z)-tetradec-11-en-1-yl acetate, can be prepared according to the methods of the invention and formulated as described above. For example, the methods of the invention can be used to prepare the (Z)-tetradec-9-en-1-yl acetate sex pheromone of the fall armyworm (Spodoptera frugiperda). The fall armyworm sex pheromone can be used in combination with a pheromone sustained-release device having a polymer container containing a mixture of the fall armyworm sex pheromone and a fatty acid ester (such as sebacate, laurate, palmitate, stearate, or arachidate) or an aliphatic alcohol (such as undecanol, dodecanol, tridecanol, tridecenol, tetradecanol, tetradecenol, tetradecadienol, pentadecanol, pentadecenol, hexadecanol, hexadecenol, hexadecadienol, octadecenol, and octadecadienol). The polymer container can be a tube, ampoule, or bag made of polyolefin or an olefin-containing copolymer. Sex pheromones of other pests, such as Helicoverpa armigera, Grapholita molesta, and Tortricidae, can be used in this type of pheromone sustained-release device. Typically, the sex pheromone contains one or more aliphatic acetate ester compounds having 10 to 16 carbon atoms (e.g., decyl acetate, decenyl acetate, decadienyl acetate, undecyl acetate, undecenyl acetate, dodecyl acetate, dodecenyl acetate, dodecadienyl acetate, tridecyl acetate, tridecenyl acetate, tridecadienyl acetate, tetradecyl acetate, tetradecenyl acetate, tetradecadienyl acetate, etc.) and / or one or more aliphatic aldehyde compounds having 10 to 16 carbon atoms (e.g., 7-hexadecenal, 11-hexadecenal, 13-octadecenal, etc.).

[0207] The pheromones prepared according to the methods of the present invention and compositions containing the pheromones can be used to control insect behavior and / or growth in various environments. For example, the pheromones can be used to attract or repel male or female insects to a specific target area. The pheromones can be used to lure insects away from vulnerable crop areas. The pheromones can also be used to attract insects as part of a strategy for, for example, insect monitoring, mass trapping, luring / attracting and killing, or mating disruption.

[0208] Mass trapping involves placing a high density of traps in a protected crop so that a high percentage of insects are removed before they cause damage to the crop. The lure / attract-and-kill technique is similar, except that insects are subjected to a killing agent when attracted to the bait. If the killing agent is an insecticide, the dispenser may contain a bait or feeding stimulant that induces the insects to ingest an effective amount of the insecticide.

[0209] Those skilled in the art will recognize that a variety of different traps are possible. Suitable examples of such traps include water traps, sticky traps, and one-way traps. There are many types of sticky traps. One example of a sticky trap has a cardboard structure with a triangular or wedge-shaped cross section, the inside of which is coated with a non-drying sticky substance. Insects are trapped by contacting the sticky surface. A water trap includes a dish of water and detergent used to capture insects. The detergent breaks the surface tension of the water, causing insects attracted to the dish to drown in the water. A one-way trap encourages insects to enter the trap but prevents them from exiting. The traps of the present invention may be brightly colored to add an attractiveness to insects.

[0210] The traps are positioned in areas where insects enter (or may enter). Typically, the traps are placed on or near trees or large plants, and pheromones attract insects to the trap, where they are captured, immobilized, and / or may be killed within the trap, for example, by a killing agent present in the trap.

[0211] Pheromones prepared according to the methods of the present invention can also be used to disrupt mating. Mating disruption strategies include confusion, trail blocking, and trail mistracking. Constant exposure of insects to high concentrations of pheromones can prevent male insects from responding to normal levels of hormones released by female insects. Trail blocking uses pheromones to disrupt the pheromone trails released by female insects. Trail mistracking is achieved by placing numerous spots of pheromone in high concentrations, presenting male insects with many false trails to follow. When released in sufficiently high amounts, male insects are unable to find the natural source of sex pheromones (female insects), and therefore mating cannot occur.

[0212] Insect populations can be surveyed or monitored by counting the number of insects in a target area (e.g., the number of insects caught in a trap). Inspections by horticulturists can provide information about the life stage of the population. Knowing where insects are present, how many insects are present, and the insect life stage allows for informed decisions to be made regarding where and when insecticides or other treatments are permitted. For example, the detection of large insect populations may necessitate the use of methods for insect removal. Early warning of the introduction of new habitats may allow action to be taken before the population becomes unmanageable. Conversely, the detection of small insect populations may lead to a decision that it is sufficient to continue monitoring the population. Insect populations can be monitored regularly so that insects are controlled only when the insect population reaches a certain threshold. This provides cost-effective control of insects and reduces the environmental impact of pesticide use.

[0213] Those skilled in the art will appreciate that the amount of pheromone or pheromone composition used in a particular application will vary depending on several factors, such as the type and level of infestation, the type of composition used, the concentration of the active ingredient, how the composition is applied, e.g., the type of dispenser used, the type of locus to be treated, the length of time the method is to be used, and environmental factors such as temperature, wind speed and direction, rainfall, and humidity. One skilled in the art will be able to determine the amount of pheromone or pheromone composition effective for use in a given application. [Example]

[0214] IV. Working Examples Example 1 Synthesis of oleyl alcohol Commercially available oleyl alcohol contains isomerization-derived impurities (i.e., elaidyl alcohol) due to the extreme conditions inherent in the heterogeneous catalysts (i.e., copper chromite) used in the process. In some cases, high-purity oleyl alcohol can be prepared using homogeneous catalysts such as [Ru-SNS] or [Ru-PNP] and relatively mild conditions (see Figure 1).

[0215] In a typical preparation, methyl oleate is combined in a reactor with a base (i.e., sodium ethoxide), an optional solvent (i.e., tetrahydrofuran), and a catalytic amount of an ester hydrogenation catalyst (i.e., [Ru-SNS] or [Ru-PNP]). The reactor is then heated to 30-60°C and pressurized with hydrogen gas to 5-30 bar. Upon completion of the reaction, the reactor is depressurized and the contents are washed with water or an aqueous solution (i.e., aqueous hydrochloric acid) to remove reaction by-products. If necessary, the product may be further purified by methods such as distillation. Oleyl alcohol produced using Ru-SNS and Ru-PNP exhibits Z selectivity of greater than 98% and double bond overreduction of less than 1.0%.

[0216] Example 2 Synthesis of oleyl acetate Condition A: A round-bottom flask equipped with a magnetic stir bar was charged with oleyl alcohol (1 molar equivalent), dichloromethane, and NEt3 (3 molar equivalents). The flask was placed under an inert atmosphere and cooled with an external ice bath. Acetic anhydride (2 molar equivalents) was added dropwise to the flask, followed by a catalytic amount of 4-dimethylaminopyridine. The reaction mixture was allowed to warm slowly to room temperature overnight. After 16 hours, the reaction was quenched with water, and the organic layer was washed with saturated aqueous ammonium chloride. After further washing with saturated aqueous solutions of both sodium bicarbonate and sodium chloride, the resulting organic layer was dried over anhydrous magnesium sulfate. The magnesium sulfate was removed by filtration, and all volatile components were removed under reduced pressure to give a yellow-to-colorless oil in greater than 95% yield.

[0217] Condition B: A round-bottom flask equipped with a magnetic stir bar was charged with oleyl alcohol (1 molar equivalent) and a catalytic amount of anhydrous sodium acetate. The flask was placed under an inert atmosphere and heated to 60°C with stirring. Acetic anhydride (1.2 molar equivalents) was added at a rate such that the reaction temperature did not exceed 60°C. After 16 hours, the reaction mixture was cooled to ambient temperature and quenched with water. The organic layer was washed with water and then dried using anhydrous magnesium sulfate. The magnesium sulfate was removed by filtration to give a yellow-colorless oil in greater than 95% yield.

[0218] Depending on the commercial source of oleyl alcohol, the Z:E ratio of oleyl acetate obtained by these procedures was as low as 80:20 and generally did not exceed 95:5.

[0219] Example 3 Synthesis of Z-internal olefins for metathesis reactions

[0220] General procedure for the synthesis of Z-internal olefins Z-internal olefins are synthesized by metathesis of terminal olefins with a cis-selective metal metathesis catalyst (e.g., tungsten or ruthenium catalyst). The ethylene produced during the metathesis reaction is sparged with an inert gas, such as nitrogen or argon. Alternatively, the ethylene can be removed by applying an appropriate vacuum while the starting materials remain in the reaction system.

