Synthesis of pheromone derivatives by z-selective olefin metathesis

Abstract

Disclosed herein are methods for synthesizing a fatty olefin metathesis product of high Z-isomeric purity from an olefin starting material of low Z-isomeric purity. The methods include contacting an olefin metathesis reaction partner (e.g., an acylated enol or enal acetal) with an internal olefin in the presence of a Z-selective metathesis catalyst to form the fatty olefin metathesis product. In various embodiments, the fatty olefin metathesis product is an insect pheromone. Also described are pheromone compositions and methods of their use.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 032,932, filed on June 1, 2020, which is incorporated herein by reference in its entirety. Background of the Invention

[0004] As the global demand for food grows, the need for effective pest control is increasing. Conventional pesticides are the most popular chemical control agents because they are readily available, fast-acting, and highly reliable. However, overuse, misuse, and abuse of these chemicals have led to resistant pests, changes in natural ecosystems, and, in some cases, environmental damage.

[0005] The use of insect pheromones to control pest populations has gained increasing popularity as a viable, safe, and environmentally friendly alternative to conventional pesticides. Since their discovery in the late 1950s, these molecules have demonstrated efficacy in reducing insect populations through a variety of methods, including mass capture, attraction and killing, and mating disruption. The latter approach, in particular, represents a non-toxic approach to pest control and exploits the ability of synthetic pheromones to mask naturally occurring pheromones, thereby causing confusion and mating disruption.

[0006] Although pheromones have significant potential for agricultural insect control, the cost of synthesizing them using currently available technologies is very high, which has prevented the widespread use of this sustainable technology outside of high-value crops. Therefore, there is a need to develop new technologies for cost-effectively producing 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 high Z-isomerically pure unsaturated fatty olefin metathesis products, including synthetic insect pheromones, from low-cost raw materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Figure 1 The catalytic hydrogenation of methyl oleate to form oleyl alcohol is shown.

[0008] Figure 2 The synthesis of Z9-14Ac via stereopreservative olefin cross-metathesis using oleyl acetate and (Z)-dec-5-ene is shown.

[0009] Figure 3 The synthesis of Z9-12Ac via stereopreservative olefin cross-metathesis using oleyl acetate and (Z)-hex-3-ene is shown.

[0010] Figure 4 The synthesis of metathesized jojoba acetate via stereopreservative olefin cross-metathesis using jojoba acetate and (Z)-hex-3-ene is shown.

[0011] Figure 5 Synthesis of cross-metathesized jojoba alcohol using commercially available jojoba oil with (Z)-hex-3-ene by stereoconvergent olefin cross-metathesis followed by reduction is shown. SUMMARY

[0012] Provided herein are methods for synthesizing a Z-enriched fatty olefin metathesis product. The method comprises 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 fatty olefin metathesis product, wherein:

[0013] the fatty olefin metathesis product is an acylated enol or enal acetal,

[0014] the olefin metathesis reaction partner comprises a mixture of Z and E olefins at a starting Z:E ratio,

[0015] the fatty olefin metathesis product comprises a mixture of Z and E olefins at a product Z:E ratio, and

[0016] the product Z:E ratio is higher than the starting Z:E ratio.

[0017] In some embodiments, the present application provides a method for synthesizing a fatty olefin metathesis product according to Formula I:

[0018]

[0019] wherein the method comprises contacting an olefin metathesis reaction partner according to Formula III with

[0020]

[0021] an internal olefin according to Formula IV

[0022]

[0023] in the presence of a metathesis catalyst to form the fatty olefin metathesis product; wherein:

[0024] R 1 is selected from the group consisting of H and C 1-6 alkyl;

[0025] R 2 is selected from the group consisting of C 1-18 alkyl and C 2-18 alkenyl;

[0026] R 3 is C 1-18 alkyl;

[0027] the subscript y is an integer from 0 to 17;

[0028] the subscript z is an integer from 0 to 17; and

[0029] The metathesis catalyst is a Z-selective Group 8 transition metal catalyst.

[0030] In some embodiments, the metathesis catalyst is a Z-selective ruthenium catalyst or a Z-selective osmium catalyst.

[0031] In some embodiments, the metathesis catalyst used in the method of synthesizing the aliphatic olefin metathesis product of Formula I is a Z-selective metathesis catalyst having a structure according to Formula V:

[0032]

[0033] wherein:

[0034] M is selected from ruthenium and osmium;

[0035] X and Y are independently selected from S and O;

[0036] Z is selected from O, S(=0), N, and halogen;

[0037] each subscript m and subscript n is an integer independently selected from 0, 1, 2, 3, and 4;

[0038] each R a is independently selected from halogen, Ci-C6alkyl, alkoxy, aryl, and heteroaryl; or one R a is taken together with an adjacent R a to form an unsubstituted or substituted bicyclic ring or an unsubstituted or substituted polycyclic ring;

[0039] each R b is independently selected from halogen, Ci-C6alkyl, alkoxy, aryl, and heteroaryl; or one R b is taken together with an adjacent R b to form an unsubstituted or substituted bicyclic ring or an unsubstituted or substituted polycyclic ring;

[0040] R c is selected from hydrogen and Ci-C6alkyl;

[0041] each R d , R e , R f , and R g is independently selected from hydrogen and Ci-C6alkyl;

[0042] R 12 , and R 13independently selected from the group consisting of 2,4,6-triisopropylphenyl, 2,6-diisopropylphenyl, 2,6-diadamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert- butylphenyl, and 2,6-di-tert-butylphenyl;

[0043] each R 14 is independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, cyclohexyl, benzyl, and phenyl; and

[0044] R 15 is selected from the group consisting of hydrogen, halogen, and Ci-C6alkyl, or R 15 and one R 14 together form a bond.

[0045] In some embodiments, the method for synthesizing a fatty olefin metathesis product of Formula I further comprises forming an olefin metathesis reaction partner of Formula III by contacting an acylating agent with an enol according to Formula II

[0046]

[0047] In some embodiments, the method for synthesizing a fatty olefin metathesis product further comprises forming an enol of Formula II by reducing an unsaturated fatty carboxyl derivative according to Formula Ila

[0048]

[0049] wherein R 4 is selected from the group consisting of H and C 1-8 alkyl.

[0050] In some embodiments, the synthesis of a fatty olefin metathesis product comprises forming an internal olefin by contacting a terminal olefin with a metathesis catalyst to form an internal olefin. DETAILED DESCRIPTION

[0051] I. INTRODUCTION

[0052] The present invention provides methods for synthesizing high purity fatty olefin derivatives (e.g., straight chain lepidopteran pheromones; SCLPs) through stereoconservative olefin cross-metathesis of internal olefins having low isomeric purity. By combining Z-selective olefin metathesis catalysts with various low purity fatty olefin derivative feedstocks and internal olefin feedstocks, a variety of high Z-purity pheromones can be obtained. The present invention allows the use of low isomeric purity, commercially available olefin feedstocks to produce high purity SCLPs, which greatly increases the industrial applicability of this technology.

[0053] II. DEFINITIONS

[0054] The following definitions and abbreviations are used to interpret the present invention. As used herein, the terms “invention” or “the invention” are non-limiting terms and are not intended to refer to any single embodiment, but encompasses all possible embodiments.

[0055] 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, a mixture, a process, a method, an article, or an apparatus that comprises a list of elements is not necessarily limited to those elements but can include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or.

[0056] The term “about / around” as used herein to modify a numerical value indicates an approximate range around that explicit value. If “X” is the value, then “about X” or “around X” indicates a value of 0.9X to 1.1X, and in certain cases, a value of 0.95X to 1.05X or a value of 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” or “around X” is intended to teach and provide written description support for a requirement limitation of, for example, “0.99X.”

[0057] As used herein, the term “substantially” describes a range of values that is 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%.

[0058] As used herein, the term “majority” refers to a proportion in the range above 50%, for example, in the range of about 51% to 100%, 75% to 99.9%, 85% to 98.5%, or about 95% to 99%.

[0059] As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a fatty olefin metathesis product" includes a single fatty olefin metathesis product as well as a combination or mixture of two or more fatty olefin metathesis products (e.g., a mixture of fatty Z-olefin and fatty E-olefin metathesis products); reference to "an unsaturated fatty carboxyl derivative" includes a single unsaturated fatty carboxyl derivative as well as a combination or mixture of two or more unsaturated fatty carboxyl derivatives; reference to "an enol" includes a single enol as well as a combination or mixture of two or more enols; reference to "a substituent" includes a single substituent as well as two or more substituents, etc.

[0060] 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 "fatty olefin metathesis product" refers to a class of olefin-containing compounds formed by a metathesis reaction (i.e., a class of metathesis products formed from an olefin and a metathesis reaction partner) having the structure RC(O)O-R', wherein R is an alkyl group as described below, and R' is a straight chain alkenyl group containing at least 4 carbon atoms, for example, 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 C4 to C 30 As a non-limiting example, an "unsaturated fatty ester acetate" is a fatty olefin metathesis product produced by the cross-metathesis of an olefin metathesis reaction partner with an olefin, wherein R of RC(O)O-R' is methyl and R' is C2 to C 26 In the context of the present invention, "C8-C 28 (Z)-unsaturated fatty ester acetates are also non-limiting examples of fatty olefin metathesis products. In some embodiments, the fatty olefin metathesis product is a pheromone, for example, a linear lepidopteran pheromone (SCLP).

[0061] As used herein, the term "metathesis reaction" refers to a catalytic reaction involving the exchange of alkylene units (i.e., R2C= units) in a compound containing one or more carbon-carbon double bonds (e.g., an olefin compound) via the formation and cleavage of the carbon-carbon double bonds. Metathesis can occur between two molecules of the same structure (commonly referred to as self-metathesis) and / or between two molecules of different structures (commonly referred to as cross-metathesis).

[0062] As used herein, the term "pheromone" refers to a substance or characteristic mixture of substances that is secreted and released by an organism and detected by a second organism of the same species or a closely related species. Typically, detection of the pheromone by the second organism promotes a specific response, such as a well-defined behavioral response or developmental process. For example, insect pheromones can influence behaviors such as mating and aggregation. Examples of pheromones include, but are not limited to, compounds produced by moths of the order Lepidoptera (i.e., flying moths and butterflies belonging to the families Geometridae, Noctuidae, Arctiidae, and Lymantriidae), such as C 10 -C 18 acetates, C 10 -C 18 alcohols, C 10 -C 18 aldehydes, and C 17 -C 23 polyenes. "Unsaturated pheromones" refer to any pheromone having at least one carbon-carbon double bond.

[0063] As used herein, the term "contacting" refers to the process of bringing at least two different substances into contact so that they can react. However, it is understood that the resulting reaction product can be made directly from the reaction between the added reagents, or from an intermediate from one or more of the added reagents that can be produced in the reaction mixture.

[0064] As used herein, the term "metathesis reaction partner" refers to a compound having a carbon-carbon double bond that can react with an alkene in a metathesis reaction to form a new carbon-carbon double bond. The metathesis reaction partner can be an aliphatic alkene-containing compound, such as an olefin metathesis reaction partner. The term "olefin metathesis reaction partner" refers to a compound having the structure R-C(O)O-R', where R is an alkyl group as described below, and R' is a linear alkenyl group comprising at least four carbon atoms, such as 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 C6to C 34 linear alkenyl group. For example, "unsaturated fatty alcohol acetate" is an olefin metathesis reaction partner where R of R-C(O)O-R' is methyl and R' is a C4to C 28 linear alkenyl group. Other non-limiting examples of olefin metathesis reaction partners include "fatty C 12 -C 30 olefin acetate" and "C 10 -C 28 fatty alkenyl alcohol acetate" where R of R-C(O)O-R' is methyl and R' is a C 10to C 28 Straight chain alkenyl.

[0065] 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 its derivatives. Olefins can be unsubstituted or substituted with one or more functional groups, including alcohol groups, protected alcohol groups, carboxyl groups, and carboxylate groups. As used herein, the term "olefin" includes hydrocarbons (e.g., dienes, trienes, etc.) having more than one carbon-carbon double bond. Hydrocarbons and their derivatives having more than one carbon-carbon double bond are also referred to as "polyenes." The term "fatty olefin" refers to an olefin having at least four carbon atoms; fatty 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 methods of the present invention have 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 from 4 to 26 carbon atoms.

[0066] As used herein, the term "internal olefin" refers to an olefin in which each olefinic carbon (i.e., the 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’ , where R 1’ and R 2’ At least one of them is not hydrogen and R 3’ and R 4’ At least one of the R is not hydrogen). The internal olefin may be disubstituted, trisubstituted, or tetrasubstituted (e.g., a disubstituted internal olefin: R 5’ HC═CHR 8’ and / or HR 6’ C═CR 7’ 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’; wherein R 5’ , R 6’ , R 7’ and R 8’ can be the same or different and are each independently an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, or a functional group.

[0067] As used herein, the term "terminal olefin" refers to an olefin in which one olefin carbon (i.e., the carbon of the carbon-carbon double bond (C=C)) is substituted with at least one non-hydrogen substituent, and the other olefin carbon is unsubstituted (e.g., R 9’ R 10’ C=CH2, wherein R 9’ and R 10’ are not hydrogen). Terminal olefins can be mono-substituted or di-substituted (e.g., mono-substituted terminal olefin: R 9’ HC=CH2and / or HR 10’ C=CH2; and di-substituted terminal olefin: R 9’ R 10’ C=CH2; wherein R 9’ and R 10’ can be the same or different and are each independently an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, or a functional group.

[0068] A "fatty olefin derivative" refers to a compound obtained from an olefin starting material or a fatty olefin starting material used in the methods of the present application. Examples of fatty olefin derivatives include, but are not limited to, unsaturated fatty alcohols (i.e., enols), unsaturated fatty alcohol acetates, and unsaturated fatty ester acetates (e.g., olefin metathesis reaction partners and fatty olefin metathesis products), unsaturated fatty aldehydes, unsaturated fatty carboxy derivatives (e.g., unsaturated fatty acids, unsaturated fatty acid alkyl esters), and polyenes. In the context of the present application, "metathesis products" and "fatty olefin metathesis products" are both classes of fatty olefin derivatives. In some embodiments, the fatty olefin derivatives used in the methods of the present application have 6 to 34 carbon atoms. In some embodiments, the fatty olefin derivatives synthesized according to the methods of the present application have 6 to 30 carbon atoms. In certain other embodiments, the fatty olefin derivatives used in the methods of the present application include a mixture of fatty olefin derivatives having 4 to 34 carbon atoms. In certain other embodiments, the fatty olefin derivatives synthesized according to the methods of the present application include a mixture of fatty olefin derivatives having 4 to 30 carbon atoms.

[0069] Δ 9 - unsaturated olefin refers to an olefin in which the ninth carbon-carbon bond from the end of the olefin chain is a double bond (e.g., Δ 9 - unsaturated fatty alcohol, Δ 9- unsaturated fatty alcohol acetate, Δ 9 - unsaturated fatty ester acetate, Δ 9 - unsaturated fatty aldehyde, Δ 9 - unsaturated fatty carboxyl derivative, Δ 9 - unsaturated fatty acid, Δ 9 - unsaturated fatty acid alkyl ester, etc.). For example, Δ 9 - unsaturated fatty acid refers to an olefin carboxylic acid in which the ninth carbon-carbon bond, counting from the carboxylic acid end of the olefin chain, is a double bond. Δ 9 - Examples 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). As another non-limiting example, Δ 9 - unsaturated fatty ester acetate refers to an olefin ester acetate in which the ninth carbon-carbon bond, counting from the acetate end of the olefin chain, is a double bond. Δ 9 - Examples of unsaturated fatty 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.

[0070] Similarly, Δ 11 - unsaturated olefin refers to an olefin in which the eleventh carbon-carbon bond, counting from the end of the olefin chain, is a double bond (e.g., Δ 11 - unsaturated fatty alcohol, Δ 11 - unsaturated fatty alcohol acetate, Δ 11 - unsaturated fatty ester acetate, Δ 11 - unsaturated fatty aldehyde, Δ 11 - unsaturated fatty carboxyl derivative, Δ 11 - unsaturated fatty acid, Δ 11 - unsaturated fatty acid alkyl ester, etc.). For example, Δ 11 - unsaturated fatty acid refers to an olefin carboxylic acid in which the eleventh carbon-carbon bond, counting from the carboxylic acid end of the olefin chain, is a double bond. Δ 11 - Examples of unsaturated fatty acids include, but are not limited to, 11-dodecenoic acid, eicosenoic acid (i.e., (Z)-eicosa-11-enoic acid or (Z)-eicosa-11-enoic acid), and trans-eicosenoic acid (i.e., (E)-eicosa-11-enoic acid or (E)-eicosa-11-enoic acid). It should be noted that the prefixes “eicosa” and “eicos” are used interchangeably to refer to a hydrocarbon chain having 20 carbons (e.g., a fully saturated C 20 hydrocarbon chain, i.e., an alkyl group; or a C 20 hydrocarbon chain, i.e., an alkenyl group or an olefin). As another non-limiting example, Δ 11- Unsaturated fatty ester acetate refers to an olefin ester acetate in which the eleventh carbon-carbon bond, counting from the acetate terminus of the olefin chain, is a double bond.Δ 11 - Examples of unsaturated fatty ester acetates include, but are not limited to, 11-decenyl acetate, (Z)-tetradec-11-en-1-yl acetate, and (E)-tetradec-11-en-1-yl acetate.

[0071] As used herein, the terms “enol” and “fatty enol” are used interchangeably and refer to a compound having the structure R’-OR, wherein R’ is a linear alkenyl group comprising at least 4 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 C6to C 34 linear alkenyl group. As non-limiting examples, “C 10 to C 28 fatty enol” is an enol (i.e., a fatty enol) in which R of R’-OR is hydrogen and R’ is a C 10 to C 28 linear alkenyl group.

[0072] As used herein, the term “unsaturated fatty carboxyl derivative” refers to a fatty alkene compound comprising a carboxyl moiety and is used in the methods of the present application. The term “carboxyl” as used herein denotes a group of the formula “-C(O)O-”. In the context of the present application, unsaturated fatty carboxyl derivatives include “unsaturated fatty acids” and “unsaturated fatty acid alkyl esters”. The term “unsaturated fatty acid” as used herein refers to a compound having the structure R’-C(O)OH, wherein R’ is a linear alkenyl group comprising 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’ of R’-C(O)OH is a C6to C 34 linear alkenyl group. As non-limiting examples, “C 12- C 30 unsaturated fatty acid” is an unsaturated fatty acid in which R’ of R’-C(O)OH is a C 11- C 29 linear alkenyl group. The term “unsaturated fatty acid alkyl ester” as used herein refers to a compound having the structure R’-C(O)O-R, wherein R’ is a linear alkenyl group comprising 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, R’ of R’-C(O)O-R is a C6to C 34Linear alkenyl. As a non-limiting example, "C 12- C 30 Unsaturated fatty acid methyl ester" is an unsaturated fatty acid alkyl ester, wherein R of R'-C(0)0-R is methyl and R' is C 10- C 28 Linear alkenyl. The unsaturated fatty carboxyl 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 carboxyl derivative is obtained from a natural oil or a natural oil derivative.

[0073] As used herein, the term "isomer" refers to a molecule having the same chemical formula but a different chemical structure as another molecule. In other words, isomers contain the same number of atoms of each element, but they have a different arrangement of their atoms. Isomers include "structural isomers" and "stereoisomers." In "structural isomers" (also known as "constitutional isomers"), the atoms have different sequences of bonding. Structural isomers have different IUPAC names and can or can not belong to the same functional group. This type of isomer includes skeletal isomers (wherein the hydrocarbon chain has a variable amount of branching) and positional isomers (which involves the position of functional groups on the chain); and functional group isomers, wherein the molecular formula is the same but the functional groups are different.

[0074] As used herein, the term "positional isomer" refers to a first compound having the same carbon skeleton and functional groups as a second compound, but a different position of the functional groups on or in the carbon skeleton. In particular embodiments, a positional isomer can have a functional group (e.g., an alkene, a hydroxyl, an aldehyde, and an acetyl group, among others) located at a different position of the carbon skeleton compared to its positional isomer. For example, a positional isomer of (Z)-tetradec-9-en-1-yl acetate is (Z)-tetradec-11-en-1-yl acetate because (Z)-tetradec-9-en-1-yl acetate is produced by cross-metathesis of (Z)-octadec-9-en-1-yl acetate with (Z)-dec-5-ene, and (Z)-tetradec-11-en-1-yl acetate is produced by cross-metathesis of (Z)-eicos-11-en-1-yl acetate with (Z)-hex-3-ene.

[0075] In stereoisomers, the bond structure is the same, but the geometric positioning of the atoms and functional groups in space is different. Such isomers include enantiomers, which are isomers that are mirror images of each other that cannot be superimposed on each other, 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 the atoms of the substituents at a bond. The double bonds within the olefins and aliphatic olefin derivatives described herein prevent rotation of the molecule by fixing it in one of two possible configurations, each of which represents a different geometric isomer of the molecule. These geometric isomers are named E (from the German word Entgegen, opposite) or Z (Zusammen, together) when the carbon chain is attached on opposite (trans) or the same (cis) side of the double bond, respectively. Thus, the olefins and aliphatic olefin derivatives described herein can be in the (E) configuration, the (Z) configuration, or a mixture of (E) and (Z) configurations. Another type of isomer, the conformational isomer / conformer, can be a rotamers, diastereomers, or enantiomers, depending on the exact compound.

[0076] 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) or, particularly, an aliphatic olefin derivative in isomerically pure form (e.g., about 90% Z-isomer or about 90% E-isomer) according to the methods described herein in the presence of a metathesis catalyst. In the context of the present application, “stereoselectivity” or “selectivity” refers to a cross-metathesis reaction that preferentially produces one stereoisomer over a second stereoisomer, i.e., produces a metathesis product or aliphatic olefin metathesis product in which the ratio of the desired stereoisomer to the less desired stereoisomer is greater than 1:1.

[0077] “Z-stereoselectivity” or “Z-selectivity” describes the ability to produce a Z-isomer of a compound (i.e., an olefin or aliphatic olefin derivative described herein) in Z-isomerically pure form or predominantly pure form or substantially pure form according to the methods described herein in the presence of a metathesis catalyst; or the ability to specifically produce a Z-isomer of an aliphatic olefin derivative from a 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 can optionally comprise a mixture of E- and Z-isomers, or which can be at least 95% Z. Further, in the context of the present invention, “Z-stereoselectivity” or “Z-selectivity” refers to a cross-metathesis reaction that preferentially produces a Z-isomer over an E-isomer, i.e., a Z-aliphatic olefin metathesis product in which the ratio of Z-isomer to E-isomer is greater than 1 : 1. A “Z-selective catalyst” refers to a Group 8 transition metal catalyst as described herein that preferentially produces a Z-aliphatic olefin metathesis product in the cross-metathesis reaction methods of the present invention. Z-selectivity can also be expressed as a percentage of isomeric product formed. For example, an aliphatic olefin derivative (e.g., a metathesis product, a aliphatic olefin metathesis product, etc.) prepared according to the methods of the present invention is at least 80% Z, typically greater than 85% Z, or 90% Z, or 95% Z, and 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.

[0078] In the case of individual isomers, the terms “isomeric 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., a metathesis product, a 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., a metathesis product, a aliphatic olefin metathesis product, etc.) prepared according to the methods of the present invention is greater than 80% Z-isomer, typically 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.

[0079] As used herein, the term “Z:E ratio” refers to the proportion of the amount of a Z-isomer (e.g., a Z-aliphatic olefin metathesis product) relative to the amount of an 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) having a higher Z:E ratio than the precursor material (e.g., a metathesis reaction partner).

[0080] As used herein, the term "low isomeric purity" refers to an olefin, metathesis reaction partner, olefin starting material, olefin-containing reactant, and fatty olefin derivative (e.g., an alkenol, an unsaturated fatty alcohol acetate, an unsaturated fatty ester acetate, an olefin metathesis reaction partner, a fatty olefin metathesis product, an unsaturated fatty aldehyde, an unsaturated fatty carboxyl derivative, a metathesis product, etc.) used in or produced by the methods of the present application that is less than 90% Z-isomer (i.e., 10% or more E-isomer).

[0081] As used herein, the term "high Z-selectivity" refers to more than 85% of the formed metathesis product and / or fatty olefin metathesis product being in the Z-configuration.

[0082] 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 appreciate that a metathesis catalyst can participate in a metathesis reaction to increase the rate of the reaction, but is not itself consumed in the reaction. A "ruthenium catalyst" refers to a metathesis catalyst having one or more ruthenium atoms. An "osmium catalyst" refers to a metathesis catalyst having one or more osmium atoms.

[0083] 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 can also include reacting an intermediate with at least one reagent to form another intermediate species or product.

[0084] The term "functional group" includes any functional group known in the art.

[0085] As used herein, the term "acyl" refers to the functional group -C(O)-R, wherein R is an alkyl group as described below.

[0086] As used herein, the term "acylation" refers to the conversion of an alcohol group (-OH) to an ester group (-OC(O)-R), wherein R is an alkyl group as described below.

[0087] As used herein, the term "acylating agent" refers to a compound that is capable of reacting with a substrate compound to add a -C(O)-R moiety to the compound. An acylating agent can be used, for example, to form an ester (i.e., -C(O)O-R) on a compound having a hydroxyl moiety (i.e., -OH). An acylating agent that can be used in the present application can be one or more C1-C 20Linear or branched alkyl or aryl carboxylic anhydrides, carboxylic halides, dienones, or acetoacetates. Examples of carboxylic anhydrides suitable for use as acylating agents in the present application 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 halides suitable for use as acylating agents in the present application include acetyl, propionyl, butyryl, hexanoyl, 2-ethylhexanoyl, lauroyl, palmitoyl, and stearoyl chlorides. Examples of acetoacetates suitable for use as acylating agents in the present application include, but are not limited to, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, and t-butyl acetoacetate.

[0088] 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 are 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).

[0089] As used herein, the term "reducing" refers to the transfer of electron density from a hydrogenation catalyst or reducing agent to a substrate compound. The transfer of electron density is typically carried out by a method that includes the addition of hydrogen to the substrate compound.

[0090] As used herein, the term "reducing agent" refers to any agent effective to reduce a carboxylic acid group (i.e., -C(0)OH) to an alcohol group (i.e., -CH2-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.

[0091] As used herein, the term "hydrogenation catalyst" refers to any catalyst effective to hydrogenate an alkyl ester group (i.e., -C(0)0-R) to an alcohol group (i.e., -CH2-OH), where R is an alkyl group as described below. The hydrogenation catalyst can be a heterogeneous catalyst or a homogeneous catalyst.

[0092] In the context of the present application, the term "heterogeneous" refers to reaction conditions in which one or more reagents or participants (i.e., heterogeneous catalyst) are not dissolved in the reaction medium; or, in other words, when mixed together, one or more reagents or participants are in a different phase (e.g., a solid catalyst) compared to other solvents, reagents, compounds, or substrates (e.g., liquid or vapor). The term "homogeneous" refers to reaction conditions in which all reagents or participants (i.e., homogeneous catalyst) are soluble in the reaction medium (i.e., when mixed together are in the same phase as other solvents, reagents, compounds, or substrates). The terms "heterogeneous" and "homogeneous" can also refer to a catalyst. For example, a "heterogeneous catalyst" refers to a catalyst that is not dissolved in the reaction medium; or, in other words, when mixed together, the catalyst is in a different phase (e.g., a solid catalyst) compared to other solvents, reagents, compounds, or substrates (e.g., liquid or vapor). A "homogeneous catalyst" refers to a catalyst that is soluble in the reaction medium (i.e., when mixed together is in the same phase as other solvents, reagents, compounds, or substrates).

[0093] As used herein, the term "aliphatic" or "aliphatic group" means a straight-chain (i.e., unbranched) or branched, substituted or unsubstituted hydrocarbon chain that is completely saturated or that contains one or more units of unsaturation, or a monocyclic, bicyclic or tricyclic hydrocarbon that is completely saturated or that contains one or more units of unsaturation, but which is not aromatic (also referred to herein as "carbocyclic" or "alicyclic") with a single point of attachment to the rest of the molecule. Unless otherwise specified, an aliphatic group contains from 1 to 30 aliphatic carbon atoms. In some embodiments, an aliphatic group contains 1 to 20 aliphatic carbon atoms. In other embodiments, an aliphatic group contains 1 to 10 aliphatic carbon atoms. In other embodiments, an aliphatic group contains 1 to 5 aliphatic carbon atoms, and in other embodiments, an aliphatic group contains 1, 2, 3, or 4 aliphatic carbon atoms. In some embodiments, "cycloaliphatic" (or "carbocyclic") refers to a monocyclic C3-C6 hydrocarbon or a C8-C12 10 dihydrocarbon that is not aromatic with a single point of attachment to the rest of the molecule. 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 groups. The term "heteroaliphatic" refers to aliphatic groups in which at least one carbon atom 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).

[0094] 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 group has about 1-40 carbon atoms in its backbone, such as 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 some embodiments, a straight-chain or linear alkyl group is C1-C 30 , and the branched alkyl group is C3-C 30 In some cases, a straight chain or branched chain alkyl group has about 1-20 carbon atoms in its backbone. In some embodiments, a straight chain or branched chain alkyl group has about 1-10 carbon atoms in its backbone, for example, 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 groups include, but are 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, wherein the lower alkyl group contains 1-4 carbon atoms (e.g., C1-C4 is a straight chain lower alkyl group).

[0095] 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 are replaced by 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.

[0096] As used herein, the term "alkoxy" refers to the moiety -OR, wherein R is an alkyl group as defined above. The term "silylalkyl" refers to an alkyl group as defined herein, wherein at least one carbon atom is substituted with a silicon atom. The term "siloxy" refers to the moiety -OSiR3, wherein each R is independently selected from H, alkyl, substituted alkyl, aryl, and substituted aryl as described herein.

[0097] As used herein, the term "cycloalkyl" refers to saturated monocyclic, bicyclic or tricyclic hydrocarbon groups 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, the cycloalkyl ring has from about 3 to 10 carbon atoms in its ring structure, where the rings are monocyclic or bicyclic, and optionally, about 5, 6, or 7 carbons in the ring structure.

[0098] As used herein, the term "alkynyl" refers to alkyl groups as defined herein having one or more triple bonds.

[0099] As used herein, the term "aryl" used alone or as part of the larger term "aralkyl," "aralkoxy," or "aryloxyalkyl," refers to a mono- or bicyclic ring system having a total of five to fourteen ring members, wherein at least one ring in the system is aromatic, and wherein each ring in the system contains from 3 to 7 ring members. The term "aryl" can be used interchangeably with the term "aryl ring." In certain embodiments of the application, "aryl" refers to aromatic ring systems including, but not limited to, phenyl, biphenyl, naphthyl, anthryl, and the like, which can have one or more substituents. Also included within the scope of the term "aryl" as used herein are groups in which an aromatic ring is fused to one or more non-aromatic rings, such as indanyl, phthalimidyl, naphthalimidyl, phenanthridinyl or tetrahydronaphthyl, and the like. The term "aryloxy" refers to the moiety -OR, wherein R is aryl as defined above.

[0100] As used herein, the terms "heteroaryl" and "heteroar-," by themselves or as part of another group, such as "heteroaralkyl" or "heteroaralkoxy," refer to groups having 5 to 10 ring atoms (i.e., a monocyclic or bicyclic ring), in some embodiments 5, 6, 9, or 10 ring atoms. In some embodiments, such rings have 6, 10, or 14 p electrons shared in a cyclic array; and, in addition to carbon atoms, between one and five heteroatoms. The term "heteroatom" refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen. Heteroaryl groups include, without limitation, 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, cycloalkyl, or heterocyclyl rings, where the radical or point of attachment is on the heteroaromatic ring. Non-limiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenoxazine, tetrahydroquinolinyl, tetrahydroisoquinoline, and pyrido[2,3-b]-l,4-oxazin-3(4H)-one. The heteroaryl group can be mono- or bicyclic. The term "heteroaryl" can be used interchangeably with the terms "heteroaryl ring," "heteroaryl group," or "heteroaromatic," wherein any of these terms includes an optionally substituted ring. The term "heteroaralkyl" refers to an alkyl group substituted with a heteroaryl, wherein the alkyl and heteroaryl portions independently are optionally substituted.