[0221] Add 1.0 mol of terminal olefin (less than 100 ppm water; less than 0.1 meq / kg peroxide value (PV)) to a reactor containing a reflux condenser and an optional inert gas inlet, and degas with inert gas for 15 minutes. When using a tungsten catalyst, add a saturated ester such as methyl caprate (1000-5000 mol ppm relative to the internal olefin). Add triethylaluminum (TEAl; 1000-3000 mol ppm relative to 1 mol of terminal olefin) and stir for 1 hour to 24 hours (e.g., 4 hours to 8 hours). When using a ruthenium catalyst, filtering the starting material through an activated alumina plug is an effective pretreatment to obtain less than 100 ppm water and less than 0.1 meq / kg PV.

[0222] Add the cis-selective catalyst (3-50 mol ppm per mol of terminal olefin) in one portion and begin stirring. Begin inert gas sparging at a flow rate of 15-30 L / h / kg. Alternatively, vacuum can be used to facilitate ethylene removal; typical pressures range from 400 Torr to 30 Torr. A reflux condenser is used to keep the starting materials in the reactor. The metathesis reaction is carried out for 1-30 hours, typically 4-8 hours.

[0223] The tungsten catalyst is deactivated with 3000–5000 mol ppm of alcohol (e.g., methanol, ethanol, isopropanol, oleyl alcohol, etc.) per mol of terminal olefin. Careful selection of the alcohol allows for recycling of starting materials and intermediates. The addition of the alcohol deactivates the metathesis catalyst and decomposes excess triethylaluminum. The ruthenium catalyst is treated with tetraethylenepentamine (TEPA; 100 molar excess relative to catalyst) and heated to reflux for 1 hour. Typical reaction yields with both catalysts are 50%–70%, with Z selectivities exceeding 97%.

[0224] Synthesis of Z5-decene The synthesis of Z5-decene involves the self-metathesis of neat 1-hexene with a Z-selective catalyst. The ethylene produced is removed from the reaction mixture under reduced pressure. Efficient removal of ethylene contributes to high yields and high Z selectivities. 40.8 g (0.49 mol) of 1-hexene (water concentration less than 50 ppm and peroxide value (PV) less than 0.1 meq / kg) was added to a 250 mL round-bottom, three-neck flask containing a reflux condenser, an inert gas inlet, and a magnetic stirrer. The material was degassed with nitrogen for 15–30 min while heating to 50 °C. Ruthenium catalyst 1 (2.6 mg, 3.92 x 10 -6 The top of the reflux condenser was connected to a diaphragm pump and a reduced pressure was applied. The reduced pressure was controlled between 160 Torr and 90 Torr. TIFF0007821747000062.tif40128

[0225] After 7 hours, GC analysis indicated a 75.9% yield of Z5-decene with a Z selectivity of 99%. TEPA (100 molar equivalents relative to catalyst) was added to quench the ruthenium catalyst. The reaction mixture was distilled under reduced pressure (boiling point 114 °C at 170 Torr) to give Z5-decene (24.2 g, 0.17 mol) in an isolated yield of 71.4% and a Z selectivity of 99%. See Runs 3-14 in Table 1.

[0226] Table 1. Synthesis of Z5-decene using ruthenium catalyst 1 TIFF0007821747000063.tif217131 a GC area (%). b [((Z+E)5-decene area % x EOR mass) / 5-decene theoretical mass] x 100

[0227] Further experiments, outlined in Table 1, demonstrated that 1-hexene was reacted with ruthenium catalyst 1 at temperatures between 20°C and 60°C to produce Z5-decene in 60%-80% yield and 99% Z selectivity. Ruthenium catalyst 1 is air- and moisture-resistant, making it particularly advantageous for ease of handling during the production of fine chemicals such as insect pheromones. Ruthenium catalyst 1 was found to consistently demonstrate improved Z:E ratios and increased yields, e.g., 10% yield increase, relative to other cis-selective catalysts. These advantages enable an exceptionally economical production process.

[0228] Synthesis of Z5-decene 1-Hexene was reacted with tungsten catalyst 2 at 20°C to 40°C to give Z5-decene in a yield of 60% to 70% and a Z selectivity of over 97%. See Tables 2 and 3. TIFF0007821747000064.tif63128

[0229] Synthesis of Z3-hexene 1-Butene is reacted with Catalyst 1 or Catalyst 2 at -10°C to 10°C to give Z3-hexene. When the Z selectivity drops to 97%, or after 24 hours, the reaction is worked up. Yields of greater than 35% are obtained.

[0230] Synthesis of Z4-octene 1-Pentene is reacted with Catalyst 1 or Catalyst 2 at 15°C to 30°C to give Z 4-octene. When the Z selectivity drops to 97%, or after 24 hours, the reaction is worked up. Yields of greater than 50% are obtained.

[0231] Synthesis of Z3-hexene and Z5-decene To increase the efficiency of 1-butene, 1-hexene saturated with 1-butene is reacted with catalyst 1 or catalyst 2 at 10°C to 40°C to produce Z5-decene, Z3-octene, and Z3-hexene. The reaction is worked up when the Z selectivity drops to 97% or after 24 hours. A combined yield of Z5-decene, Z3-octene, and Z3-hexene of over 60% relative to the 1-hexene and 1-butene used is obtained.

[0232] Table 2: Synthesis of Z5-decene using tungsten catalyst 2 TIFF0007821747000065.tif23844*Deca-5-ene yield is calculated by multiplying the GC-FID area % (E+Z) by the end of reaction (EOR) mass and dividing by the theoretical mass of dec-5-ene.

[0233] Table 3. Synthesis of Z5-decene using tungsten catalyst 2 TIFF0007821747000066.tif23856*Deca-5-ene yield is calculated by multiplying the GC-FID area % (E+Z) by the end of reaction (EOR) mass and dividing by the theoretical mass of dec-5-ene.

[0234] Synthesis of Z7-tetradecene 1-Octene is reacted with Catalyst 1 or Catalyst 2 at 15°C to 30°C to give Z7-tetradecene. When the Z selectivity drops to 97%, or after 24 hours, the reaction is worked up. Yields of greater than 50% are obtained.

[0235] Synthesis of Z9-octadecene 1-Decene is reacted with Catalyst 1 or Catalyst 2 at 15°C to 30°C to give Z9-octadecene. When the Z selectivity drops to 97%, or after 24 hours, the reaction is worked up. Yields of greater than 60% are obtained.

[0236] Self-metathesis of methyl 9-decenoate (9-DAME) to Z9-octadecene-dioate 1,18-dimethyl ester (ODDA) 9-DAME is reacted with catalyst 1 or catalyst 2 at 20°C to 40°C under reduced pressure of less than 1 Torr to give ODDA. The reaction is worked up when the Z selectivity drops to 97% or after 24 hours. ODDA is purified by thin-film evaporation.

[0237] Self-metathesis of 9-decenyl acetate to Z9-octadecenedinyl 1,18-diacetate (ODDAc2) 9-Decenyl acetate is reacted with catalyst 1 or catalyst 2 at 20°C to 40°C under reduced pressure of less than 1 Torr to give ODDAc2. The reaction is worked up when the Z selectivity drops to 97% or after 24 hours. ODDAc2 is purified by thin-film evaporation.

[0238] Self-metathesis of 8-nonenyl acetate to Z8-hexadecenedinyl 1,16-diacetate (HDDAc2) 8-Nonenyl acetate is reacted with catalyst 1 or catalyst 2 at 20°C to 40°C under reduced pressure of less than 1 Torr to give HDDAc2. The reaction is worked up when the Z selectivity drops to 97% or after 24 hours. HDDAc2 is purified by thin-film evaporation.

[0239] Self-metathesis of 7-octenyl acetate to Z7-tetradecenedinyl 1,14-diacetate (TDDAc2) Reaction of 7-octenyl acetate with catalyst 1 or catalyst 2 at 20°C-40°C and a reduced pressure of less than 1 Torr affords Z7-tetradecene-dinyl 1,14-diacetate TDDAc2. When Z selectivity drops to 97% or after 24 hours, the reaction is worked up. TDDAc2 is purified by thin-film evaporation.