[0101] Examples of aryl and heteroaryl groups include, but are not limited to, phenyl, pyrrolyl, furanyl, thienyl, imidazolyl, oxazolyl, thiazolyl, triazolyl, pyrazolyl, pyridyl, pyrazinyl, pyridazinyl, and pyrimidinyl, among others. It will be appreciated that when aryl and heteroaryl groups are used as ligands to a coordinated metal center, the aryl and heteroaryl groups can have sufficient ionic character to coordinate the metal center. For example, when a heteroaryl group such as pyrrole is used as a nitrogen-containing ligand, as described herein, it will be appreciated that the pyrrole group has sufficient ionic character (e.g., is sufficiently deprotonated to define a pyrrolyl group) to coordinate the metal center. In some cases, for example, an aryl or heteroaryl group can include at least one functional group having sufficient ionic character to coordinate the metal center, such as a diphenoide group.

[0102] As used herein, the terms "heterocycle," "heterocyclyl," "heterocyclic radical" and "heterocyclic" are used interchangeably and mean a stable 5- to 7-membered monocyclic or 7-10 membered bicyclic heterocyclic moiety which is either saturated or partially unsaturated and which, except for the ring atoms, has from one to four heteroatoms per ring atom which are independently examples, in a saturated or partially unsaturated ring having from 1-3 heteroatoms selected from oxygen, sulfur or nitrogen, the nitrogen can be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl) or + NR (as in N-substituted pyrrolidinyl).

[0103] The heterocycle can be attached at any heteroatom or carbon atom of the ring to its side group to give a stable structure, and any ring atom can optionally be substituted. Examples of such saturated or partially unsaturated heterocyclyl groups include, but are not limited to, tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepanyl, oxazepanyl, thiazepanyl, morpholinyl, and quinuclidinyl. The terms "heterocycle," "heterocyclyl," "heterocyclyl ring," "heterocyclic radical," "heterocyclic moiety," and "heterocyclic radical" are used interchangeably herein, and also include groups in which the heterocyclyl ring is fused to one or more aryl, heteroaryl, or cycloalkyl rings, such as indolinyl, 3H-indolyl, chromanonyl, phenanthridinyl, or tetrahydroquinolinyl. The heterocyclyl group can be mono- or bicyclic. The term "heterocyclylalkyl" means an alkyl group substituted with a heterocyclyl group, wherein the alkyl and heterocyclyl portions independently are optionally substituted.

[0104] The terms "halogen" and "halo" are used interchangeably and mean F, CI, Br, or I.

[0105] As used herein, the term "protecting group" refers to a chemical moiety that renders a functional group unreactive but which can also be removed to restore the functional group. 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-butoxycarbonyl (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); acetamido; phthalimido; and the like. Other alcohol protecting groups and amine protecting groups are known to those skilled in the art, including, for example, those described by Green and Wuts (Protective Groups in Organic Synthesis, 4th ed. 2007, Wiley-Interscience, New York).

[0106] As described herein, the compounds of the present application can contain "optionally substituted" moieties. In general, the term "substituted", whether preceded by the term "optionally" or not, means that one or more hydrogens of the designated moiety are replaced by a suitable substituent. Unless otherwise indicated, an "optionally substituted" group can have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure can be substituted with more than one substituent selected from a specified group, the substituent can be either the same or different at every position. Combinations of substituents envisioned by this application are typically those that result in the formation of stable or chemically feasible compounds. The term "stable", as used herein, refers to compounds that are substantially unaltered when subjected to conditions that would allow for their production, detection, and in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.

[0107] Suitable monovalent substituents on substitutable carbon atoms of "optionally substituted" groups are independently halogen; -(CH2) 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(ORα )2; -(CH2) 0-4 SR α ; -(CH2) 0-4 Ph, which can be substituted by R α ; -(CH2) 0-4 O(CH2) 0-1 Ph, which can be substituted by R α ; -CH=CHPh, which can be substituted by R α ; -(CH2) 0-4 O(CH2) 0-1 -pyridyl, which can be substituted by R α ; -NO2; -CN; -N3; -(CH2) 0-4 N(R α )2; -(CH2) 0-4 N(R α )C(O)R α ; -N(R°)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- 4SR-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(NOR α )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)2NR 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 straight or branched chain alkylene)O-N(R α )2; or -(C 1-4 straight or branched chain alkylene)C(O)O-N(R α )2, wherein each R α may be substituted and independently hydrogen, C 1-6 aliphatic, -CH2Ph, -O(CH2) 0- 1Ph, -CH2-(5-6 membered heteroaryl ring), or a 5-6 membered saturated, partially unsaturated, or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or two independent occurrences of R αwith their intervening atoms form a 3-12 membered saturated, partially saturated, or aromatic monocyclic or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, which can be substituted as defined below.

[0108] R α (or by two independently occurring R α groups on the same carbon atom) or R 0-2 is taken together with the atom to which they are attached to form a 3-7 membered saturated, partially saturated, or aromatic ring having 0-2 heteroatoms independently selected from nitrogen, oxygen, and sulfur, which can be substituted as defined below. β ; -(haloR 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 straight or branched chain alkylene)C(O)OR β ; or -SSR β ; wherein each R β is unsubstituted or substituted only with one or more halogens, and is independently selected from C 1-4 aliphatic, -CH2Ph, -O(CH2) 0-1 Ph, or a 5-6 membered saturated, partially saturated, or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. R α Suitable divalent substituents on a saturated carbon atom include =O and =S.

[0109] Suitable divalent substituents on a saturated carbon atom of an "optionally substituted" group include the following: =O; =S; =NNR γ 2; =NNHC(O)Rγ ; =N NHC(O)OR γ ; =N NHS(O)2R γ ; =NR γ ; =NOR γ ; -O(C(R γ 2)) 2-3 O-; or -S(C(R γ 2)) 2-3 S-; wherein each independent occurrence of R γ is selected from hydrogen, C 1-6 aliphatic, or an unsubstituted 5-6 membered saturated, partially unsaturated, or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. Suitable divalent substituents bound to ortho-substitutable carbons of an "optionally substituted" group include: -O(CR β 2) 2-3 O-, wherein each independent occurrence of R β is selected from hydrogen, C 1-6 aliphatic, or an unsubstituted 5-6 membered saturated, partially unsaturated, or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0110] R γ aliphatic groups include halogen, -R δ , -(haloR δ ), -OH, -OR δ , -O(haloR δ ), -CN, -C(O)OH, -C(O)OR δ , -NH2, -NHR δ , -NR δ 2, or -NO2, wherein each R δ is unsubstituted or substituted by "halo" only by one or more halogens, and is independently C 1-4 aliphatic, -CH2Ph, -O(CH2) 0-1 Ph, or a 5-6 membered saturated, partially unsaturated, or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0111] 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)2NRε 2, -C(S)NR ε 2, -C(NH)NR ε 2, or -N(R ε )S(O)2R ε ; wherein each R ε is independently hydrogen, a C 1-6 aliphatic group, unsubstituted -OPh, or an unsubstituted 5-6 membered saturated, partially unsaturated, or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or, notwithstanding the definition above, two independent occurrences of R ε , together with their intervening atom(s), form an unsubstituted 3-12 membered saturated, partially unsaturated, or aromatic monocyclic or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0112] R ε aliphatic group is independently halogen, -R δ , -(haloR δ ), -OH, -OR δ , -CN, -C(O)OH, -C(O)OR δ , -NH2, -NHR δ , -NR δ 2, or -NO2, wherein each R δ is unsubstituted or substituted with only one or more halogen, and is independently a C 1-4 aliphatic group, -CH2Ph, -O(CH2) 0-1 Ph, or a 5-6 membered saturated, partially unsaturated, or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0113] In some embodiments, the term "substituted" is contemplated to include all permissible substituents of organic compounds, "permissible" being in the context of the valency chemistry of the organic compounds. In some instances, "substituted" can generally mean substituted with a substituent described herein. However, as used herein, "substituted" does not encompass any substitution or alteration that would otherwise destroy the fundamental functionality of the molecule as described herein. For example, "substituted phenyl" groups must still include a phenyl moiety, and cannot be modified by substitution to become, for example, a cyclohexyl group. Broadly speaking, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described herein. The permissible substituents can be one or more and the same or different for each substituent group. For example, a substituted alkyl group can be CF3. For purposes of this application, the heteroatoms of heteroatom-containing

[0114] Examples of substituents include, but are not limited to, alkyl, aryl, arylalkyl, cycloalkyl, heterocycloalkyl, hydroxy, alkoxy, aryloxy, perhaloalkoxy, arylalkoxy, heteroaryl, heteroaryloxy, heteroarylalkyl, heteroarylalkoxy, azido, amino, halogen, alkylthio, oxo, acylalkyl, carboxyl ester, carboxyl, carboxamido, nitro, acyloxy, aminoalkyl, alkylaminoaryl, alkylaryl, alkylaminoalkyl, alkoxyaryl, arylamino, arylalkylamino, alkylsulfonyl, carboxamidoalkylaryl, carboxamidoaryl, hydroxyalkyl, haloalkyl, alkylaminoalkylcarboxyl, carbamidoalkyl, cyano, alkoxyalkyl, perhaloalkyl, arylalkoxyalkyl, and the like.

[0115] As used herein, the term "natural oil" refers to an oil derived from a plant or an animal source. The term "natural oil" includes natural oil derivatives unless otherwise indicated. The plant or animal source can be a modified plant or animal source (e.g., a genetically modified plant or animal source) unless otherwise indicated. Examples of natural oils include, but are not limited to, vegetable oils, algal oils, fish oils, animal fats, tall oils, derivatives of these oils, combinations of any of these oils, and the like.

[0116] The term "plant oil" refers to a natural oil or natural oil derivative from any suitable component of a plant (e.g., a plant, fruit, leaf, stem, shrub, flower, seed, or tree nut), or any combination thereof. Representative, non-limiting examples of plant oils include almond oil, canola oil, avocado oil, argan oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, grape seed oil, olive oil, palm oil, peanut oil, hemp oil, European nut oil, safflower oil, sesame oil, soybean oil, sunflower oil, flaxseed oil, palm kernel oil, tung oil, jatropha oil, jojoba oil, mustard oil, oilseed rape oil, borage oil, and castor oil. Representative, non-limiting examples of animal fats include lard, tallow, poultry fat, butter, and fish oil. Tall oil is a byproduct of wood pulp manufacture. "Natural seed oil" refers to a natural plant oil obtained specifically from the seed of a plant, as opposed to the fruit (or other component) of a plant. Thus, not all plant oils are seed oils. For example, olive oil and peanut oil are not natural seed oils. Representative, non-limiting examples of natural seed oils include almond oil, canola oil, avocado oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, grape seed oil, hemp oil, European nut oil, safflower oil, sesame oil, soybean oil, sunflower oil, flaxseed oil, palm kernel oil, tung oil, jatropha oil, jojoba oil, mustard oil, oilseed rape oil, borage oil, and castor oil.

[0117] "Natural oil derivative" refers to a compound (or mixture of compounds) derived from a natural oil using any one or combination of methods known in the art. These methods include, but are not limited to, saponification, fat splitting, interesterification, esterification, hydrogenation (partial or complete), isomerization, oxidation, reduction, and metathesis. Representative, non-limiting examples of natural oil derivatives include gums, phospholipids, soapstock, acidulated soapstock, distillate or distillate residue, fatty acids, and fatty acid alkyl esters (e.g., non-limiting examples such as 2-ethylhexyl esters) and hydroxyl-substituted variants thereof. For example, a natural oil derivative can be a fatty acid methyl ester ("FAME") derived from a natural oil glyceride.

[0118] The term "contaminant" broadly and without limitation refers to any impurity mixed with a substrate for olefin metathesis, regardless of the amount of its presence. "Catalyst-poisoning contaminants" refer to contaminants that can adversely affect the performance of a metathesis catalyst. Examples of catalyst-poisoning contaminants include, but are not limited to, water, peroxides, and hydroperoxides.

[0119] III. Methods of synthesis of fatty olefin metathesis products

[0120] In some embodiments, the present application provides a method for synthesizing a Z- enriched fatty olefin metathesis product, the method 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 fatty olefin metathesis product, wherein:

[0121] The fatty olefin metathesis product is a mixture of Z-olefin and E-olefin at a product Z:E ratio,

[0122] The olefin metathesis reaction partner comprises a mixture of Z-olefin and E-olefin at a starting Z:E ratio,

[0123] The fatty olefin metathesis product comprises a mixture of Z-olefin and E-olefin at a product Z:E ratio, and

[0124] The product Z:E ratio is higher than the starting Z:E ratio.

[0125] The process of the present application is highly Z-selective, wherein over 80% of the formed metathesis product is in the Z-configuration. More specifically, the process of the present application produces a fatty olefin metathesis product, e.g., a compound of Formula I, that is at least 97% Z. Furthermore, the present application provides a process for producing a fatty olefin metathesis product of high Z-isomeric purity from an olefin starting material of low Z-isomeric purity.

[0126] In some embodiments, a process for synthesizing a fatty olefin metathesis product according to Formula I is provided.

[0127]

[0128] The process comprises contacting an olefin metathesis reaction partner according to Formula III

[0129]

[0130] with an internal olefin according to Formula IV

[0131]

[0132] in the presence of a metathesis catalyst to form a fatty olefin metathesis product; wherein:

[0133] R 1 is selected from the group consisting of H and C 1-6 alkyl;

[0134] R 2 is selected from the group consisting of C 1-18 alkyl and C 2-18 alkenyl;

[0135] R 3 is C 1-18 alkyl;

[0136] the subscript y is an integer from 0 to 17;

[0137] the subscript z is an integer from 0 to 17; and

[0138] The metathesis catalyst is a Z-selective Group 8 transition metal catalyst.

[0139] In some embodiments, the aliphatic olefin metathesis product is an enal of formula VI:

[0140]

[0141] The metathesis reaction partner is a compound of formula VII:

[0142]

[0143] The internal olefin is a compound of formula IV

[0144]

[0145] R 1 is C 1-6 alkyl;

[0146] R 2 is selected from C 1-18 alkyl and C 2-18 alkenyl;

[0147] R 3 is C 1-18 alkyl;

[0148] the subscript y is an integer from 0 to 17;

[0149] the subscript z is an integer from 0 to 17; and

[0150] The Group 8 transition metal metathesis catalyst is a Z-selective Group 8 transition metal catalyst.

[0151] Metathesis of aliphatic olefin derivatives

[0152] In some embodiments, the method for synthesizing an aliphatic olefin metathesis product according to formula I

[0153]

[0154] comprises contacting an olefin metathesis reaction partner according to formula III

[0155]

[0156] with an internal olefin according to formula IV

[0157]

[0158] in the presence of a Z-selective Group 8 transition metal catalyst metathesis catalyst (e.g., a Z-selective ruthenium catalyst or a Z-selective osmium catalyst) to form the aliphatic olefin metathesis product; wherein:

[0159] R 1 is selected from H and C 1-6 alkyl;

[0160] R 2 selected from C 1-18 alkyl and C 2-18 alkenyl;

[0161] R 3 is C 1-18 alkyl;

[0162] the subscript y is an integer from 0 to 17; and

[0163] the subscript z is an integer from 0 to 17.

[0164] In some embodiments, the method for synthesizing a fatty olefin metathesis product of Formula I further comprises forming an olefin metathesis reaction partner of Formula III by contacting an acylating agent with an enol according to Formula II

[0165]

[0166] In some embodiments, the acylating agent used to contact the enol of Formula II to form the olefin metathesis reaction partner of Formula III is acetic anhydride.