[0240] Self-metathesis of 9-decenal acetal to Z9-octadecene-1,18-dial 1,18-diacetal (ODDA(acetal)2) 9-Decenal acetal (the acetal can be, but is not limited to, dimethyl acetal, diethyl acetal, ethylene glycol acetal, or propylene glycol acetal) is reacted with catalyst 1 or catalyst 2 at 20°C to 40°C and a reduced pressure of less than 1 Torr to yield ODDA(acetal) 2. The reaction is worked up when the Z selectivity drops to 97% or after 24 hours. ODDA(acetal) 2 is purified by thin-film evaporation.

[0241] Example 4 Cross-metathesis of oleyl acetate with (Z)-dec-5-ene Commercially available oleyl acetate (Z9-18Ac) is a low-cost commodity feedstock for the production of Z9 pheromones, such as Z9-12Ac and Z9-14Ac. However, due to the nature of the hydrogenation and distillation used in the production of oleyl acetate, a significant amount (approximately 20%) of cis / trans isomerization occurs, resulting in the formation of elaidyl alcohol (E9-18Ac). Therefore, metathesis products prepared from available materials were expected to contain significant amounts of E-olefin impurities. However, as detailed below, it has now been found that surprisingly high Z contents (greater than 99%) in the products were obtained when metathesis reactions were carried out with catalysts such as Catalyst 3, Catalyst 4, and Catalyst 5.

[0242] As shown in Figure 2, cross-metathesis of oleyl acetate (Z9-18Ac or "OA") with (Z)-dec-5-ene in the presence of catalyst 3, catalyst 4, or catalyst 5 forms (Z)-tetradec-9-en-1-yl acetate (Z9-14Ac) and a metathesis co-product.

[0243] General Procedure for Cross-Metathesis Screening Reactions The olefin feedstock (i.e., OA and (Z)-dec-5-ene) and a magnetic stir bar were added to a vial under an inert atmosphere. A stock solution of the metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) in dichloromethane was prepared. The required amount of catalyst solution was added to the vial containing oleyl acetate and (Z)-dec-5-ene, and the resulting mixture was stirred at ambient temperature (approximately 30°C). The reaction was typically stirred for 2 hours, after which an excess of tris(hydroxymethyl)phosphine relative to the amount of metathesis catalyst added was added. Water and dichloromethane were then added to the quenched sample. The organic layer was then separated, dried over magnesium sulfate, and analyzed by gas chromatography (GC). GC analysis was performed using an HP-5 or HP-88 capillary column. GC data was analyzed using the following equation: TIFF0007821747000067.tif63128

[0244] Pretreatment of oleyl acetate to maximize catalyst efficiency Using the general procedure described above for cross-metathesis, 0.5 mmol of oleyl acetate (pretreated or unpretreated), 1.5 mmol of (Z)-dec-5-ene, and 0.113 μmol or 0.038 μmol of catalyst 3 or catalyst 4 were combined. The pretreated oleyl acetate was purified by storage on an alumina bed or by reaction with homogeneous magnesium aluminum isopropoxide (MgAl2(Oi-Pr)8). In the case of pretreatment using MgAl2(Oi-Pr)8, the reagents and oleyl acetate raw material were mixed and stored at ambient temperature for approximately 20 hours, after which the screening reaction was carried out without removing the pretreatment reagent. The reactions were analyzed using GC. The effect of oleyl acetate pretreatment on catalyst efficiency is shown in Table 4.

[0245] (Table 4) TIFF0007821747000068.tif87137

[0246] Triethylaluminum (TEAl) may be used for pretreatment, as described below.

[0247] Optimization of magnesium aluminum isopropoxide pretreatment conditions Using the general procedure described above for cross-metathesis, 0.5 mmol of oleyl acetate (pretreated or unpretreated with MgAl(Oi-Pr)), 1.5 mmol of (Z)-dec-5-ene, and 0.113 μmol or 0.038 μmol of catalyst 3 or catalyst 4 were combined. The pretreated oleyl acetate was purified by homogeneous reaction with MgAl(Oi-Pr) in which the MgAl(Oi-Pr) and oleyl acetate starting materials were mixed and stored at ambient temperature for approximately 1, 2, 4, 8, or 20 days before the screening reaction was performed without removing the pretreatment reagent. The results of GC analysis of these pretreatment optimization screening reactions are shown in Table 5.

[0248] (Table 5) TIFF0007821747000069.tif166163

[0249] Kinetics of product E / Z isomerization in the cross-metathesis of oleyl acetate with (Z)-dec-5-ene Using the general procedure described above, 0.5 mmol of oleyl acetate, 1.5 mmol of (Z)-dec-5-ene, and 0.113 μmol of catalyst 3 or catalyst 4 were combined. Aliquots were taken 0.5, 1, 2, 3, 4, or 5 hours after the start of the reaction and analyzed by GC to determine the effect of extended reaction time on the Z content of the product. The results of the GC analysis of these E / Z isomerization screening reactions are shown in Table 6.

[0250] (Table 6) TIFF0007821747000070.tif88128

[0251] Preparative-scale cross-metathesis of oleyl acetate with (Z)-dec-5-ene In an argon-filled glovebox, a 3 L round-bottom flask equipped with a stir bar was charged with (Z)-dec-5-ene (620.4 g, 4.42 mol) and oleyl acetate (458.5 g, 1.48 mol), both of which had been treated with activated alumina. Ruthenium catalyst 3 (0.375 g, 0.442 mmol) was added to the flask, and the reaction mixture was stirred at ambient temperature. After 5 h, the contents of the flask were transferred to a jacketed 5 L flask. Tris(hydroxymethyl)phosphine (30 mL of a 1 M solution in isopropanol, 68 equivalents) was added, and the contents were stirred at 60 °C for 18 h. The reaction mixture was then washed twice with 1 L of water. The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered through a fritted medium-porosity funnel to yield a pale yellow liquid. The mixture was purified by vacuum fractional distillation at less than 0.1 Torr. A main fraction of 183 g, determined by GC analysis to be 85% pure Z9-14Ac (0.63 mol, 43% molar yield relative to oleyl acetate), was collected at a head temperature of 89-100°C.

[0252] Example 5 Cross-metathesis of oleyl acetate with (Z)-hex-3-ene As shown in Figure 3, cross-metathesis of oleyl acetate (Z9-18Ac or "OA") with (Z)-hex-3-ene in the presence of catalyst 3 forms (Z)-dodec-9-en-1-yl acetate (Z9-12Ac) and a metathesis co-product (not shown).

[0253] To a flask equipped with a stir bar, (Z)-hex-3-ene (3 mol) and oleyl acetate (1 mol), both of which have been previously purified, are added. The amount of catalyst 3 required to reach equilibrium conversion is added to the flask, and the reaction is stirred at ambient temperature. When the reaction is complete, the catalyst is deactivated by the addition of tris(hydroxymethyl)phosphine, and the contents are heated with stirring. The reaction mixture is then washed with water, and the organic layer is separated. The organic layer is dried and then purified by vacuum fractional distillation to yield pure (Z)-dodec-9-en-1-yl acetate (Z9-12Ac).

[0254] Example 6 Examination of starting material composition in the cross-metathesis of oleyl acetate with (Z)-dec-5-ene Synthesis of Z9-14Ac (Z9-tetradecenyl acetate) from oleyl acetate and Z5-decene Oleyl alcohol (Jarchem or BASF) was acetylated with acetic anhydride and catalytic amounts of sodium acetate, worked up, and purified by thin-film evaporation. The Z:E ratio of the oleyl acetate was low, at 80:20, and generally did not exceed 95:5. To a 2 L round-bottom, three-neck flask equipped with an inert gas inlet and a magnetic stirrer, oleyl acetate (310 g, 1.0 mol) and Z5-decene (700 g, 5.0 mol), both with a water concentration of less than 100 ppm and a PV of less than 0.1 meq / kg, were added. The reaction mixture was degassed with nitrogen for 30 minutes. Magnesium aluminum isopropoxide (CAS No. 69207-83-6) (10 g, 1 wt%) was added, and the reaction was stirred at 45 °C for 24 hours. Ruthenium stereoretaining metathesis catalyst 4 (304 mg, 0.4 mmol; 50 mol ppm relative to 1 mol of internal double bonds) was added in one portion, and stirring was initiated. The reaction was stirred at 45°C for 5 hours. After 5 hours, TEPA (100 molar excess relative to catalyst) was added and heated to 120°C for 1 hour. The reaction was cooled to 45°C, and the excess and TEPA-catalyst complex were removed with 250 mL of 1 M HCl. Sodium bicarbonate (200 mL, saturated aqueous solution) was added, mixed, and the aqueous phase was removed.

[0255] The crude reaction mixture was purified by vacuum distillation in a fractionating column containing a minimum of eight theoretical plates. Z5-decene and Z5-tetradecene were removed under a reduced pressure of 160 Torr. The product Z9-14Ac (203 g, 0.8 mol, boiling point 105–110 °C at 0.2 Torr) was obtained in good yield and excellent selectivity with ruthenium catalyst 4. The product was isolated with a purity of 95% and a Z selectivity of 99.4%. The major impurity was Z9-octadecene (3%). The Z9-octadecene concentration can be minimized by adding more equivalents of Z5-decene in the metathesis reaction and by using modified distillation conditions. Furthermore, ruthenium catalyst 4 is a crystalline material that does not tend to develop static charge, which is particularly advantageous for handling during production.

[0256] The effect of bond geometry in unfunctionalized olefins, such as Z5-decene, was also examined. Oleyl acetate was reacted with a mixture of 5-decene isomers with different E / Z ratios. This isomer mixture was prepared by mixing Z5-decene (95% Z) with a thermodynamic mixture of 5-decene isomers with different ratios (E / Z = 81.5 / 18.5%). The results are shown in Table 7 below. A significant Z selectivity of approximately 95% was observed even when the decene starting material was approximately 60% E5-decene.

[0257] (Table 7) TIFF0007821747000071.tif41164 a Yield calculated by GC area %.

[0258] Example 7 Synthesis of jojoba oil acetate Commercially available jojoba oil (3.5 kg) was reduced in a round-bottom flask using 1.2 molar equivalents of sodium bis(2-methoxyethoxy)aluminum hydride in toluene at approximately 0°C. The reaction mixture was quenched with aqueous sulfuric acid and washed with water. The crude jojoba oil alcohol was then acetylated in toluene at 75-95°C using excess acetic anhydride and a catalytic amount of anhydrous sodium acetate. After workup, the final molar yield of jojoba oil acetate was greater than 85%. GC analysis showed that the composition of the final product was 5.2 area% (Z)-octadec-9-en-1-yl acetate, 55.6 area% (Z)-icos-11-en-1-yl acetate, 30.4 area% (Z)-docos-13-en-1-yl acetate, 6.17 area% (Z)-tetracos-15-en-1-yl acetate, and 2.6 area% unidentified.

[0259] Example 8 Cross-metathesis of jojoba oil acetate with (Z)-hex-3-ene As shown in Figure 4, cross-metathesis of a mixture of jojoba oil acetate ("JOA") prepared from commercial jojoba oil and (Z)-hex-3-ene in the presence of Catalyst 3, Catalyst 4, or Catalyst 5 forms (Z)-dodec-9-en-1-yl acetate (Z9-12Ac), (Z)-tetradec-11-en-1-yl acetate (Z11-14Ac), (Z)-hexadec-13-en-1-yl acetate (Z13-16Ac), (Z)-octadec-15-en-1-yl acetate (Z15-18Ac), and metathesis co-products.

[0260] General Procedure for Cross-Metathesis Screening Reactions In an inert atmosphere, a flask was charged with the olefin feedstock (i.e., jojoba oil acetate and a 2-4 molar excess of (Z)-hex-3-ene) and a magnetic stir bar. A stock solution of catalyst 3 or catalyst 4 in dichloromethane was prepared. The required amount of catalyst solution was added to the flask containing jojoba oil acetate (JOA) and (Z)-hex-3-ene, and the resulting mixture was stirred at ambient temperature (approximately 30°C). The reaction was typically stirred for 2 hours, after which an excess of tris(hydroxymethyl)phosphine relative to the amount of metathesis catalyst added was added. Water and dichloromethane were then added to the quenched sample. The organic layer was then separated, dried over magnesium sulfate, and analyzed by gas chromatography (GC). GC analysis was performed using an HP-5 or HP-88 capillary column. GC data were analyzed using the following equation: TIFF0007821747000072.tif46142

[0261] Cross-metathesis of jojoba oil acetate with various amounts of (Z)-hex-3-ene Using the general procedure described above for cross-metathesis, 100 mmol of the prepared JOA and 2 or 4 molar equivalents of (Z)-hex-3-ene were combined with 75 ppm (mol) of catalyst 3 per double bond for 1 hour to investigate the effect of substrate loading on reaction yield and selectivity. The reactions were analyzed using GC. The results are shown in Table 8.

[0262] (Table 8) TIFF0007821747000073.tif28142

[0263] Cross-metathesis of jojoba oil acetate with (Z)-hex-3-ene using catalyst 3 or catalyst 4 Using the general procedure described above for cross-metathesis, 100 mmol of the prepared JOA and 300 mmol of (Z)-hex-3-ene were combined with 2000 ppm, 300 ppm, or 150 ppm (mol) of catalyst 3 or catalyst 4 per double bond to investigate the effect of catalyst on reaction yield and selectivity. The reactions were analyzed using GC. The results are shown in Table 9.

[0264] (Table 9) TIFF0007821747000074.tif61149

[0265] Cross-metathesis of jojoba oil acetate with (Z)-hex-3-ene using various amounts of catalyst Using the general procedure described above for cross-metathesis, 100 mmol of the prepared JOA and 300 mmol of (Z)-hex-3-ene were combined with 2000 ppm, 300 ppm, or 150 ppm (mol) of catalyst 3 per double bond to investigate the effect of catalyst loading on reaction yield and selectivity. The reactions were analyzed using GC. The results are shown in Table 10.

[0266] (Table 10) TIFF0007821747000075.tif48152

[0267] Example 9 Cross-metathesis of jojoba oil with (Z)-hex-3-ene As shown below in Figure 5, cross-metathesis of commercially available jojoba oil (i.e., a mixture of fatty acids) with (Z)-hex-3-ene in the presence of Catalyst 4 or Catalyst 6 forms cross-metathesised jojoba oil fatty acids and metathesis co-products (not shown). The cross-metathesised jojoba oil fatty acids are then reduced to the corresponding cross-metathesised jojoba oil alcohols, (Z)-dodec-9-en-1-ol (Z9-12OH), (Z)-tetradec-11-en-1-ol (Z11-14OH), (Z)-hexadec-13-en-1-ol (Z13-16OH), and (Z)-octadec-15-en-1-ol (Z15-18OH).

[0268] Cross-metathesis of jojoba oil with (Z)-hex-3-ene using catalyst 4 or catalyst 6 Using the general procedure for cross-metathesis described above, commercially available jojoba oil ("JO") (50 mmol) and (Z)-hex-3-ene (300 mmol) were subjected to cross-metathesis using metathesis catalyst 4 or metathesis catalyst 6. The reaction was carried out at ambient temperature for 2 hours. Prior to GC analysis, the cross-metathesis JO sample (i.e., the mixture of cross-metathesis jojoba oil fatty acids) was subjected to reduction using sodium bis(2-methoxyethoxy)aluminum hydride according to the procedure described in Example 7, "Synthesis of Jojoba Oil Acetate." The resulting cross-metathesis JO alcohol was then analyzed without further analysis to determine the content of (Z)-tetradec-11-en-1-ol (Z11-14OH) and the Z selectivity of the Z11-14OH product. The GC data were analyzed using the following equations: The results are shown in Table 11. TIFF0007821747000076.tif47159

[0269] (Table 11) TIFF0007821747000077.tif44164

[0270] Example 10 Synthesis of functionalized olefin products for use in agricultural applications General cross-metathesis reaction conditions with ruthenium stereoretaining metathesis catalysts. A reactor equipped with an inert gas inlet is charged with 1.0 mol of a functionalized internal olefin (e.g., oleyl acetate) and 3–6 molar equivalents of a non-functionalized Z-internal olefin (e.g., Z5-decene), both with less than 100 ppm water and less than 0.1 meq / kg PV. The internal olefin is degassed with inert gas for 15 minutes. Triethylaluminum (1000–3000 mol ppm per mol of internal olefin) is added and stirred for 1–24 hours. Alternatively, filtering the starting material through an activated alumina plug is an effective pretreatment to obtain less than 100 ppm water and less than 0.1 meq / kg PV. A ruthenium stereoretaining metathesis catalyst (3–50 ppm per internal double bond), such as Catalyst 3, Catalyst 4, or Catalyst 5, is added in one portion and stirring is initiated. The reaction is typically carried out at 20–60°C. TEPA (100 molar excess relative to the catalyst) is added and heated to reflux for 1 hour to deactivate the catalyst. Typical reaction yields over both catalysts are 50%-85% with Z selectivities greater than 97%. Purification and isolation are achieved by packed-bed vacuum fractional distillation.