[0167] Any acylating agent suitable for forming an olefin metathesis reaction partner of Formula III can be used in the methods of the present application. Examples of suitable acylating reagents include acid anhydrides (e.g., acetic anhydride), acid chlorides (e.g., acetyl chloride), active esters (e.g., pentafluorophenyl esters of carboxylic acids), and carboxylic acids used with coupling agents such as dicyclohexylcarbodiimide or carbonyldiimidazole. Typically, 1-10 molar equivalents of the acylating agent are used relative to the enol. For example, 1-5 molar equivalents of the acylating agent or 1-2 molar 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) are used relative to the enol to form the olefin metathesis reaction partner of Formula III.

[0168] Base can be used to promote the acylation of acylating agent to enol.The example of suitable base includes potassium carbonate, sodium carbonate, sodium acetate, Huenig base (that is, N, N-diisopropylethylamine), lutidine (including 2,6-lutidine (that is, 2,6-lutidine)), triethylamine, tributylamine, pyridine, 2,6-di-tert-butylpyridine, 1,8-diazabicycloundec-7-ene (DBU), quinuclidine and collidine. A combination of two or more bases can be used. Typically, in the method of the present invention, relative to enol, less than 1 molar equivalent of base is used. For example, 0.05-0.9 molar equivalent or 0.1-0.5 molar equivalent of base can be used. In some embodiments, in conjunction with acylating agent (for example, acetic anhydride), use about 0.05, 0.1, 0.15 or 0.2 molar equivalent of base (for example, sodium acetate) relative to enol to form the olefin metathesis reaction partner of formula III.

[0169] Any suitable solvent can be used to acylate enol. Suitable solvents include but are not limited to toluene, dichloromethane, ethyl acetate, acetonitrile, tetrahydrofuran, benzene, chloroform, ether, dimethylformamide, dimethyl sulfoxide, petroleum ether and mixtures thereof. Alternatively, enol such as (Z)-octadec-9-ene-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 the need for additional solvent. Acylation reaction is generally carried out at a temperature of about 25 ° C to about 100 ° C for a sufficiently long time to form the olefin metathesis reaction partner of formula III. According to the specific enol and acylating agent used in the reaction, the reaction can be carried out for several minutes to several hours or longer. 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.

[0170] Thus, in some embodiments, the present invention provides methods for synthesizing aliphatic olefin metathesis products according to Formula I:

[0171]

[0172] wherein the method comprises contacting an acylating agent with an enol according to formula II

[0173]

[0174] To form an olefin metathesis reaction partner according to formula III

[0175] as well as

[0176] Contacting the olefin metathesis reaction partner with an internal olefin of formula IV in the presence of a Z-selective ruthenium catalyst or a Z-selective osmium catalyst

[0177]

[0178] to form a fatty olefin metathesis product; wherein:

[0179] R 1 is selected from the group consisting of H and C 1-6 alkyl;

[0180] R 2 is selected from the group consisting of C 1-18 alkyl and C 2-18 alkenyl;

[0181] R 3 is C 1-18 alkyl;

[0182] the subscript y is an integer from 0 to 17; and

[0183] the subscript z is an integer from 0 to 17.

[0184] In some embodiments, the method for synthesizing a fatty olefin metathesis product further comprises forming an enol of Formula II by reducing an unsaturated fatty carboxyl derivative according to Formula Ila

[0185]

[0186] wherein R 4 is selected from the group consisting of H and C 1-8 alkyl.

[0187] In some embodiments, forming an enol of Formula II comprises contacting an unsaturated fatty carboxyl derivative of Formula Ila 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 a coordination transition metal catalyst (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 using a silane reagent (Mimoun, H. J. Org. Chem. 1999, 64, 2582.; U.S. Patent No. 6,533,960). Examples of heterogeneous conditions include, but are not limited to, hydrogenolysis of the unsaturated fatty carboxyl derivative of Formula Ila to form the enol of Formula II using ZnO or CuO / ZnO supported on chromite, alumina, or other materials. Any suitable combination of conditions for reducing the unsaturated fatty carboxyl derivative of Formula Ila to the enol of Formula II can be used in the methods of the present application.

[0188] In some embodiments, the hydrogenation catalyst used to form the enol of Formula II from the unsaturated aliphatic carboxyl derivative of Formula Ila 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 dichloro-triphenylphosphine[2-(diphenylphosphino)-N-(2-pyridylmethyl)ethylamine]ruthenium(II). Those skilled in the art will be able to select a suitable hydrogenation catalyst for reducing an unsaturated aliphatic carboxyl derivative (e.g., an alkyl ester-containing compound) to the corresponding enol (e.g., an alcohol-containing compound). Other homogeneous transition metal catalysts suitable for hydrogenating alkyl ester groups to alcohol groups are known to those skilled in the art, including, for example, those described in Werkmeister, S. et al., Org. Process Res. Dev. 2014, 18, 289-302. Generally, the hydrogenation catalyst is used in substoichiometric amounts (e.g., catalytic amounts) in the presence of hydrogen gas and a suitable base (e.g., sodium ethoxide, sodium methoxide, sodium tert-butoxide, and the like). In some embodiments, forming the enol of Formula II comprises contacting the unsaturated aliphatic carboxyl derivative of Formula Ila with a base in the presence of a hydrogenation catalyst and hydrogen gas, wherein the unsaturated aliphatic carboxyl derivative is an unsaturated aliphatic acid alkyl ester. In some embodiments, forming the enol of Formula II comprises contacting the unsaturated aliphatic carboxyl derivative of Formula Ila with a base in the presence of a hydrogenation catalyst and hydrogen gas, wherein R 4 is C 1-8 alkyl.

[0189] In some embodiments, forming the enol of Formula II comprises contacting the unsaturated aliphatic carboxyl derivative of Formula Ila with a reducing agent. Any suitable reducing agent can be used to reduce the unsaturated aliphatic carboxyl derivative of Formula Ila to the enol of Formula II, such as sodium borohydride, sodium triacetoxyborohydride, sodium cyanoborohydride, lithium aluminum hydride, diisobutylaluminum hydride (CN103319704; Chandrasekhar et al., Tetrahedron Lett. 1998, 39, 909), and sodium bis(2-methoxyethoxy)aluminum hydride (“SMEAH”; also known by the trade names RED-AL, SYNHYDRIDE, and VITRIDE). In some embodiments, the reducing agent is sodium bis(2-methoxyethoxy)aluminum hydride.

[0190] Generally, 1-2 molar equivalents of reducing agent relative to the unsaturated fatty carboxyl derivative will be used. In some embodiments, about 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5 molar equivalents of reducing agent relative to the unsaturated fatty carboxyl derivative are used to form the corresponding enol. In some embodiments, forming the enol of Formula II comprises contacting the unsaturated fatty carboxyl derivative of Formula Ila, wherein the unsaturated fatty carboxyl derivative is an unsaturated fatty acid, with a reducing agent. In some embodiments, forming the enol of Formula II comprises contacting the unsaturated fatty carboxyl derivative of Formula Ila, wherein R of Formula Ila is H. The unsaturated fatty acid reduction reaction is generally carried out at a temperature of about -78 °C to about 25 °C for a period of time sufficient to form the enol. The reaction can be carried out for a few minutes to a few hours or more, depending on the specific unsaturated fatty acid and reducing agent used in the reaction. For example, reduction of (Z)-eicos-11-enoic acid with an aluminum reagent (e.g., sodium bis(2-methoxyethoxy)aluminum hydride) can be carried out at a temperature of about 0 °C to about 20 °C for 1-2 hours. 4 The unsaturated fatty acid reduction reaction is generally carried out at a temperature of about -78 °C to about 25 °C for a period of time sufficient to form the enol. The reaction can be carried out for a few minutes to a few hours or more, depending on the specific unsaturated fatty acid and reducing agent used in the reaction. For example, reduction of (Z)-eicos-11-enoic acid with an aluminum reagent (e.g., sodium bis(2-methoxyethoxy)aluminum hydride) can be carried out at a temperature of about 0 °C to about 20 °C for 1-2 hours.

[0191] Any suitable solvent can be used to reduce the unsaturated fatty carboxyl derivative of Formula Ila (e.g., with a hydrogenation catalyst and hydrogen gas or a reducing agent). Suitable solvents include, but are not limited to, toluene, dichloromethane, ethyl acetate, acetonitrile, tetrahydrofuran, benzene, chloroform, diethyl ether, dimethylformamide, dimethyl sulfoxide, petroleum ether, and mixtures thereof.

[0192] Accordingly, in some embodiments, the present application provides a method for synthesizing a fatty olefin metathesis product according to Formula I:

[0193]

[0194] wherein the method comprises reducing an unsaturated fatty carboxyl derivative according to Formula Ila

[0195]

[0196] to form an enol according to Formula II

[0197]

[0198] contacting an acylating agent with the enol to form an olefin metathesis reaction partner according to Formula III

[0199] and

[0200] contacting the olefin metathesis reaction partner with an internal olefin of Formula IV in the presence of a Z-selective ruthenium catalyst or a Z-selective osmium catalyst

[0201]

[0202] to form a fatty olefin metathesis product; wherein:

[0203] R 1 is selected from the group consisting of H and C 1-6 alkyl;

[0204] R 2 is selected from the group consisting of C 1-18 alkyl and C 2-18 alkenyl;

[0205] R 3 is C 1-18 alkyl;

[0206] R 4 is selected from the group consisting of H and C 1-8 alkyl;

[0207] the subscript y is an integer from 0 to 17; and

[0208] the subscript z is an integer from 0 to 17.

[0209] In some embodiments, synthesizing a fatty olefin metathesis product of Formula I according to any one of the methods described herein optionally further comprises contacting the olefin metathesis reaction partner of Formula III with a pretreatment reagent prior to contacting the olefin metathesis reaction partner with the olefin. In some embodiments, the pretreatment reagent is selected from the group consisting of aluminum oxide and magnesium aluminum isopropoxide. In some embodiments, the pretreatment reagent is aluminum oxide. In some embodiments, the pretreatment reagent is magnesium aluminum isopropoxide.

[0210] In some embodiments, R 1 is selected from the group consisting of H and C 1-6 alkyl. In some embodiments, R 1 is H. In some embodiments, R 1 is C 1-6 alkyl. In some embodiments, R 1 is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-butyl, i-butyl, t-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. In some embodiments, R 1is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl. 1 Selected from H and C 1-3 In some embodiments, R 1 is selected from H, methyl, ethyl and propyl. In some embodiments, R 1 In some embodiments, R 1 In some embodiments, R 1 It's methyl.

[0211] In some embodiments, R of Formula IIa, Formula II, and Formula III 2 Selected from C 1-18 Alkyl and C 2-18 In some embodiments, R 2 It is C 1-18 In some embodiments, R 2 It is C 2-18 In some embodiments, R 2 Selected from 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 2 Selected from C 2-18 Alkenyl, C 3-18 Alkenyl, C 4-18 Alkenyl, C 5-18 Alkenyl, 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 17-18alkenyl. In some embodiments, R 2 is a linear C 1-18 alkyl. In some embodiments, R 2 is a linear C 2-18 alkenyl having a carbon-carbon double bond at any position within the hydrocarbon chain, wherein C 2-18 alkenyl is selected from the group consisting of ethenyl, 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.

[0212] In some embodiments, R 2 is selected from the group consisting of C 1-12 alkyl and C 2-12 alkenyl. 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, n-dodecyl, ethenyl, propenyl, n-butenyl, n-pentenyl, n-hexenyl, n-heptenyl, n-octenyl, n-nonenyl, n-decenyl, n-undecenyl, and n-dodecenyl. In some embodiments, R 2 is C 1-12 alkyl. 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. In some embodiments, R 2 is selected from the group consisting of n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. In some embodiments, R 2 is selected from the group consisting of n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-nonyl. In some embodiments, R 2 is selected from the group consisting of n-hexyl, n-heptyl, and n-octyl. In some embodiments, R 2 is n-octyl. In some embodiments, R 2 is not H.

[0213] In some embodiments, R 3 is C 1-18 alkyl. In some embodiments, R 3 is selected from the group consisting of C 1-18 alkyl, C 1-17 alkyl, C 1-16 alkyl, C 1-15 alkyl, C1-14 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 alkyl. In some embodiments, R 3 is a linear C 1-18 alkyl. In some embodiments, R 3 is a C 1-12 alkyl. 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. In some embodiments, R 3 is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. In some embodiments, R 3 is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl. In some embodiments, R 3 is selected from the group consisting of ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl. In some embodiments, R 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.

[0214] In some embodiments, R 4 is selected from the group consisting of H and C 1-8 alkyl. In some embodiments, R 4 is H. In some embodiments, R 4 is a C 1-8 alkyl. In some embodiments, R 4selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-butyl, i-butyl, t-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. In some embodiments, R 4 selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. In some embodiments, R 4 is selected from the group consisting of H and C 1-3 alkyl. In some embodiments, R 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. When R 4 is H, the unsaturated fatty carboxyl derivative of Formula IIa is an unsaturated fatty acid. When R 4 is C 1-8 alkyl or C 1-3 alkyl, the unsaturated fatty carboxyl derivative of Formula IIa is an unsaturated fatty acid alkyl ester.

[0215] In some embodiments, subscript y of Formula I, Formula Ila, Formula II, and Formula III is an integer from 0 to 17. In some embodiments, 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, subscript y is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16. In some embodiments, subscript y is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. In some embodiments, subscript y is an integer from 5 to 15. In some embodiments, subscript y is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. In some embodiments, subscript y is 6, 7, 8, 9, 10, 11, 12, or 13. In some embodiments, subscript y is 7, 9, 11, or 13. In some embodiments, subscript y is 7. In some embodiments, subscript y is 9. In some embodiments, subscript z of Formula I and Formula IV is an integer from 0 to 17. In some embodiments, 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, subscript z is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14. In some embodiments, subscript z is an integer from 0 to 7. In some embodiments, subscript z is 0, 1, 2, 3, 4, 5, 6, or 7. In some embodiments, subscript z is an integer from 0 to 5. In some embodiments, subscript z is 0, 1, 2, 3, 4, or 5. In some embodiments, subscript z is 1, 2, 3, or 4. In some embodiments, subscript z is 1. In some embodiments, subscript z is 2. In some embodiments, subscript z is 3.

[0216] In some embodiments, the methods described herein are used to make a fatty olefin metathesis product according to Formula I, wherein y is 0 and z is 4; or y is 1 and z is 3; or y is 3 and z is 1; or y is 4 and z is 0; or y is 0 and z is 5; or y is 1 and z is 4; or y is 2 and z is 3; or y is 3 and z is 2; or y is 4 and z is 1; or y is 5 and z is 0; or y is 0 and z is 6; or y is 1 and z is 5; or y is 2 and z is 4; or y is 4 and z is 2; or y is 5 and z is 1; or y is 6 and z is 0; or 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; or y is 7 and z is 11 ; or y is 8 and z is 10; or y is 10 and z is 8; or y is 11 and z is 7; or y is 12 and z is 6; or y is 13 and z is 5; or y is 14 and z is 4; or y is 15 and z is 3; or y is 16 and z is 2;or y is 17 and z is 1. In some embodiments, y and z are each 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17.

[0217] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein R 1 is C 1-3 alkyl, R 2 is C 1-12 alkyl, R 3 is C 1-12 alkyl, y is an integer from 5 to 15, and z is an integer from 0 to 7. In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein R 1 is selected from 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 methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl; y is an integer from 6 to 14, and z is an integer from 1 to 4. In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein R 1 is methyl; R 2 is selected from n-hexyl, n-heptyl, and n-octyl; R 3 is selected from ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; y is an integer selected from 7, 9, 11, and 13; and z is an integer selected from 1, 2, and 3. In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein R 1 is methyl; R 2 is n-octyl; R 3 is selected from ethyl and n-butyl; y is an integer selected from 7, 9, 11, and 13; and z is an integer selected from 1 and 3.