[0271] Synthesis of Z9-14Ac from ODDAc2 and Z5-decene ODDAc2 (1 mol) and Z5-decene (4–8 mol of Z5-decene per mol of ODDAc2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereoretaining metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-14Ac is isolated by packed-bed vacuum fractional distillation to give Z9-14Ac with a Z selectivity of >97%.

[0272] Synthesis of Z9-12Ac (Z7-dodecenyl acetate) from oleyl acetate and Z3-hexene Oleyl alcohol is converted to oleyl acetate and purified as described above. Oleyl acetate (1 mol) and Z3-hexene (3–6 mol of Z3-hexene per mol of oleyl acetate) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereoretaining metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-12Ac is isolated by packed-bed vacuum fractional distillation with a Z selectivity of >97%. Impurities such as Z9-octadecene are maintained at levels below 3%.

[0273] Synthesis of Z9-12Ac from ODDAc2 and Z3-decene ODDAc2 (1 mol) and Z3-hexene (4-8 mol of Z3-hexene per mol of ODDAc2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum for 1-8 hours. A ruthenium stereoretaining metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-12Ac is isolated by packed-bed vacuum fractional distillation to give Z9-12Ac with a Z selectivity of over 97%.

[0274] Synthesis of Z9-14Ac and Z9-12Ac from oleyl acetate and Z3-octene Oleyl alcohol is converted to oleyl acetate and purified as described above. Oleyl acetate (1 mol) and Z3-octene (3–6 mol of Z3-octene per mol of oleyl acetate) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereoretaining metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-14Ac and Z9-12Ac are isolated by packed-bed vacuum fractional distillation. Both Z9-14Ac and Z9-12Ac are isolated with purities greater than 95% and Z selectivities greater than 97%. Impurity levels, such as Z9-octadecene, are maintained below 3%.

[0275] Synthesis of Z9-14Ac and Z9-12Ac from ODDAc2 and Z3-octene ODDAc2 (1 mol) and Z3-octene (4–8 mol of Z3-octene per mol of ODDAc2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereoretaining metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-14Ac and Z9-12Ac are isolated by packed-bed vacuum fractional distillation. Both Z9-14Ac and Z9-12Ac are isolated with purities greater than 95% and Z selectivities greater than 97%.

[0276] Synthesis of Z8-12Ac (Z8-dodecenyl acetate) from HDDAc2 and Z4-octene HDDAc2 (1 mol) and Z4-octene (3–6 mol of Z4-octene per mol of HDDAc2) are stirred, degassed with nitrogen for 15 min, and treated with triethylaluminum. A ruthenium stereoretaining metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) is added, and the reaction is monitored by GC analysis. Z8-12Ac is isolated by packed-bed vacuum fractional distillation with a purity of >95% and a Z selectivity of >97%.

[0277] Synthesis of Z7-12Ac from TDDAc2 and Z5-decene TDDAc2 (1 mol) and Z5-decene (3–6 mol of Z5-decene per mol of TDDAc2) are stirred, degassed with nitrogen for 15 min, and treated with triethylaluminum. A ruthenium stereoretaining metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) is added, and the reaction is monitored by GC analysis. Z7-12Ac is isolated by packed-bed vacuum fractional distillation with a purity of >95% and a Z selectivity of >97%.

[0278] Synthesis of Z9-16Ac (Z9-hexadecenyl acetate) from oleyl acetate and Z7-tetradecene Oleyl alcohol is converted to oleyl acetate and purified as described above. Oleyl acetate (1 mol) and Z7-tetradecene (4–8 mol of Z7-tetradecene per mol of oleyl acetate) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereoretaining metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-16Ac is isolated by packed-bed vacuum fractional distillation with a purity of >95% and a Z selectivity of >97%. Impurities such as Z9-octadecene are maintained at levels below 1%.

[0279] Synthesis of Z9-16Ac from ODDAc2 and Z7-tetradecene ODDAc2 (1 mol) and Z7-tetradecene (4–8 mol of Z7-tetradecene per mol of ODDAc2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereoretaining metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-16Ac is isolated by packed-bed vacuum fractional distillation with a purity of >95% and a Z selectivity of >97%.

[0280] Synthesis of Z9-16 acetal (Z9-16 acetal refers to Z9-hexadecenal acetal) from ODDA(acetal)2 and Z7-tetradecene ODDA(acetal)2 (1 mol) and Z7-tetradecene (4–8 mol of Z7-tetradecene per mol of ODDA(acetal)2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereoretaining metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-16 acetal is isolated by packed-bed vacuum fractional distillation with a purity of >90% and a Z selectivity of >95%.

[0281] Synthesis of Z9-18Ac (Z9-18Ac means Z9-octadecenyl acetate) from ODDAc2 and Z9-octadecene ODDAc2 (1 mol) and Z9-octadecene (4–8 mol of Z9-octadecene per mol of ODDAc2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereoretaining metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-18Ac is isolated by packed-bed vacuum fractional distillation with a purity of >95% and a Z selectivity of >97%.

[0282] Synthesis of Z9-18 acetal (Z9-18 acetal refers to Z9-octadecenal acetal) from ODDA(acetal)2 and Z9-octadecene ODDA (acetal) 2 (1 mol) and Z9-octadecene (4–8 mol of Z9-octadecene per mol of ODDAc2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereoretaining metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-18 acetal is isolated by packed-bed vacuum fractional distillation with a purity of >90% and a Z selectivity of >95%.

[0283] Synthesis of jojoba acetate by reduction of jojoba oil to jojoba acetate and subsequent acetylation. Jojoba oil (Greenchem) is diluted with an equal volume of anhydrous toluene and reduced to 1 mole of jojoba esters with 1.5 molar equivalents of Vitride. After reduction is complete, the reaction is carefully diluted with sulfuric acid until the aqueous phase has a pH below 1 and washed with brine. The organic phase is isolated and made anhydrous by azeotropic removal of water. Anhydrous jojoba alcohol is acetylated as previously described for oleyl acetate. Jojoba acetate is purified by thin-film evaporation in approximately 80% yield. The composition of jojoba acetate is approximately 5% Z9-18Ac, approximately 55% Z11-20Ac, approximately 35% Z13-22Ac, and approximately 5% Z15-24Ac.

[0284] Synthesis of Z9-12Ac, Z11-14Ac (Z11-tetradecenyl acetate), and Z13-16Ac (Z13-hexadecenyl acetate) from jojoba acetate and Z3-hexene Jojoba acetate (1 mol) and Z3-hexene (4-8 mol of Z3-hexene per mol of jojoba acetate) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereoretaining metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-12Ac, Z11-14Ac, and Z13-16Ac are isolated by packed-bed vacuum fractional distillation. Z9-12Ac, Z11-14Ac, and Z13-16Ac are isolated with purities greater than 95% and Z selectivities greater than 97%.

[0285] Synthesis of Z9-14Ac, Z11-16Ac (Z11-hexadecenyl acetate), and Z13-18Ac (Z13-hexadecenyl acetate) from jojoba acetate and Z5-decene Jojoba acetate (1 mol) and Z5-decene (4-8 mol of Z5-decene per mol of jojoba acetate) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereoretaining metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-14Ac, Z11-16Ac, and Z13-18Ac are isolated by packed-bed vacuum fractional distillation. Z9-14Ac, Z11-16Ac, and Z13-18Ac are isolated with purities greater than 95% and Z selectivities greater than 97%.

[0286] Synthesis of jojoba acetal from jojoba oil by reduction, oxidation, and acetal formation Jojoba alcohol is prepared as described above. Anhydrous jojoba alcohol is oxidized to an aldehyde (e.g., by Stahl oxidation, Swern oxidation, tetrapropylammonium perruthenate (TPAP) oxidation, etc.). The jojoba aldehyde is converted to an acetal (e.g., dimethyl acetal, diethyl acetal, ethylene glycol acetal, or propylene glycol acetal) using an excess of alcohol and a catalytic amount of acid. The acetal is purified by thin-film evaporation in approximately 70% isolated yield. The composition of the jojoba acetal is approximately 5% Z9-18 acetal, approximately 55% Z11-20 acetal, approximately 35% Z13-22 acetal, and approximately 5% Z15-24 acetal.

[0287] Synthesis of Z9-14 acetal (Z9-tetradecenal acetal), Z11-16 acetal (Z11-hexadecenal acetal), and Z13-18 acetal (Z13-octadecenal acetal) from jojoba acetal and Z5-decene Jojoba acetal (1 mol) and Z5-decene (4-8 mol of Z5-decene per mol of jojoba acetal) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereoretaining metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-14 acetal, Z11-16 acetal, and Z13-18 acetal are isolated by packed-bed vacuum fractional distillation. Z9-14 acetal, Z11-16 acetal, and Z13-18 acetal are isolated with purities greater than 80% and Z selectivities greater than 90%.

[0288] Exemplary Embodiments Exemplary embodiments provided in accordance with the subject matter disclosed herein include, but are not limited to, the embodiments set forth in the claims and described below.

[0289] 1. A method for synthesizing a Z-enriched aliphatic olefin metathesis product, comprising contacting an olefin metathesis reaction partner with an internal olefin in the presence of a Group 8 transition metal metathesis catalyst to form a Z-enriched aliphatic olefin metathesis product, wherein the aliphatic olefin metathesis product is an acylated alkenol or alkenal acetal; the olefin metathesis reaction partners comprise a mixture of Z olefins and E olefins in a starting Z:E ratio; the aliphatic olefin metathesis product comprises a mixture of Z olefins and E olefins in a product Z:E ratio; A process wherein the product Z:E ratio is higher than the starting Z:E ratio.

[0290] 2. The aliphatic olefin metathesis product has the formula I: TIFF0007821747000078.tif16128 is an acylated alkenol; The metathesis reaction partner is of formula III: TIFF0007821747000079.tif16128 compound; The internal olefin is of formula IV: TIFF0007821747000080.tif10128 compound; R 1 But H and C 1~6 selected from the group consisting of alkyl; R 2 But C 1~18 Alkyl and C 2~18 alkenyl; R 3 C 1~18 is alkyl; The subscript y is an integer ranging from 0 to 17; The subscript z is an integer ranging from 0 to 17; the Group 8 transition metal metathesis catalyst is a Z-selective Group 8 transition metal catalyst; The method of embodiment 1.

[0291] 3. The method of embodiment 1 or 2, wherein the metathesis catalyst is a Z-selective ruthenium catalyst or a Z-selective osmium catalyst.

[0292] 4. The method of any one of embodiments 1-3, wherein the aliphatic olefin metathesis product is at least 97% Z.

[0293] 5. The method of any one of embodiments 1-3, wherein the aliphatic olefin metathesis product is greater than 98% Z.

[0294] 6. The method of any one of embodiments 1-3, wherein the aliphatic olefin metathesis product is greater than 99% Z.

[0295] 7. The method of any one of embodiments 1-6, wherein the metathesis reaction partner is about 1% to about 50% E.

[0296] 8. The synthesis of aliphatic olefin metathesis products is carried out by reacting an acylating agent with a compound of formula II: TIFF0007821747000081.tif10128 with an alkenol of formula III to form an olefin metathesis reaction partner of formula III.

[0297] 9. The method of embodiment 8, wherein the acylating agent is acetic anhydride.

[0298] 10. The synthesis of an aliphatic olefin metathesis reaction partner is carried out by reacting a compound of formula IIa: TIFF0007821747000082.tif16128 (in the formula, R 4 is H and C 1~8 alkyl) 10. The method of claim 8 or 9, comprising reducing an unsaturated aliphatic carboxylic derivative of formula II to form an alkenol of formula II.

[0299] 11. The method of embodiment 10, wherein the step of forming the alkenol of formula II comprises contacting an unsaturated aliphatic carboxylic derivative with a base in the presence of a hydrogenation catalyst and hydrogen gas.

[0300] 12. The method of embodiment 10, wherein forming the alkenol of formula II comprises contacting an unsaturated aliphatic carboxylic derivative with a reducing agent.

[0301] 13. The method of embodiment 12, wherein the reducing agent is sodium bis(2-methoxyethoxy)aluminum hydride.

[0302] 14. The method of any one of embodiments 8-13, wherein the alkenol of formula II is about 1% to about 50% E.

[0303] 15. The aliphatic olefin metathesis product has the formula VI: TIFF0007821747000083.tif16128 is an alkenal acetal; The metathesis reaction partner is of formula VII: TIFF0007821747000084.tif16128 compound; The internal olefin is of formula IV: TIFF0007821747000085.tif10128 compound; R 1 C 1~6 is alkyl; R 2 But C 1~18 Alkyl and C 2~18 alkenyl; R 3 C 1~18 is alkyl; The subscript y is an integer ranging from 0 to 17; The subscript z is an integer ranging from 0 to 17; the Group 8 transition metal metathesis catalyst is a Z-selective Group 8 transition metal catalyst; The method of embodiment 1.

[0304] 16. The metathesis product is reacted with a compound of formula VIII: The method of embodiment 15, further comprising converting TIFF0007821747000086.tif16128 to an alkenal.

[0305] 17. The method of any one of embodiments 1-16, wherein synthesizing an aliphatic olefin metathesis product comprises contacting a terminal olefin with a metathesis catalyst to form an internal olefin.

[0306] 18. The internal olefin is represented by formula VIa: TIFF0007821747000087.tif12128 compound; The terminal olefin is of formula IVb: The method of embodiment 20, wherein the compound is a compound of TIFF0007821747000088.tif10128.

[0307] 19. The method of embodiment 17 or 18, wherein the metathesis catalyst for forming the internal olefin is a Z-selective ruthenium catalyst or a Z-selective tungsten catalyst.

[0308] 20. Formula I: 1. A method for synthesizing an aliphatic olefin metathesis product of TIFF0007821747000089.tif16128, comprising: Formula III: TIFF0007821747000090.tif16128 to form an olefin metathesis reaction partner of Formula II: with an alkenol of formula (I); and To form an aliphatic olefin metathesis product, an olefin metathesis reaction partner and an aliphatic olefin metathesis reaction partner of Formula IV: and an internal olefin of formula (I) in the presence of a Z-selective ruthenium catalyst or a Z-selective osmium catalyst, wherein R 1 But H and C1~6 selected from the group consisting of alkyl; R 2 But C 1~18 Alkyl and C 2~18 alkenyl; R 3 C 1~18 is alkyl; The subscript y is an integer ranging from 0 to 17; The subscript z is an integer ranging from 0 to 17; The method wherein the aliphatic olefin metathesis product is at least 97% Z.

[0309] 21. The method of embodiment 20, wherein the acylating agent is acetic anhydride.

[0310] 22. The method of embodiment 20 or 21, wherein the alkenol of formula II is about 1% to about 50% E.

[0311] 23. Formula I: 1. A method for synthesizing an aliphatic olefin metathesis product of TIFF0007821747000093.tif16128, comprising: Formula II: to form an alkenol of formula IIa: reducing the unsaturated aliphatic carboxyl derivative of TIFF0007821747000095.tif16128; Formula III: contacting an acylating agent with an alkenol to form an olefin metathesis reaction partner of formula (TIFF0007821747000096.tif16128); and To form an aliphatic olefin metathesis product, an olefin metathesis reaction partner and an aliphatic olefin metathesis reaction partner of Formula IV: TIFF0007821747000097.tif10128 with an internal olefin in the presence of a Z-selective ruthenium catalyst or a Z-selective osmium catalyst, wherein R 1 But H and C 1~6selected from the group consisting of alkyl; R 2 But C 1~18 Alkyl and C 2~18 alkenyl; R 3 C 1~18 is alkyl; R 4 But H and C 1~8 selected from the group consisting of alkyl; The subscript y is an integer ranging from 0 to 17; The subscript z is an integer ranging from 0 to 17; The method wherein the aliphatic olefin metathesis product is at least 97% Z.

[0312] 24. The method of embodiment 23, wherein reducing the unsaturated aliphatic carboxyl derivative of Formula IIa to form the alkenol of Formula II comprises contacting the unsaturated aliphatic carboxyl derivative with a base in the presence of a hydrogenation catalyst and hydrogen gas.

[0313] 25. The method of embodiment 23, wherein reducing the unsaturated aliphatic carboxyl derivative of Formula IIa to form the alkenol of Formula II comprises contacting the unsaturated aliphatic carboxyl derivative with a reducing agent.

[0314] 26. The method of embodiment 25, wherein the reducing agent is sodium bis(2-methoxyethoxy)aluminum hydride.