[0218] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the metathesis reaction partner according to Formula III is a fatty C 12 -C 30 alkene fatty acid ester; the internal olefin according to Formula IV is a C4-C 20 internal olefin; and the fatty olefin metathesis product according to Formula I is a C8-C 28(Z)-unsaturated fatty ester acetic acid ester. In some embodiments, the metathesis reaction partner according to Formula III is a fatty C 16 -C 28 olefin acetic acid ester; the internal olefin according to Formula IV is a C4-C 12 internal olefin; and the fatty olefin metathesis product according to Formula I is a C 12 -C 24 (Z)-unsaturated fatty ester acetic acid ester. In some embodiments, the metathesis reaction partner according to Formula III is a fatty C 18 -C 26 olefin acetic acid ester; the internal olefin according to Formula IV is a C6-C 10 internal olefin; and the fatty olefin metathesis product according to Formula I is a C 14 -C 22 (Z)-unsaturated fatty ester acetic acid ester.

[0219] In some embodiments, the present application provides a method for synthesizing a fatty olefin metathesis product according to Formula I as described herein, wherein the olefin metathesis reaction partner of Formula III is selected from octadec-9-en-1-yl acetate, eicosa-11-en-1-yl acetate, docosa-13-en-1-yl acetate, tetracos-15-en-1-yl acetate, or mixtures thereof. In some embodiments, the olefin metathesis reaction partner consists of octadec-9-en-1-yl acetate and at least one member selected from eicosa-11-en-1-yl acetate, docosa-13-en-1-yl acetate, and tetracos-15-en-1-yl acetate. In some embodiments, the olefin metathesis reaction partner is selected from octadec-9-en-1-yl acetate, eicosa-11-en-1-yl acetate, docosa-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 eicosa-11-en-1-yl acetate. In some embodiments, the olefin metathesis reaction partner is docosa-13-en-1-yl acetate. In some embodiments, the olefin metathesis reaction partner is tetracos-15-en-1-yl acetate.

[0220] In some embodiments, the present application provides a method for synthesizing a fatty olefin metathesis product according to Formula I as described herein, wherein the alkene of Formula IV is selected from hexadeca-8-ene, tetradeca-7-ene, dodeca-6-ene, dec-5-ene, oct-4-ene, or hex-3-ene. In some embodiments, the alkene is selected from hexadeca-8-ene, tetradeca-7-ene, dodeca-6-ene, dec-5-ene, oct-4-ene, and hex-3-ene. In some embodiments, the alkene is selected from tetradeca-7-ene, dodeca-6-ene, dec-5-ene, oct-4-ene, and hex-3-ene. In some embodiments, the alkene is selected from dodeca-6-ene, dec-5-ene, oct-4-ene, and hex-3-ene. In some embodiments, the alkene is selected from dec-5-ene, oct-4-ene, and hex-3-ene. In some embodiments, the alkene is dec-5-ene. In some embodiments, the alkene is oct-4-ene. In some embodiments, the alkene is hex-3-ene.

[0221] In some embodiments, the present invention provides a method for synthesizing a fatty olefin metathesis product according to Formula I as described herein, wherein the fatty olefin metathesis product is selected from (Z)-tetradec-9-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, (Z)-eicos-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, (Z)-octadec-15-en-1-yl acetate, or a mixture 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)-eicos-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.

[0222] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the olefin metathesis reaction partner according to Formula III comprises at least one member selected from (Z)-octadec-9- en-1-yl acetate, (Z)-eicos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl acetate; the internal olefin according to Formula IV is selected from (Z)-dec-5-ene, (Z)-oct-4-ene, and (Z)-hex-3-ene; and the fatty olefin metathesis product according to Formula I comprises at least one member selected from (Z)-tetradec-9-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, (Z)-eicos-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.

[0223] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the olefin metathesis reaction partner according to Formula III comprises at least one member selected from (Z)-octadec-9- en-1-yl acetate, (Z)-eicos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl acetate; the internal olefin according to Formula IV is (Z)-dec-5-ene; and the fatty olefin metathesis product according to Formula I comprises at least one member selected from (Z)-tetradec-9-en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, and (Z)-eicos-15-en-1-yl acetate.

[0224] In some embodiments, the method for synthesizing fatty olefin metathesis products according to Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the olefin metathesis reaction partner according to Formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-eicosa-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 fatty olefin metathesis products according to Formula I comprise 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.

[0225] In some embodiments, the method for synthesizing fatty olefin metathesis products according to Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the olefin metathesis reaction partner according to Formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-eicosa-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 fatty olefin metathesis products according to Formula I comprise 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.

[0226] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the olefin metathesis reaction partner according to Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin of Formula IV is (Z)-dec-5-ene; and the fatty olefin metathesis product according to Formula I is (Z)-tetradec-9-en-1-yl acetate. In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the olefin metathesis reaction partner according to Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin of Formula IV is (Z)-hex-3-ene; and the fatty olefin metathesis product according to Formula I is (Z)-dodec-9-en-1-yl acetate. In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the olefin metathesis reaction partner according to Formula III is (Z)-eicosa-11-en-1-yl acetate; the internal olefin of Formula IV is (Z)-hex-3-ene; and the fatty olefin metathesis product according to Formula I is (Z)-tetradec-11-en-1-yl acetate.

[0227] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an acylating agent with an enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein R 1 is C 1-3 alkyl, R 2 is C 1-12 alkyl, R 3 is C 1-12 alkyl, y is an integer from 5 to 15, and z is an integer from 0 to 7. In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an acylating agent with an enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein R 1 is selected from H and methyl; R 2 is n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; R 3selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl; y is an integer from 6 to 14, and z is an integer from 1 to 4. In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an acylating agent with an enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein R 1 is methyl; R 2 is selected from n-hexyl, n-heptyl, and n-octyl; R 3 is selected from ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; y is an integer selected from 7, 9, 11, and 13; and z is an integer selected from 1, 2, and 3. In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an acylating agent with an enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein R 1 is methyl; R 2 is n-octyl; R 3 is selected from ethyl and n-butyl; y is an integer selected from 7, 9, 11, and 13; and z is an integer selected from 1 and 3.

[0228] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an acylating agent with an enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the enol according to Formula II is a C 10 -C 28 fatty enol; the metathesis reaction according to Formula III is a C 10 -C 28 acetate of a fatty enol; the internal olefin according to Formula IV is a C4-C 20 internal olefin; and the fatty olefin metathesis product according to Formula I is a C8-C 28 (Z)-unsaturated fatty ester acetate. In some embodiments, the enol according to Formula II is a C 14 -C 26 fatty enol; the metathesis reaction partner according to Formula III is a C 14 -C 26 acetate of a fatty enol; the internal olefin according to Formula IV is a C4-C 12 internal olefin; and the fatty olefin metathesis product according to Formula I is a C 12 -C 24 (Z)-unsaturated fatty ester acetate. In some embodiments, the enol according to Formula II is a C 16 -C 24fatty alkenyl alcohol; the metathesis reaction partner according to Formula III is C 16 -C 24 acetate of a fatty alkenyl alcohol; the internal olefin according to Formula IV is C6-C 10 internal olefin; and the fatty alkenyl metathesis product according to Formula I is C 14 -C 22 (Z)-unsaturated fatty ester acetate.

[0229] In some embodiments, the present application provides a method for synthesizing a fatty alkenyl metathesis product according to Formula I as described herein, wherein the alkenyl alcohol according to Formula II is selected from octadeca-9-en-1-ol, eicosa-11-en-1-ol, docosa-13-en-1-ol, tetracosa-15-en-ol, or mixtures thereof. In some embodiments, the alkenyl alcohol is selected from octadeca-9-en-1-ol, eicosa-11-en-1-ol, docosa-13-en-1-ol, and tetracosa-15-en-ol. In some embodiments, the alkenyl alcohol is octadeca-9-en-1-ol. In some embodiments, the alkenyl alcohol is eicosa-11-en-1-ol. In some embodiments, the alkenyl alcohol is docosa-13-en-1-ol. In some embodiments, the alkenyl alcohol is tetracosa-15-en-ol.

[0230] In some embodiments, the method for synthesizing a fatty alkene metathesis product according to Formula I comprises contacting an acylating agent with an enol according to Formula II to form an alkene metathesis reaction partner according to Formula III, and contacting the alkene metathesis reaction partner of Formula III with an internal alkene according to Formula IV, wherein the enol according to Formula II comprises at least one member selected from the group consisting of (Z)-octadeca-9- en-1-ol, (Z)-eicaosa-11-en-1-ol, (Z)-docosa-13-en-1-ol, and (Z)-tetracosa-15- en-1-ol; the alkene metathesis reaction partner according to Formula III comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-yl acetate, (Z)-eicaosa-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate, and (Z)-tetracosa-15-en-1-yl acetate; the internal alkene according to Formula IV is selected from the group consisting of (Z)-dec-5-ene, (Z)-oct-4-ene, and (Z)-hex-3-ene; and the fatty alkene metathesis product according to Formula I comprises at least one member selected from the group consisting of (Z)-tetradeca-9-en-1-yl acetate, (Z)-hexadeca-11-en-1-yl acetate, (Z)-octadeca-13-en-1-yl acetate, (Z)-eicaosa-15-en-1-yl acetate, (Z)-trideca-9-en-1-yl acetate, (Z)-pentadeca-11-en-1-yl acetate, (Z)-heptadeca-13-en-1-yl acetate, (Z)-nonadeca-15-en-1-yl acetate, (Z)-dodeca-9-en-1-yl acetate, (Z)-tetradeca-11-en-1-yl acetate, (Z)-hexadeca-13-en-1-yl acetate, and (Z)-octadeca-15-en-1-yl acetate.

[0231] In some embodiments, the method for synthesizing a fatty alkene metathesis product according to Formula I comprises contacting an acylating agent with an enol according to Formula II to form an alkene metathesis reaction partner according to Formula III, and contacting the alkene metathesis reaction partner of Formula III with an internal alkene according to Formula IV, wherein the enol according to Formula II comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-ol, (Z)-eicos-11-en-1-ol, (Z)-docos-13-en-1-ol, and (Z)-tetracos-15-en-1-ol; the alkene metathesis reaction partner according to Formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-eicos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl acetate; the internal alkene according to Formula IV is (Z)-dec-5-ene; and the fatty alkene metathesis product according to 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)-eicos-15-en-1-yl acetate.

[0232] In some embodiments, the method for synthesizing a fatty alkene metathesis product according to Formula I comprises contacting an acylating agent with an enol according to Formula II to form an alkene metathesis reaction partner according to Formula III, and contacting the alkene metathesis reaction partner of Formula III with an internal alkene according to Formula IV, wherein the enol according to Formula II comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-ol, (Z)-eicos-11-en-1-ol, (Z)-docos-13-en-1-ol, and (Z)-tetracos-15-en-1-ol; the alkene metathesis reaction partner according to Formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-eicos-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl acetate; the internal alkene according to Formula IV is (Z)-oct-4-ene; and the fatty alkene metathesis product according to 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.

[0233] In some embodiments, the method for synthesizing a fatty alkene metathesis product according to Formula I comprises contacting an acylating agent with an enol according to Formula II to form an alkene metathesis reaction partner according to Formula III, and contacting the alkene metathesis reaction partner of Formula III with an internal alkene according to Formula IV, wherein the enol according to Formula II comprises at least one member selected from the group consisting of (Z)-octadeca-9- en-1-ol, (Z)-eicaosa-11-en-1-ol, (Z)-docosa-13-en-1-ol, and (Z)-tetracosa-15- en-1-ol; the alkene metathesis reaction partner according to Formula III comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-yl acetate, (Z)-eicaosa-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate, and (Z)-tetracosa-15-en-1-yl acetate; the internal alkene according to Formula IV is (Z)-hex-3-ene; and the fatty alkene metathesis product according to Formula I comprises at least one member selected from the group consisting of (Z)-dodeca-9-en-1-yl acetate, (Z)-tetradeca-11-en-1-yl acetate, (Z)-hexadeca-13-en-1-yl acetate, and (Z)-octadeca-15-en-1-yl acetate.

[0234] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an acylating agent with an enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the enol according to Formula II is (Z)-octadec-9-en-1-ol; the olefin metathesis reaction partner according to Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin according to Formula IV is (Z)-dec-5-ene; and the fatty olefin metathesis product according to Formula I is (Z)-tetradec-9-en-1-yl acetate. In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an acylating agent with an enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the enol according to Formula II is (Z)-octadec-9-en-1-ol; the olefin metathesis reaction partner according to Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin according to Formula IV is (Z)-hex-3-ene; and the fatty olefin metathesis product according to Formula I is (Z)-dodec-9-en-1-yl acetate. In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises contacting an acylating agent with an enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the enol according to Formula II is (Z)-eicos-11-en-1-ol; the olefin metathesis reaction partner according to Formula III is (Z)-eicos-11-en-1-yl acetate; the internal olefin according to Formula IV is (Z)-hex-3-ene; and the fatty olefin metathesis product according to Formula I is (Z)-tetradec-11-en-1-yl acetate.

[0235] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises reducing an unsaturated fatty carboxyl derivative according to Formula IIa to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein R 1 is C 1-3 alkyl, R 2 is C 1-12 alkyl, R 3 is C 1-12 alkyl, R 4 is selected from H and C 1-3 alkyl, y is an integer from 5 to 15, and z is an integer from 0 to 7. In some embodiments, R 1 is C1-3 alkyl, R 2 is C 1-12 alkyl, R 3 is C 1-12 alkyl, R 4 is C 1-3 alkyl, y is 7, and z is an integer from 1 to 5. In some embodiments, R 1 is C 1-3 alkyl, R 2 is C 1-12 alkyl, R 3 is C 1-12 alkyl, R 4 is H, y is an integer from 5 to 15, and z is an integer from 1 to 5.

[0236] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises reducing an unsaturated fatty carboxyl derivative according to Formula Ila to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein R 1 is selected from 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 methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl; R 4 is selected from H and methyl; y is an integer from 6 to 14, and z is an integer from 1 to 4. In some embodiments, R 1 is methyl; R 2 is selected from n-hexyl, n-heptyl, and n-octyl; R 3 is selected from ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; R 4 is methyl; y is an integer selected from 7, 9, 11, and 13; and z is an integer selected from 1, 2, and 3. In some embodiments, R 1 is methyl; R 2 is selected from n-hexyl, n-heptyl, and n-octyl; R 3 is selected from ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; R 4 is H; y is an integer selected from 7, 9, 11, and 13; and z is an integer selected from 1, 2, and 3.

[0237] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I includes reducing an unsaturated fatty carboxyl derivative according to Formula Ila to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to 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; 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.

[0238] In some embodiments, when R 4 of Formula Ila is C 1-8 alkyl (e.g., C 1-3 alkyl, methyl, etc.), the unsaturated fatty carboxyl derivative is an unsaturated fatty acid alkyl ester. Accordingly, in some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I includes reducing an unsaturated fatty acid alkyl ester according to Formula Ila to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the unsaturated fatty acid alkyl ester according to Formula Ila is a C 11- C 29 unsaturated fatty acid methyl ester; the enol according to Formula II is a C 10 -C 28 fatty enol; the metathesis reaction partner according to Formula III is a C 10 -C 28 acetic acid ester of a fatty enol; and the internal olefin according to Formula IV is a C4-C20 internal olefin; and the fatty olefin metathesis product according to Formula I is C8-C 28 (Z)-unsaturated fatty ester acetate. In some embodiments, the unsaturated fatty acid alkyl ester according to Formula IIa is C 15- C 27 unsaturated fatty acid methyl ester; the enol according to Formula II is C 14 -C 26 fatty enol; the metathesis reaction partner according to Formula III is C 14 -C 26 fatty enol acetate; the internal olefin according to Formula IV is C6-C 12 internal olefin; and the fatty olefin metathesis product according to Formula I is C8-C 12- C 24 (Z)-unsaturated fatty ester acetate. In some embodiments, the unsaturated fatty acid alkyl ester according to Formula IIa is C 17- C 25 unsaturated fatty acid methyl ester; the enol of Formula II is C 16 -C 24 fatty enol; the metathesis reaction partner according to Formula III is C 16 -C 24 fatty enol acetate; the internal olefin according to Formula IV is C6-C 10 internal olefin; and the fatty olefin metathesis product according to Formula I is C8-C 14 -C 22 (Z)-unsaturated fatty ester acetate.