[0315] 27. The method of any one of embodiments 23 to 26, wherein the acylating agent is acetic anhydride.

[0316] 28. The method of any one of embodiments 23-27, wherein the alkenol of formula II is about 1% to about 50% E.

[0317] 29. R 1 C 1~3 alkyl, and R 2 C 1~12 alkyl, and R 3 C 1~12The method of any one of embodiments 2-28, wherein y is an integer ranging from 5 to 15, and z is an integer ranging from 0 to 7.

[0318] 30. R 1 C 1~3 alkyl, and R 2 C 1~12 alkyl, and R 3 C 1~12 alkyl, and R 4 C 1~3 25. The method of any one of embodiments 10, 11, 23, and 24, wherein: y is 7; and z is an integer ranging from 1 to 5.

[0319] 31. R 1 C 1~3 alkyl, and R 2 C 1~12 alkyl, and R 3 C 1~12 alkyl, and R 4 is H; y is an integer in the range of 5 to 15; and z is an integer in the range of 1 to 5.

[0320] 32. The metathesis reaction partner of formula III is an aliphatic C 12 ~C 30 olefin acetate; The internal olefin of formula IV is C4-C 20 is an internal olefin; The aliphatic olefin metathesis product of formula I is C8-C 28 (Z)-unsaturated aliphatic ester acetate, The method according to any one of aspects 2 to 7.

[0321] 33. The olefin metathesis reaction partner of formula III is (Z)-octadec-9-en-1-yl acetate; The internal olefin of formula IV is (Z)-dec-5-ene; The aliphatic olefin metathesis product of formula I is (Z)-tetradec-9-en-1-yl acetate. The method of any one of embodiments 2 to 7 and 32.

[0322] 34. The olefin metathesis reaction partner of formula III is (Z)-octadec-9-en-1-yl acetate; The internal olefin of formula IV is (Z)-hex-3-ene; The aliphatic olefin metathesis product of formula I is (Z)-dodec-9-en-1-yl acetate; The method of any one of embodiments 2 to 7 and 32.

[0323] 35. The olefin metathesis reaction partner of formula III is (Z)-icosa-11-en-1-yl acetate; The internal olefin of formula IV is (Z)-hex-3-ene; The aliphatic olefin metathesis product of formula I is (Z)-tetradec-11-en-1-yl acetate; The method of any one of embodiments 2 to 7 and 32.

[0324] 36. The alkenol of formula II is C 10 ~C 28 is an aliphatic alkenol; The olefin metathesis reaction partner of formula III is C 10 ~C 28 acetate esters of aliphatic alkenols; The internal olefin of formula IV is C4-C 20 is an internal olefin; The aliphatic olefin metathesis product of formula I is C8-C 28 (Z)-unsaturated aliphatic ester acetate, The method according to any one of embodiments 8 to 31.

[0325] 37. The alkenol of formula II is (Z)-octadec-9-en-1-ol; the olefin metathesis reaction partner of formula III is (Z)-octadec-9-en-1-yl acetate; The internal olefin of formula IV is (Z)-dec-5-ene; The aliphatic olefin metathesis product of formula I is (Z)-tetradec-9-en-1-yl acetate. The method according to any one of embodiments 10 to 36.

[0326] 38. The alkenol of formula II is (Z)-octadec-9-en-1-ol; the olefin metathesis reaction partner of formula III is (Z)-octadec-9-en-1-yl acetate; The internal olefin of formula IV is (Z)-hex-3-ene; The aliphatic olefin metathesis product of formula I is (Z)-dodec-9-en-1-yl acetate; The method according to any one of embodiments 10 to 36.

[0327] 39. The alkenol of formula II is (Z)-icosa-11-en-1-ol; the olefin metathesis reaction partner of formula III is (Z)-icosa-11-en-1-yl acetate; The internal olefin of formula IV is (Z)-hex-3-ene; The aliphatic olefin metathesis product of formula I is (Z)-tetradec-11-en-1-yl acetate; The method according to any one of embodiments 10 to 36.

[0328] 40. The method of any one of embodiments 1 to 38, wherein the synthesis of the aliphatic olefin metathesis product comprises contacting the olefin metathesis reaction partner with a pretreatment reagent prior to contacting with the internal olefin.

[0329] 41. The method of embodiment 40, wherein the pretreatment reagent is selected from the group consisting of alumina, triethylaluminum, and magnesium aluminum isopropoxide.

[0330] 42. The method of any one of aspects 10-12 and 23-25, wherein the unsaturated aliphatic carboxylic derivative is derived from a natural oil.

[0331] 43. The method of embodiment 42, wherein the natural oil is selected from the group consisting of almond oil, canola oil, avocado oil, argan oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, grapeseed oil, olive oil, palm oil, peanut oil, hempseed oil, macadamia oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil, jojoba oil, mustard oil, shepherd's purse oil, cabbage oil, castor oil, and combinations thereof.

[0332] 44. The method of embodiment 42 or 43, further comprising distilling the unsaturated aliphatic carboxylic derivative of Formula IIa, the alkenol of Formula II, or the olefin metathesis reaction partner of Formula III prior to metathesis to remove plant-based impurities.

[0333] 45. The method of embodiment 44, wherein the plant-based impurities include one or more proteins.

[0334] 46. ​​A Z-selective metathesis catalyst having the structure of formula V: TIFF0007821747000098.tif38128, During the ceremony, M is selected from the group consisting of ruthenium and osmium; X and Y are independently selected from the group consisting of S and O; Z is selected from the group consisting of O, S(=O), N, and halogen; each subscript m and subscript n is an integer independently selected from 0, 1, 2, 3, and 4; Each R a are independently selected from the group consisting of halogen, C1-C6 alkyl, alkoxy, aryl, and heteroaryl; or one R a is the adjacent R a together to form an unsubstituted or substituted bicyclic or unsubstituted or substituted polycyclic ring; Each R b are independently selected from the group consisting of halogen, C1-C6 alkyl, alkoxy, aryl, and heteroaryl; or one R b is the adjacent R b together to form an unsubstituted or substituted bicyclic or unsubstituted or substituted polycyclic ring; R c is selected from the group consisting of hydrogen and C1-C6 alkyl; Each R d , R e , R f , and R g are independently selected from the group consisting of hydrogen and C1-C6 alkyl; R 12 and R 13 is independently selected from the group consisting of 2,4,6-tri-isopropylphenyl, 2,6-di-isopropylphenyl, 2,6-di-adamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl; Each R 14 is independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl, and phenyl; R 15 is selected from the group consisting of hydrogen, halogen, and C1-C6 alkyl, or R 15 and one R 14 come together to form a bond, The method according to any one of embodiments 2 to 45.

[0335] 47. M is ruthenium; X and Y are S; Z is selected from the group consisting of O and S(=O); The subscript m is 2; The subscript n is 0; Each R a are independently selected from the group consisting of halogen, C1-C6 alkyl, and aryl; Rc is hydrogen; Each R d , R e , R f , and R g is hydrogen; Each R 14 is independently selected from the group consisting of methyl, isopropyl, benzyl, and tert-butyl; The method of embodiment 46.

[0336] 48. The metathesis catalyst is selected from the group consisting of: 48. The method of embodiment 46 or 47, wherein the antibody is selected from TIFF0007821747000099.tif48137.

[0337] Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity and understanding, those skilled in the art will recognize that certain changes and modifications can be practiced within the scope of the appended claims. All publications, patents, patent applications, and sequence accession numbers cited herein are incorporated by reference in their entirety for all purposes.