[0239] In some embodiments, the present application provides a method for synthesizing a fatty olefin metathesis product of Formula I as described herein, wherein the unsaturated fatty acid alkyl ester of Formula IIa is selected from the group consisting of methyl octadeca-9-enoate, methyl eicosa-11-enoate, methyl docos-13-enoate, methyl tetracos-15-enoate, or mixtures thereof. In some embodiments, the unsaturated fatty acid alkyl ester consists of methyl octadeca-9-enoate and at least one member selected from the group consisting of methyl eicosa-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 octadeca-9-enoate, methyl eicosa-11-enoate, methyl docos-13-enoate, and methyl tetracos-15-enoate. In some embodiments, the unsaturated fatty acid alkyl ester is methyl octadeca-9-enoate. In some embodiments, the unsaturated fatty acid alkyl ester is methyl eicosa-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.

[0240] In some embodiments, the method for synthesizing a fatty alkene metathesis product according to Formula I comprises reducing an unsaturated fatty acid alkyl ester according to Formula Ha to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an alkene metathesis reaction partner according to Formula III, and contacting the alkene metathesis reaction partner of Formula III with an internal alkene according to Formula IV, wherein the unsaturated fatty acid alkyl ester according to Formula Ha comprises at least one member selected from the group consisting of (Z)-octadec-9-enoic acid methyl ester, (Z)-eicosa-11-enoic acid methyl ester, (Z)-docos-13-enoic acid methyl ester, and (Z)-tetracos-15-enoic acid methyl ester; the enol according to Formula II comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-ol, (Z)-eicosa-11-en-1-ol, (Z)-docos-13-en-1-ol, and (Z)-tetracos-15-en-1-ol; the alkene metathesis reaction partner according to Formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-eicosa-11-en-1-yl ester, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl acetate; the internal alkene according to Formula IV is selected from the group consisting of (Z)-dec-5-ene, (Z)-oct-4-ene, and (Z)-hex-3-ene; and the fatty alkene metathesis product according to 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, (Z)-eicosa-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.

[0241] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises reducing an unsaturated fatty acid alkyl ester according to Formula Ila to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the unsaturated fatty acid alkyl ester according to Formula Ila is (Z)-octadec-9-enoic acid methyl ester; the enol according to Formula II is (Z)-octadec-9-en-1-ol; the olefin metathesis reaction partner according to Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin according to Formula IV is (Z)-dec-5-ene; and the fatty olefin metathesis product according to Formula I is (Z)-tetradec-9-en-1-yl acetate.

[0242] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises reducing an unsaturated fatty acid alkyl ester according to Formula Ila to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the unsaturated fatty acid alkyl ester according to Formula Ila is (Z)-octadec-9-enoic acid methyl ester; the enol according to Formula II is (Z)-octadec-9-en-1-ol; the olefin metathesis reaction partner according to Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin according to Formula IV is (Z)-hex-3-ene; and the fatty olefin metathesis product according to Formula I is (Z)-dodec-9-en-1-yl acetate.

[0243] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I includes reducing an unsaturated fatty acid alkyl ester according to Formula Ila to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the unsaturated fatty acid alkyl ester according to Formula Ila is (Z)-icos-11- enoic acid methyl ester; the enol according to Formula II is (Z)-icos-11-en-1-ol; the olefin metathesis reaction partner according to Formula III is (Z)-icos-11-en-1-yl acetate; the internal olefin of Formula IV is (Z)-hex-3-ene; and the fatty olefin metathesis product according to Formula I is (Z)-tetradec-11-en-1-yl acetate. The prefixes “icos” and “eicos” are used interchangeably to refer to a hydrocarbon chain having 20 carbons (i.e., (Z)-icos-11-enoic acid methyl ester, (Z)-icos-11-en-1-ol, and (Z)-icos-11-en-1-yl acetate correspond to (Z)-eicos-11-enoic acid methyl ester, (Z)-eicos-11-en-1-ol, and (Z)-eicos-11-en-1-yl acetate).

[0244] In some embodiments, when R 4 of Formula Ila is H, the unsaturated fatty carboxyl derivative is an unsaturated fatty acid. Thus, in some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I includes reducing an unsaturated fatty acid according to Formula Ila to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the unsaturated fatty acid according to Formula Ila is C 10- C 28 unsaturated fatty acid; the enol according to Formula II is C 10- C 28 fatty enol; the metathesis reaction partner according to Formula III is C 10- C 28 fatty enol acetate; the internal olefin of Formula IV is C4-C 20 internal olefin; and the fatty olefin metathesis product according to Formula I is C8-C 28 (Z)-unsaturated fatty ester acetate. In some embodiments, the unsaturated fatty acid alkyl ester according to Formula Ila is C 14- C 26 unsaturated fatty acid methyl ester; the enol according to Formula II is C 14 -C 26 fatty enol; the metathesis reaction partner according to Formula III is C 14-C 26 Acetate of a fatty olefin; the internal olefin according to formula IV is C4-C 12 Internal olefin; and the fatty olefin metathesis product according to formula I is C 12- C 24 (Z)-unsaturated fatty acid ester acetate. In some embodiments, the unsaturated fatty acid alkyl ester according to Formula IIa is C 16- C 24 Unsaturated fatty acid methyl ester; the enol according to formula II is C 16- C 24 Fatty enolate; The metathesis partner according to formula III is C 16- C 24 Acetate of a fatty olefin; the internal olefin according to formula IV is C6-C 10 Internal olefin; and the fatty olefin metathesis product according to formula I is C 14 -C 22 (Z)-Unsaturated fatty ester acetate.

[0245] In some embodiments, the present invention provides a method for synthesizing a fatty olefin metathesis product according to Formula I as described herein, wherein the unsaturated fatty acid according to Formula IIa is selected from octadec-9-enoic acid, eicos-11-enoic acid, docos-13-enoic acid, tetracos-15-enoic acid, or a mixture thereof. In some embodiments, the unsaturated fatty acid is composed of octadec-9-enoic acid and at least one member selected from eicos-11-enoic acid, docos-13-enoic acid, and tetracos-15-enoic acid. In some embodiments, the unsaturated fatty acid is selected from octadec-9-enoic acid, eicos-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 eicos-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.

[0246] In some embodiments, the method for synthesizing a fatty alkene metathesis product according to Formula I comprises reducing an unsaturated fatty acid according to Formula Ha to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an alkene metathesis reaction partner according to Formula III, and contacting the alkene metathesis reaction partner of Formula III with an internal alkene according to Formula IV, wherein the unsaturated fatty acid according to Formula Ha comprises at least one member selected from the group consisting of (Z)-octadec-9-enoic acid, (Z)-eicosa-11-enoic acid, (Z)-docos-13-enoic acid, and (Z)-tetracos-15-enoic acid; the enol according to Formula II comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-ol, (Z)-eicosa-11-en-1-ol, (Z)-docos-13-en-1-ol, and (Z)-tetracos-15-en-1-ol; the alkene metathesis reaction partner according to Formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-eicosa-11-en-1-yl acetate, (Z)-docos-13-en-1-yl acetate, and (Z)-tetracos-15-en-1-yl acetate; the internal alkene according to Formula IV is selected from the group consisting of (Z)-dec-5-ene, (Z)-oct-4-ene, and (Z)-hex-3-ene; and the fatty alkene metathesis product according to 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, (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-13-en-1-yl acetate, and (Z)-octadec-15-en-1-yl acetate.

[0247] In some embodiments, the unsaturated fatty carboxyl derivative of Formula IIa is derived from a natural oil. In some embodiments, the unsaturated fatty carboxyl 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 processes of the present application include natural oils and / or derivatives thereof comprising (Z)-octadeca-9-enoic acid, (Z)-eicosa-11-enoic acid, (Z)-docos-13-enoic acid, (Z)-tetracosa-15-enoic acid, or mixtures thereof. In some embodiments, the unsaturated fatty acid of Formula IIa is obtained 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, grape seed oil, olive oil, palm oil, peanut oil, hemp oil, macadamia oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil, jojoba oil, mustard oil, oilseed rape oil, borage oil, castor oil, and combinations thereof. In some embodiments, the unsaturated fatty acid of Formula IIa is obtained from a natural oil 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 acid of Formula IIa is obtained from a natural oil 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 acid of Formula IIa is obtained from a natural oil selected from the group consisting of canola oil, avocado oil, jojoba oil, and combinations thereof. In some embodiments, the unsaturated fatty acid of Formula IIa is obtained from a natural oil selected from the group consisting of canola oil and jojoba oil. In some embodiments, the unsaturated fatty acid of Formula IIa is obtained from jojoba oil.

[0248] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises reducing an unsaturated fatty acid according to Formula Ila to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the unsaturated fatty acid according to Formula Ila is obtained from a natural oil or a derivative thereof, and comprises at least one member selected from the group consisting of (Z)-octadeca-9-enoic acid, (Z)-eicaosa-11-enoic acid, (Z)-docos-13-enoic acid, and (Z)-tetracos-15-enoic acid; the enol according to Formula II comprises at least one member selected from the group consisting of (Z)-octadeca-9-ene-1-ol, (Z)-eicaosa-11-ene-1-ol, (Z)-docos-13-ene-1-ol, and (Z)-tetracos-15-ene-1-ol; the olefin metathesis reaction partner according to Formula III comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-yl acetate, (Z)-eicaosa-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 fatty olefin metathesis product according to Formula I comprises at least one member selected from the group consisting of (Z)-tetradeca-9-en-1-yl acetate, (Z)-hexadeca-11-en-1-yl acetate, (Z)-octadeca-13-en-1-yl acetate, and (Z)-eicaosa-15-en-1-yl acetate.

[0249] In some embodiments, the method for synthesizing a fatty olefin metathesis product according to Formula I comprises reducing an unsaturated fatty acid according to Formula Ila to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the unsaturated fatty acid according to Formula Ila 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)-eicosa-11-enoic acid, (Z)-docos-13-enoic acid, and (Z)-tetracos-15-enoic acid; the enol according to Formula II comprises at least one member selected from the group consisting of (Z)-octadec-9-ene-1-ol, (Z)-eicosa-11-ene-1-ol, (Z)-docos-13-ene-1-ol, and (Z)-tetracos-15-ene-1-ol; the olefin metathesis reaction partner according to Formula III comprises at least one member selected from the group consisting of (Z)-octadec-9-en-1-yl acetate, (Z)-eicosa-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 fatty olefin metathesis product according to 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.

[0250] In some embodiments, a method for synthesizing a fatty olefin metathesis product according to Formula I comprises reducing an unsaturated fatty acid according to Formula IIa to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the unsaturated fatty acid according to 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)-eicos-11-enoic acid, (Z)-docosa-13-enoic acid, and (Z)-tetracos-15-enoic acid; and the enol according to Formula II comprises at least one member selected from the group consisting of: (Z)-octadec-9-en-1-ol, (Z)-eicos-11-eno-1 -ol, (Z)-docosa-13-en-1-ol and (Z)-tetracosa-15-en-ol; the olefin metathesis reaction partner according to formula III comprises at least one member selected from the group consisting of: (Z)-octadec-9-en-1-yl acetate, (Z)-eicos-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate and (Z)-tetracosa-15-en-1-yl acetate; the internal olefin according to formula IV is (Z)-hex-3-ene; and the aliphatic olefin metathesis product according to formula I comprises at least one member selected from the group consisting of: (Z)-dodec-9-en-1-yl acetate, (Z)-tetracosa-11-en-1-yl acetate, (Z)-hexadec-13-en-1-yl acetate and (Z)-octadec-15-en-1-yl acetate.

[0251] In some embodiments, a method for synthesizing a fatty olefin metathesis product according to Formula I comprises reducing an unsaturated fatty acid according to Formula IIa to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the unsaturated fatty acid according to Formula IIa is (Z)-octadec-9-enoic acid; the enol according to Formula II is (Z)-octadec-9-en-1-ol; the olefin metathesis reaction partner according to Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin according to Formula IV is (Z)-dec-5-ene; and the fatty olefin metathesis product according to Formula I is (Z)-tetradec-9-en-1-yl acetate.

[0252] In some embodiments, a method for synthesizing a fatty olefin metathesis product according to Formula I comprises reducing an unsaturated fatty acid according to Formula IIa to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the unsaturated fatty acid according to Formula IIa is (Z)-octadec-9-enoic acid; the enol according to Formula II is (Z)-octadec-9-en-1-ol; the olefin metathesis reaction partner according to Formula III is (Z)-octadec-9-en-1-yl acetate; the internal olefin according to Formula IV is (Z)-hex-3-ene; and the fatty olefin metathesis product according to Formula I is (Z)-dodec-9-en-1-yl acetate.

[0253] In some embodiments, a method for synthesizing a fatty olefin metathesis product according to Formula I comprises reducing an unsaturated fatty acid according to Formula IIa to form an enol according to Formula II, contacting an acylating agent with the enol according to Formula II to form an olefin metathesis reaction partner according to Formula III, and contacting the olefin metathesis reaction partner of Formula III with an internal olefin according to Formula IV, wherein the unsaturated fatty acid according to Formula IIa is (Z)-eicos-11-enoic acid; the enol according to Formula II is (Z)-eicos-11-en-1-ol; the olefin metathesis reaction partner according to Formula III is (Z)-eicos-11-en-1-yl acetate; the internal olefin according to Formula IV is (Z)-hex-3-ene; and the fatty olefin metathesis product according to Formula I is (Z)-tetradec-11-en-1-yl acetate.

[0254] (Z)-metathesis products from (E)-reaction partners and olefins

[0255] The methods described herein are useful for preparing aliphatic olefin metathesis products of Formula I from a metathesis reaction partner and an olefin, wherein the aliphatic olefin metathesis product is substantially in the Z-configuration and the metathesis reaction partner and / or the olefin comprises an isomer in the E-configuration. In some embodiments, aliphatic olefin metathesis products comprising greater than 97% Z-isomers are formed according to the methods described herein, wherein the metathesis reaction partner comprises 1% or more E-isomers and the olefin comprises from 0% to 15% or more E-isomers.

[0256] Thus, in some embodiments, the present invention provides methods for synthesizing aliphatic olefin metathesis products according to Formula I:

[0257]

[0258] wherein the method comprises contacting an olefin metathesis reaction partner according to Formula III

[0259]

[0260] with an internal olefin according to Formula IV

[0261]

[0262] to form a fatty olefin metathesis product; wherein:

[0263] R 1 is selected from the group consisting of H and C 1-6 alkyl;

[0264] R 2 is selected from the group consisting of C 1-18 alkyl and C 2-18 alkenyl;

[0265] R 3 is C 1-18 alkyl;

[0266] the subscript y is an integer from 0 to 17;

[0267] the subscript z is an integer from 0 to 17; and

[0268] the fatty olefin metathesis product is at least 97% Z.

[0269] In some embodiments, a method for synthesizing a fatty olefin metathesis product according to Formula I:

[0270]

[0271] comprises contacting an acylating agent with an enol according to Formula II

[0272]

[0273] to form an olefin metathesis reaction partner according to Formula III

[0274] and

[0275] contacting the olefin metathesis reaction partner with an internal olefin of Formula IV in the presence of a Z-selective ruthenium catalyst or a Z-selective osmium catalyst

[0276]

[0277] to form a fatty olefin metathesis product; wherein:

[0278] R 1 is selected from the group consisting of H and C 1-6alkyl;

[0279] R 2 selected from C 1-18 alkyl and C 2-18 alkenyl;

[0280] R 3 is C 1-18 alkyl;

[0281] the subscript y is an integer from 0 to 17;

[0282] the subscript z is an integer from 0 to 17; and

[0283] the fatty olefin metathesis product is at least 97% Z.