Claims

1. 1. A method for synthesizing a Z-enriched aliphatic olefin metathesis product, comprising contacting an olefin metathesis reaction partner with an internal olefin in the presence of a Z-selective Group 8 transition metal metathesis catalyst to form a Z-enriched aliphatic olefin metathesis product, wherein the olefin metathesis reaction partners comprise a mixture of Z olefins and E olefins in a starting Z:E ratio; the aliphatic olefin metathesis product comprises a mixture of Z olefins and E olefins in a product Z:E ratio; the product Z:E ratio is higher than the starting Z:E ratio; The aliphatic olefin metathesis product has Formula I: is an acylated alkenol of; The metathesis reaction partner is of formula III: is a compound of; The internal olefin is of formula IV: is a compound of; R 1 is selected from the group consisting of H and C 1-6 alkyl; R 2 is selected from the group consisting of C 1-18 alkyl and C 2-18 alkenyl; R 3 is C 1-18 alkyl; The subscript y is an integer in the range 0 to 17; The subscript z is an integer ranging from 0 to 17; The Z-selective metathesis catalyst has the structure of Formula V: and During the ceremony, M is selected from the group consisting of ruthenium and osmium; X and Y are independently selected from the group consisting of S and O; Z is selected from the group consisting of S(=O), O, and N; The subscript m is an integer selected from 2, 4, 3, 1, and 0; The subscript n is an integer selected from 0, 1, 2, 3, or 4; Each R a are independently halogen, C 1 ~C 6 selected from the group consisting of alkyl, alkoxy, aryl, and heteroaryl; or one R a is the adjacent R a together to form an unsubstituted or substituted bicyclic or unsubstituted or substituted polycyclic ring; Each R b are independently halogen, C 1 ~C 6 selected from the group consisting of alkyl, alkoxy, aryl, and heteroaryl; or one R b is the adjacent R b together to form an unsubstituted or substituted bicyclic or unsubstituted or substituted polycyclic ring; R c is hydrogen and C 1 ~C 6 selected from the group consisting of alkyl; Each R d , R e , R f , and R g are independently hydrogen and C 1 ~C 6 selected from the group consisting of alkyl; R 12 and R 13 is independently selected from the group consisting of 2,6-di-isopropylphenyl, 2,4,6-tri-isopropylphenyl, 2,6-di-adamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl; Each R 14 is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl, phenyl, and hydrogen; R 15 is hydrogen, halogen, and C 1 ~C 6 alkyl, or R 15 and one R 14 come together to form a bond, method.

2. 10. The method of claim 1, wherein the aliphatic olefin metathesis product is greater than 97% Z.

3. 10. The method of claim 1, wherein the metathesis reaction partner is 1% to 50% E.

4. M is ruthenium; X and Y are S; Z is selected from the group consisting of S(=O) and O; The subscript m is 2; The subscript n is 0; Each R a are independently halogen, C 1 ~C 6 selected from the group consisting of alkyl, and aryl; R c is hydrogen; Each R d , R e , R f , and R g is hydrogen; Each R 14 is independently selected from the group consisting of methyl, isopropyl, benzyl, and tert-butyl; 10. The method of claim 1.

5. The metathesis catalyst is selected from the group consisting of:

2. The method of claim 1, wherein the method is selected from the group consisting of:

6. The synthesis of aliphatic olefin metathesis products is carried out by reacting an acylating agent with a compound of formula II: with an alkenol of formula III to form an olefin metathesis reaction partner of formula III.

7. The synthesis of an aliphatic olefin metathesis reaction partner is carried out by reacting a compound of formula IIa: (In the formula, R 4 H and C 1～8 7. The method of claim 6, comprising reducing an unsaturated aliphatic carboxylic derivative of an alkyl group selected from the group consisting of alkyl groups to form an alkenol of formula II.

8. 8. The method of claim 7, wherein the step of forming the alkenol of formula II comprises contacting an unsaturated aliphatic carboxylic derivative with a base in the presence of a hydrogenation catalyst and hydrogen gas.

9. 8. The method of claim 7, wherein forming the alkenol of formula II comprises contacting an unsaturated aliphatic carboxylic derivative with a reducing agent.

10. 8. The method of claim 7, wherein the unsaturated aliphatic carboxyl derivative is derived from a natural oil selected from the group consisting of almond oil, canola oil, avocado oil, argan oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, grapeseed oil, olive oil, palm oil, peanut oil, hempseed oil, macadamia oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil, jojoba oil, mustard oil, shepherd's purse oil, cabbage oil, castor oil, and combinations thereof.

11. 10. The method of claim 1, wherein synthesizing the aliphatic olefin metathesis product comprises forming an internal olefin by contacting a terminal olefin with a metathesis catalyst to form an internal olefin.

12. R 1 C 1～3 alkyl, and R 2 C 1～12 alkyl, and R 3 C 1～12 2. The method of claim 1, wherein y is an integer ranging from 5 to 15 and z is an integer ranging from 0 to 7.

13. The metathesis reaction partner of formula III is an aliphatic C 12 ~C 30 olefin acetate; The internal olefin of formula IV is C 4 ~C 20 is an internal olefin; The aliphatic olefin metathesis product of formula I is C 8 ~C 28 (Z)-unsaturated aliphatic ester acetate, 10. The method of claim 1.

14. the olefin metathesis reaction partner of formula III is (Z)-octadec-9-en-1-yl acetate; The internal olefin of formula IV is (Z)-dec-5-ene; The aliphatic olefin metathesis product of formula I is (Z)-tetradec-9-en-1-yl acetate.

10. The method of claim 1.

15. the olefin metathesis reaction partner of formula III is (Z)-octadec-9-en-1-yl acetate; The internal olefin of formula IV is (Z)-hex-3-ene; The aliphatic olefin metathesis product of formula I is (Z)-dodec-9-en-1-yl acetate; 10. The method of claim 1.

16. the olefin metathesis reaction partner of formula III is (Z)-icosa-11-en-1-yl acetate; The internal olefin of formula IV is (Z)-hex-3-ene; The aliphatic olefin metathesis product of formula I is (Z)-tetradec-11-en-1-yl acetate; 10. The method of claim 1.

17. 10. The method of claim 1, wherein the synthesis of the aliphatic olefin metathesis product comprises contacting the olefin metathesis reaction partner with a pretreatment reagent prior to contacting with the internal olefin.

18. 18. The method of claim 17, wherein the pretreatment reagent is selected from the group consisting of alumina, triethylaluminum, and magnesium aluminum isopropoxide.

19. The internal olefin of claim VIa: is a compound of; The terminal olefin has formula IVb: is a compound of The subscript z is an integer in the range 0 to 17, 12. The method of claim 11.

20. A method for synthesizing a Z-enriched aliphatic olefin metathesis product, comprising contacting an olefin metathesis reaction partner with an internal olefin in the presence of a Z-selective Group 8 transition metal metathesis catalyst to form a Z-enriched aliphatic olefin metathesis product, wherein the olefin metathesis reaction partners comprise a mixture of Z olefins and E olefins in a starting Z:E ratio; the aliphatic olefin metathesis product comprises a mixture of Z olefins and E olefins in a product Z:E ratio; the product Z:E ratio is higher than the starting Z:E ratio; The aliphatic olefin metathesis product has the formula VI: is an alkenal acetal of; The metathesis reaction partner is of formula VII: is a compound of; The internal olefin is of formula IV: is a compound of; R 1 C 1～6 is alkyl; R 2 But C 1～18 Alkyl and C 2～18 alkenyl; R 3 C 1～18 is alkyl; The subscript y is an integer in the range 0 to 17; The subscript z is an integer ranging from 0 to 17; The Z-selective metathesis catalyst has the structure of Formula V: and During the ceremony, M is selected from the group consisting of ruthenium and osmium; X and Y are independently selected from the group consisting of S and O; Z is selected from the group consisting of S(=O), O, and N; The subscript m is an integer selected from 2, 4, 3, 1, and 0; The subscript n is an integer selected from 0, 1, 2, 3, or 4; each R a is independently selected from the group consisting of halogen, C 1 -C 6 alkyl, alkoxy, aryl, and heteroaryl; or one R a is joined with an adjacent R a to form an unsubstituted or substituted bicyclic or unsubstituted or substituted polycyclic ring; each R b is independently selected from the group consisting of halogen, C 1 -C 6 alkyl, alkoxy, aryl, and heteroaryl; or one R b is joined with an adjacent R b to form an unsubstituted or substituted bicyclic or unsubstituted or substituted polycyclic ring; R c is selected from the group consisting of hydrogen and C 1 -C 6 alkyl; each R d , R e , R f , and R g is independently selected from the group consisting of hydrogen and C 1 -C 6 alkyl; R 12 and R 13 are independently selected from the group consisting of 2,6-di-isopropylphenyl, 2,4,6-tri-isopropylphenyl, 2,6-di-adamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl; each R 14 is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl, phenyl, and hydrogen; R 15 is selected from the group consisting of hydrogen, halogen, and C 1 -C 6 alkyl; or R 15 and one R 14 together form a bond; method.

21. The method of claim 20, wherein the aliphatic olefin metathesis product is a compound of formula VIII:

21. The method of claim 20, further comprising converting the alkenal of formula (I) to the alkenal of formula (I).

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