[0284] In some embodiments, a method for synthesizing a fatty olefin metathesis product according to Formula I:

[0285]

[0286] comprises reducing an unsaturated fatty carboxyl derivative according to Formula IIa

[0287]

[0288] to form an enol according to Formula II

[0289]

[0290] contacting an acylating agent with the enol to form an olefin metathesis reaction partner according to Formula III

[0291] and

[0292] contacting the olefin metathesis reaction partner with an internal olefin of Formula IV in the presence of a Z-selective ruthenium catalyst or a Z-selective osmium catalyst

[0293]

[0294] to form the fatty olefin metathesis product; wherein:

[0295] R 1 is selected from H and C 1-6 alkyl;

[0296] R 2 is selected from C 1-18 alkyl and C 2-18 alkenyl;

[0297] R 3 is C 1-18 alkyl;

[0298] R 4selected from H and C 1-8 alkyl;

[0299] the subscript y is an integer from 0 to 17;

[0300] the subscript z is an integer from 0 to 17; and

[0301] the fatty olefin metathesis product is at least 97% Z.

[0302] In some embodiments, the methods described herein are used to make a fatty olefin metathesis product according to Formula I, wherein the fatty olefin metathesis product is greater than 97% Z. In some embodiments, the fatty olefin metathesis product of Formula I is about 97.1% Z to about 99.9% Z. In some embodiments, the fatty 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 fatty olefin metathesis product of Formula I is greater than 98% Z. In some embodiments, the fatty olefin metathesis product of Formula I is greater than 99% Z. In some embodiments, the fatty 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.

[0303] Accordingly, the present application provides a method for synthesizing a fatty olefin metathesis product of Formula I as described herein, wherein the fatty olefin metathesis product is selected from (Z)-tetradec-9- en-1-yl acetate, (Z)-hexadec-11-en-1-yl acetate, (Z)-octadec-13-en-1-yl acetate, (Z)-eicos-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, (Z)-octadec-15-en-1-yl acetate, or mixtures thereof, wherein the fatty olefin metathesis product is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0304] In some embodiments, the fatty 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)-eicos-15-en-1-yl acetate, wherein the fatty olefin metathesis product is at least 97% Z, greater than 98% Z, or greater than 99% Z. In some embodiments, the fatty 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 fatty olefin metathesis product is at least 97% Z, greater than 98% Z, or greater than 99% Z. In some embodiments, the fatty 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)-tetradec-11-en-1-yl acetate, (Z)-hexadec-13-en-1-yl acetate, and (Z)-octadec-15-en-1-yl acetate, wherein the fatty olefin metathesis product is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0305] 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 (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 (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 fatty 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.

[0306] In some embodiments, the fatty olefin metathesis product according to Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, wherein one or more of the unsaturated fatty carboxyl derivative of Formula Ila, the enol of Formula II, the olefin metathesis reaction partner of Formula III, and the olefin of Formula IV is at least 1% E. In some embodiments, the unsaturated fatty carboxyl derivative of Formula Ila, the enol of Formula II, the olefin metathesis reaction partner of Formula III, and / or the olefin of Formula IV is about 1.5% E to about 50% E. In some embodiments, the fatty olefin metathesis product according to Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and one or more of the unsaturated fatty carboxyl derivative of Formula Ila, the enol of Formula II, the olefin metathesis reaction partner of Formula III, 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, one or more of the unsaturated fatty carboxyl derivative of Formula Ila, the enol of Formula II, the olefin metathesis reaction partner of Formula III, and / or the olefin of Formula IV is 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 of one or more of the unsaturated fatty carboxyl derivative of Formula Ila, the enol 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.

[0307] In some embodiments, the aliphatic olefin metathesis product according to 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 according to 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 according to 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 according to 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 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 (cis:trans) ratio of the olefin metathesis reaction partner 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 according to Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0308] Thus, in some embodiments, the fatty olefin metathesis product of Formula I prepared according to any one 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 octadeca-9- en-1-yl acetate, eicosa-11-en-1-yl acetate, docosa-13-en-1-yl acetate, tetracosa-15-en-1-yl acetate, or mixtures thereof, wherein the olefin metathesis reaction partner 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 fatty 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 consists of octadeca-9-en-1-yl acetate and at least one member selected from eicosa-11-en-1-yl acetate, docosa-13-en-1-yl acetate, and tetracosa-15-en-1-yl acetate, wherein the olefin metathesis reaction partner 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 fatty 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 octadeca-9-en-1-yl acetate, eicosa-11-en-1-yl acetate, docosa-13-en-1-yl acetate, and tetracosa-15-en-1-yl acetate, wherein the olefin metathesis reaction partner is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0309] In some embodiments, the fatty 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 about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the fatty 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 eicos-11-en-1-yl acetate, wherein the eicos-11-en-1-yl acetate 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 fatty 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 about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the fatty 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 about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0310] In some embodiments, the fatty olefin metathesis product according to Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, with the olefin of Formula IV being at least 1% E. In some embodiments, the fatty olefin metathesis product according to 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 fatty olefin metathesis product according to 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 fatty olefin metathesis product according to 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 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 (cis:trans) 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 fatty olefin metathesis product according to Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0311] Accordingly, in some embodiments, the fatty 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 hexadeca-8-ene, tetradeca-7-ene, dodeca-6-ene, dec-5-ene, oct-4-ene, or hex-3-ene, wherein the olefin 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 fatty 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 hexadeca-8-ene, tetradeca-7-ene, dodeca-6-ene, dec-5-ene, oct-4-ene, and hex-3-ene, wherein the olefin 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 fatty 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 tetradeca-7-ene, dodeca-6-ene, dec-5-ene, oct-4-ene, and hex-3-ene, wherein the olefin is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0312] In some embodiments, the fatty 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 dodeca-6-ene, dec-5-ene, oct-4-ene, and hex-3-ene, wherein the olefin 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 fatty 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 dec-5-ene, oct-4-ene, and hex-3-ene, wherein the olefin 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 fatty 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, wherein the dec-5-ene 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 fatty 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, wherein the oct-4-ene 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 fatty 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 about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0313] In some embodiments, the fatty olefin metathesis product according to Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, wherein the enol of Formula II is at least 1% E. In some embodiments, the fatty olefin metathesis product according to Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the enol of Formula II is about 1.5% E to about 50% E. In some embodiments, the fatty olefin metathesis product according to Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the enol 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 fatty olefin metathesis product according to Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the enol of Formula II is 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 (cis:trans) ratio of the enol 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 fatty olefin metathesis product according to Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0314] Accordingly, in some embodiments, the fatty olefin metathesis product of Formula I prepared according to any one of the methods described herein is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the enol of Formula II is selected from octadec-9-en-1-ol, eicos-11-en-1-ol, docos-13-en-1-ol, tetracos-15-enol, or mixtures thereof, wherein the enol 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 fatty olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the enol is selected from octadec-9-en-1-ol, eicos-11-en-1-ol, docos-13-en-1-ol, and tetracos-15-enol, wherein the enol is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0315] In some embodiments, the fatty olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the enol of Formula II is octadec-9-en-1-ol, wherein the octadec-9-en-1-ol 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 fatty olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the enol is eicos-11-en-1-ol, wherein the eicos-11-en-1-ol 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 fatty olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the enol is docos-13-en-1-ol, wherein the docos-13-en-1-ol 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 fatty olefin metathesis product of Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the enol is tetracos-15-en-ol, wherein the tetracos-15-en-ol is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0316] In some embodiments, the fatty olefin metathesis product according to Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, wherein the unsaturated fatty carboxyl derivative of Formula Ila is at least 1% E. In some embodiments, the fatty olefin metathesis product according to Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, wherein the unsaturated fatty carboxyl derivative of Formula Ila is about 1.5% E to about 50% E. In some embodiments, the fatty olefin metathesis product according to Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty carboxyl derivative of Formula Ila 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 fatty olefin metathesis product according to Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty carboxyl derivative of Formula Ila is 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 (cis:trans) ratio of the unsaturated fatty carboxyl derivative of Formula Ila 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 fatty olefin metathesis product according to Formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0317] Thus, in some embodiments, the fatty alkene metathesis product of Formula I prepared according to any one 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 Ha is selected from the group consisting of methyl octadeca-9-enoate, methyl eicosa-11-enoate, methyl docos-13-enoate, methyl tetracos-15-enoate, or mixtures thereof, wherein the unsaturated fatty acid alkyl ester 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 fatty alkene 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 consists of methyl octadeca-9-enoate and at least one member selected from the group consisting of methyl eicosa-11-enoate, methyl docos-13-enoate, and methyl tetracos-15-enoate, wherein the unsaturated fatty acid alkyl ester 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 fatty alkene 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 octadeca-9-enoate, methyl eicosa-11-enoate, methyl docos-13-enoate, and methyl tetracos-15-enoate, wherein the unsaturated fatty acid alkyl ester is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0318] In some embodiments, the fatty 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 Ha is methyl octadeca-9-enoate, wherein the methyl octadeca-9-enoate 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 fatty 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 eicosa-11-enoate, wherein the methyl eicosa-11-enoate 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 fatty 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 about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the fatty 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 about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0319] Thus, in some embodiments, the fatty olefin metathesis product of Formula I prepared according to any one of the methods described herein is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid according to Formula Ha is selected from octadeca-9-enoic acid, eicosa-11-enoic acid, docos-13-enoic acid, tetracos-15-enoic acid, or mixtures thereof, wherein the unsaturated fatty 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 fatty 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 consists of octadeca-9-enoic acid and at least one member selected from eicosa-11-enoic acid, docos-13-enoic acid, and tetracos-15-enoic acid, wherein the unsaturated fatty 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 fatty 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 selected from octadeca-9-enoic acid, eicosa-11-enoic acid, docos-13-enoic acid, and tetracos-15-enoic acid, wherein the unsaturated fatty acid is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0320] In some embodiments, the fatty 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 Ha is octadec-9-enoic acid, wherein the octadec-9-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 fatty 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 about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the fatty 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 fatty 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.

[0321] Metathesis catalyst

[0322] In some embodiments, the metathesis catalyst used in the method for synthesizing a fatty olefin metathesis product as described above is a Z-selective metathesis catalyst having a structure according to Formula V:

[0323]

[0324] wherein:

[0325] M is selected from ruthenium and osmium;

[0326] X and Y are independently selected from S and O;

[0327] Z is selected from O and S(=0);

[0328] each subscript m and subscript n is an integer independently selected from 0, 1, 2, 3, and 4;

[0329] each R a is independently selected from halogen, Ci-C6alkyl, alkoxy, aryl, and heteroaryl; or one R a is taken together with an adjacent R a to form an unsubstituted or substituted bicyclic ring or an unsubstituted or substituted polycyclic ring;

[0330] each R bindependently selected from the group consisting of halogen, C1-C6alkyl, alkoxy, aryl, and heteroaryl; or one R b together with an adjacent R b form an unsubstituted or substituted bicyclic ring or an unsubstituted or substituted polycyclic ring;

[0331] R c is selected from the group consisting of hydrogen and C1-C6alkyl;

[0332] each R d , R e , R f , and R g are independently selected from the group consisting of hydrogen and C1-C6alkyl;

[0333] R 12 , and R 13 are independently selected from the group consisting of 2,4,6-triisopropylphenyl, 2,6-diisopropylphenyl, 2,6-diamantylphenyl, 2-isopropyl-6-tert- butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl;

[0334] each R 14 is independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, cyclohexyl, benzyl, and phenyl; and

[0335] R 15 is selected from the group consisting of hydrogen, halogen, and C1-C6alkyl, or R 15 and one R 14 together form a bond.

[0336] 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); subscript m is 2; subscript n is 0; each R a is independently selected from the group consisting of halogen, C1-C6alkyl, and aryl; R c is hydrogen; each R d , R e , R f , and R g is hydrogen; R 12 , and R 13 are independently selected from the group consisting of 2,4,6-triisopropylphenyl, 2,6-diisopropylphenyl, 2,6-diamantylphenyl, 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, i-propyl, benzyl, and t-butyl; and R 15 is selected from the group consisting of hydrogen, halogen, and C1-C6alkyl, or R 15 and one R 14 together form a bond.

[0337] In some embodiments, the metathesis catalyst used in the process for synthesizing the aliphatic olefin metathesis product of Formula I is a Z-selective metathesis catalyst selected from the group consisting of:

[0338]

[0339] In some embodiments, the catalyst is:

[0340]

[0341] Other catalysts that can be used for the methods provided herein include, but are not limited to, 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, which are incorporated herein by reference in their entirety. Catalysts described by Zachmann et al. (Chem. Eur. J. 2021, 27, 7663-7666) and Grudzień et al. (Chem. Eur. J. 2014, 20, 2819-2828) can also be used.

[0342] Metathesis reaction conditions

[0343] Z-selective metathesis

[0001] Catalyst is usually provided in the reaction mixture with substoichiometric (for example, catalytic amount). In certain embodiments, depending on which reagent is in stoichiometric excess, relative to the limiting reagent of the chemical reaction, this amount is about 0.001 to about 50mol% (0.1-5000ppm). In some embodiments, relative to the limiting reagent, catalyst exists with an amount less than or equal to about 40mol%. In some embodiments, relative to the limiting reagent, catalyst exists with an amount less than or equal to about 30mol%. In some embodiments, relative to the limiting reagent, catalyst exists with an amount less than about 20mol%, less than about 10mol%, less than about 5mol%, less than about 2.5mol%, less than about 1mol%, less than about 0.5mol%, less than about 0.1mol%, less than about 0.015mol%, less than about 0.01mol%, less than about 0.0015mol% or less amount. In some embodiments, relative to the limiting reagent, catalyst exists with a scope of about 2.5mol% to about 5mol%. In some embodiments, the reaction mixture contains 0.01-0.1 mol% catalyst (e.g., about 0.5 mol% catalyst).In instances where the molecular formula of the catalyst complex comprises more than one metal, the amount of catalyst complex used in the reaction can be adjusted accordingly.

[0344] The catalyst loading can also be expressed relative to the olefin content of the reaction mixture. For example, the metathesis catalyst can be present in an amount of 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 0.1-100 ppm of catalyst per double bond, or about 1-100 ppm, or about 1-75 ppm, or about 1-50 ppm, or about 3-50 ppm.

[0345] In some cases, the methods described herein can be performed 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 can be suitable for use in the present application include, but are not limited to, benzene, p-cresol, toluene, xylene, diethyl ether, ethylene glycol, diethyl ether, petroleum ether, hexane, cyclohexane, pentane, dichloromethane, chloroform, carbon tetrachloride, dioxane, tetrahydrofuran (THF), dimethyl sulfoxide, dimethylformamide, hexamethylphosphoramide, ethyl acetate, pyridine, triethylamine, picoline, and the like, and mixtures thereof. In some embodiments, the solvent is selected from benzene, toluene, pentane, dichloromethane, and THF. In certain embodiments, the solvent is benzene.

[0346] In some embodiments, the process is conducted under reduced pressure. This can be advantageous in cases where volatile byproducts such as ethylene can be produced during the metathesis reaction. For example, removal of ethylene byproducts from the reaction vessel can advantageously shift the equilibrium of the metathesis reaction toward formation of the desired product. In some embodiments, the process is conducted at a pressure of about less than 760 Torr. In some embodiments, the process is conducted at a pressure of about less than 700 Torr. In some embodiments, the process is conducted at a pressure of about less than 650 Torr. In some embodiments, the process is conducted at a pressure of about less than 600 Torr. In some embodiments, the process is conducted at a pressure of about less than 550 Torr. In some embodiments, the process is conducted at a pressure of about less than 500 Torr. In some embodiments, the process is conducted at a pressure of about less than 450 Torr. In some embodiments, the process is conducted at a pressure of about less than 400 Torr. In some embodiments, the process is conducted at a pressure of about less than 350 Torr. In some embodiments, the process is conducted at a pressure of about less than 300 Torr. In some embodiments, the process is conducted at a pressure of about less than 250 Torr. In some embodiments, the process is conducted at a pressure of about less than 200 Torr. In some embodiments, the process is conducted at a pressure of about less than 150 Torr. In some embodiments, the process is conducted at a pressure of about less than 100 Torr. In some embodiments, the process is conducted at a pressure of about less than 90 Torr. In some embodiments, the process is conducted at a pressure of about less than 80 Torr. In some embodiments, the process is conducted at a pressure of about less than 70 Torr. In some embodiments, the process is conducted at a pressure of about less than 60 Torr. In some embodiments, the process is conducted at a pressure of about less than 50 Torr. In some embodiments, the process is conducted at a pressure of about less than 40 Torr. In some embodiments, the process is conducted at a pressure of about less than 30 Torr. In some embodiments, the process is conducted at a pressure of about less than 20 Torr. In some embodiments, the process is conducted at a pressure of about 20 Torr.

[0347] 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. The method is carried out in some embodiments 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.

[0348] In some embodiments, the two metathesis reactants (i.e., the metathesis reaction partners and the olefin) are present in equimolar amounts. In some embodiments, the two metathesis reactants are not present in equimolar amounts. In certain 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.

[0349] In some embodiments, one molar equivalent of the olefin is contacted with one molar equivalent of the olefin metathesis reaction partner. In some embodiments, about 1.5, 2, 2.5, or 3 molar equivalents of the olefin are contacted with one molar equivalent of the metathesis reaction partner. In some embodiments, about 1.5 molar equivalents of the olefin are contacted with one molar equivalent of the metathesis reaction partner.

[0350] Generally, reactions with many of the Z-selective metathesis catalysts disclosed herein obtain yields greater than 15%, such as greater than 50%, greater than 75%, or greater than 90%. In addition, the reactants and products are selected to obtain a difference in boiling point of at least 5°C, such as a difference greater than 20°C, or a difference greater than 40°C. In addition, the use of Z-selective metathesis catalysts allows for the formation of products faster than the formation of byproducts, and it can be desirable to perform these reactions as quickly as possible. In particular, the reactions are performed in less than about 24 hours, such as less than 12 hours, or less than 8 hours, or less than 4 hours. Advantageously, the methods of the present application provide metathesis products ranging from milligrams to hundreds of kilograms or more. For example, the methods can be performed using about 1-10 g of the internal olefin of Formula IV or about 10-100 g of the internal olefin of Formula IV or about 100-500 g of the internal olefin of Formula IV or about 500-1000 g of the internal olefin of Formula IV. The methods can be performed using at least 1, 5, 10, 25, 50, 100, or 1,000 kg of starting material. The metathesis reactions can be performed using a metathesis reactor such as described in WO 2011 / 046872, which can be operated in conjunction with one or more downstream separation units to isolate and / or recycle specific product or byproduct streams (e.g., an olefin stream, a C2-C3 compound stream, or a C3-C5 compound stream). The metathesis reactor and separation unit(s) can be operated in conjunction with one or more adsorption beds to facilitate separation of the metathesis products from the catalyst, as well as washing and drying units to purify the target products. The reduction, acylation, and metathesis reactions can be performed to obtain products in the metric ton scale.

[0351] Those skilled in the art will recognize that time, temperature, and solvent can be interdependent, and that changing one can require changing others to produce metathesis products in the processes of the present application. The metathesis step can be carried out at a variety of temperatures and times. Generally, the reactions in the processes of the present application are carried out using reaction times ranging from a few minutes to several days. For example, reaction times ranging from about 12 hours to about 7 days can be used. In some embodiments, reaction times ranging from 1-5 days can be used. In some embodiments, reaction times ranging from about 10 minutes to about 10 hours can be used. Generally, the reactions in the processes of the present application are carried out at temperatures ranging from about 0 °C to about 200 °C. For example, the reactions can be carried out at 15-100 °C. In some embodiments, the reactions can be carried out at 20-80 °C (e.g., 20-60 °C). In some embodiments, the reactions can be carried out at 100-150 °C.

[0352] The olefins, metathesis reaction partners, olefin starting materials, olefin-containing reactants, and fatty olefin derivatives (e.g., enol, unsaturated fatty alcohol acetate, unsaturated fatty ester acetate, olefin metathesis reaction partner, fatty olefin metathesis product, unsaturated fatty aldehyde, unsaturated fatty carboxy derivative, metathesis product, etc.) and other materials used in the processes of the present application can be obtained from any suitable source. In some embodiments, the metathesis reaction partners used in the processes of the present application are obtained from natural oils and / or derivatives thereof (e.g., unsaturated fatty acids described above).

[0353] In some embodiments, the materials reacted in the metathesis reaction, including those derived from natural oils, will contain one or more contaminants and can have the potential to adversely affect the performance of the metathesis catalyst. Such contaminants can be referred to as "catalyst poisons" or "catalyst poisoning contaminants." The methods described herein can reduce the level of contaminants. In some embodiments, the feedstock contains multiple contaminants and the method includes reducing the level of two or more contaminants. In some embodiments, the feedstock contains multiple contaminants and the method includes reducing the level of three or more contaminants. In some embodiments, the feedstock contains multiple contaminants and the method includes reducing the level of four or more contaminants. In some embodiments, the feedstock contains multiple contaminants and the method includes reducing the level of five or more contaminants.

[0354] Representative contaminants include, but are not limited to, water, peroxides, peroxide decomposition products, hydroperoxides, protic species, polar species, Lewis basic catalyst poisons, and the like and combinations thereof. It will be appreciated that some contaminants can be appropriately classified in multiple categories (e.g., an alcohol can be considered both a protic species and a polar species). It will also be appreciated that different catalysts can have different sensitivities to particular contaminants, and to contaminants that adversely affect the performance of one catalyst.

[0355] Representative protic species that can be present in the species reacted in the metathesis reaction include, but are not limited to, species having hydrogen atoms bonded to oxygen (e.g., carboxylic acids, alcohols, etc.) and / or hydrogen atoms bonded to nitrogen (e.g., primary amines, secondary amines, etc.). In some embodiments, particularly but not exclusively in natural oil substrates, the protic species contaminants can comprise carboxylic acid functionality, hydroxyl functionality, or combinations thereof. In some embodiments, the protic species is selected from free fatty acids, hydroxyl-containing species, MAGs, DAGs, and the like, and combinations thereof.

[0356] Representative polar species that can be present in the species reacted in the metathesis reaction include, but are not limited to, heteroatom-containing species, such as oxygen-containing compounds. In some embodiments, the polar species is selected from alcohols, aldehydes, ethers, and the like, and combinations thereof.

[0357] Representative Lewis base catalysts that can be present in the species reacted in the metathesis reaction include, but are not limited to, heteroatom-containing species. In some embodiments, the Lewis base catalyst poisons are selected from N-containing species, P-containing species, S-containing species, and the like, and combinations thereof.

[0358] The contaminant-containing reaction species can be treated with one or more moderators that mitigate the potentially deleterious effects of one or more contaminants. Moderators that can be used in the processes of the present application (individually, or in combination, sequentially or simultaneously) include: heat, molecular sieves, alumina (aluminum oxide), silica gel, montmorillonite clay, bleaching earth, bleaching clay, diatomaceous earth, zeolites, kaolin clay, 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 CaH2, etc.), 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, etc.), metal carbonates (e.g., calcium carbonate, sodium carbonate, etc.), metal silicates (e.g., magnesium silicate, etc.), phosphorous pentoxide, metal aluminum hydrides (e.g., alkali metal aluminum hydrides such as LiAlH4, NaAlH4, etc.), alkyl aluminum hydrides (e.g., DIBALH), metal boron hydrides (e.g., alkali metal boron hydrides such as LiBH4, NaBH4, etc.), organometallic reagents (e.g., Grignard reagents; organolithium reagents such as n-butyllithium, t-butyllithium, sec-butyllithium; trialkylaluminums such as triethylaluminum, tributylaluminum, triisobutylaluminum, triisopropylaluminum, trioctylaluminum, etc.), amido metals (e.g., diisopropylamido lithium, bis(trimethylsilyl)amido metals such as KHMDS, etc.), palladium on carbon (Pd / C) catalysts, and combinations thereof.

[0359] In some embodiments, the conditioning 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., eicosyl). Examples of metal alkyl compounds include, but are not limited to, Mg(CH3)2, Mg(C2H5)2, Mg(C2H5)(C4H9), Mg(C4H9)2, Mg(C6H 13 )2, Mg(C 12 H 25 )2, Zn(CH3)2, Zn(C2H5)2, Zn(C4H9)2, Zn(C4H9)(C8H 17 ), Zn(C6H 13 )2, Zn(C6H3)2, Al(C2H5)3, Al(CH3)3, Al(n-C4H9)3, Al(C8H 17 )3, Al(i-C4H9)3, Al(C 12 H 25 )3, and combinations thereof. Metal alkyl compounds also include species having one or more halogen or hydride groups, such as ethyl aluminum dichloride, diethyl aluminum chloride, diethyl aluminum hydride, Grignard reagents, diisobutyl aluminum hydride, and the like.

[0360] In some embodiments, the treatment of the metathesis reactant species (e.g., a natural oil or natural oil derivative) can include contacting the reactant species with a metal alkyl compound, and simultaneously or separately contacting the reactant species with a hydride-containing compound. In some embodiments, where the reactant species is contacted with both a metal alkyl compound and a hydride-containing compound simultaneously, the hydride-containing compound can be included in the metal alkyl compound. For example, in some cases, the methods used to manufacture certain metal alkyl compounds, such as trialkyl aluminum compounds, can result in the formation of a certain concentration of hydride-containing compounds. However, in other embodiments, the metal alkyl compound can be combined with one or more hydride-containing compounds. Alternatively, in some embodiments, the metathesis reactant species can be treated with a hydride-containing compound in a separate treatment step, which can be performed prior to, after, or both prior to and after treatment of the reactant species with a metal alkyl.

[0361] Any suitable hydride-containing compound can be used. In some embodiments, the hydride-containing compound is selected from metal aluminum hydrides (e.g., alkali metal aluminum hydrides, such as LiAIH4, NaAlH4, and the like), alkyl aluminum hydrides (e.g., DIBALH), and combinations thereof. In some embodiments, the hydride-containing compound is an alkyl aluminum hydride, such as DIBALH.

[0362] In some embodiments, the metathesis reactant is contacted with the hydride- containing compound in the same step in which the reactant is contacted 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 2: 1, or 5: 1, or 10: 1, or 15: 1, or 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.

[0363] In certain instances, the efficacy of a Z-selective metathesis catalyst can be improved (e.g., the number of turnovers can be increased or the overall catalyst loading can be reduced) by slowly adding the catalyst to the substrate. When added slowly, the overall catalyst loading to achieve the same number of turnovers can be reduced by at least 10%, at least 20%, or at least 30% as compared to the overall catalyst loading achieved in a single full batch load. Slow addition of the overall catalyst loading can include adding a partial catalyst load to the reaction mass at an average rate of about 10 ppm catalyst by weight 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 slowly added at a rate of about 0.01-10 ppmwt / hr, 0.05-5 ppmwt / hr, or 0.1-1 ppmwt / hr. The catalyst can be slowly added in batch loads at a frequency of every 5 minutes, 15 minutes, 30 minutes, 1 hour, 2 hours, 4 hours, 12 hours, or 1 day. In other embodiments, the slow addition is performed during a continuous addition process.

[0364] In some embodiments, the internal olefin (Z5-decene) and the metathesis reaction partner (e.g., oleyl acetate) are combined in a 2: 1 to 10: 1 (e.g., 5: 1) ratio and treated with an aluminum reagent (e.g., 1 wt% magnesium aluminum isopropoxide) prior to the addition of the metathesis catalyst (e.g., ruthenium catalyst 3 as described below) at a loading of 1-100 ppm per double bond (e.g., 3-50).

[0365] Preparation of internal olefins

[0366] In some embodiments, the synthesis of the fatty olefin metathesis product includes forming an internal olefin by contacting a terminal olefin with a metathesis catalyst to form an internal olefin. In some embodiments, the internal olefin is a compound of Formula Via:

[0367] and

[0368] The terminal olefin is a compound of Formula IVb:

[0369]

[0370] 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 is prepared using a metathesis catalyst having a structure according to Formula XI:

[0371]

[0372] wherein:

[0373] M is tungsten,

[0374] R 206a is each optionally substituted aryl, heteroaryl, alkyl, or cycloalkyl;

[0375] R 210a is each optionally substituted pyrrolyl, imidazolyl, indolyl, pyrazolyl, azaindolyl, or indazolyl;

[0376] R 211a is optionally substituted aryl;

[0377] R 208a is a hydrogen atom, alkyl, or alkoxy;

[0378] 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; and

[0379] R 207c and R 207d are independently a hydrogen atom, C 1-6 alkyl, C 1-6 alkoxy, a halogen atom, -NO2, amide, or sulfonamide.

[0380] In some embodiments, R 210a is each optionally substituted pyrrolyl, imidazolyl, pyrazolyl, azaindolyl, or indazolyl; and R 208a is a hydrogen atom. R 206a is phenyl, 2,6-dichlorophenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2- trifluoromethylphenyl, pentafluorophenyl, t-butyl, or 1-adamantyl. In some embodiments, R 207b is methoxy, R 207c is hydrogen, and R 207d is hydrogen. In some embodiments, R 206a is:

[0381]

[0382] In some embodiments, the internal olefin is prepared using a metathesis catalyst having a structure according to Formula XII:

[0383]

[0384] wherein:

[0385] M 300 is ruthenium;

[0386] L 301 is a ligand having the structure,

[0387]

[0388] wherein:

[0389] Q 300 is selected from alkylene, substituted alkylene, heteroatom-containing alkylene, or substituted heteroatom-containing alkylene, wherein two or more substituents on adjacent atoms within Q can also be linked to form an additional cyclic structure, and

[0390] R 303 and R 304 are independently selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

[0391] Q 301 is a bond between the carbon atom of M 300 and R 303 ;

[0392] R 305 , R 306 , R 307 , and R 308 are each independently selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenoxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfenyl, 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 boronate, wherein any combination of R 305 , R 306 , R 307 , and R 308 may be linked to form one or more cyclic groups;

[0393] X 301selected from halide, nitrate, alkyl, aryl, alkoxy, alkyl carboxylate, aryloxy, alkoxycarbonyl, aryloxycarbonyl, aryl carboxylate, acyl, acyloxy, alkyl sulfonate, aryl sulfonate, alkyl sulfanyl, aryl sulfonyl, alkyl sulfinyl, and aryl sulfinyl;

[0394] Y 300 is a heteroatom selected from N, O, S, and P;

[0395] when Y 300 is O or S, subscript q is 1, and when Y 300 is N or P, subscript q is 2; and

[0396] Z 300 is selected from hydrogen, alkyl, aryl, functionalized alkyl, or functionalized aryl, wherein the functional group is independently selected from 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.

[0397] “Hydrocarbyl” refers to a monovalent hydrocarbon group containing from 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including straight- chain, branched-chain, cyclic, saturated, and unsaturated species, such as alkyl, alkenyl, aryl, and the like. “Hvdrocarbylene” refers to a divalent hydrocarbon moiety containing from 1 to about 30 carbon atoms.

[0398] In some embodiments, Q 300 is a hydrocarbylene (e.g., ethylene). In some embodiments, ligand L 301 is a 1,3 disubstituted 4,5-dihydroimidazol-2-ylidene moiety. In some embodiments, R 303 is adamantyl or substituted adamantyl, or substituted C 3-12 cycloalkyl. In some embodiments, R 304 is disubstituted aryl (e.g., phenyl wherein both ortho ring positions are substituted, such as phenyl substituted with isopropyl) or trisubstituted aryl (e.g., phenyl wherein both ortho ring positions and the para ring position are substituted, such as phenyl substituted with methyl).

[0399] In some embodiments, R 305 , R 306 , R 307 , and R 308 are hydrogen. In some embodiments, Y 300 is O. In some embodiments, Z 300 is alkyl (e.g., isopropyl). In some embodiments, X301 is nitrate.

[0400] Metathesis reactions for preparing internal olefins (e.g., Z5-decene) from terminal olefins (e.g., 1-hexene) can be carried out as described above for preparing acylated enol metathesis products and enal acetal metathesis products. In some embodiments, a terminal olefin according to Formula IVb (e.g., 1-hexene) is combined with a ruthenium catalyst as shown below:

[0401]

[0402] In some embodiments, the catalyst is present in an amount of 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 of about 20 °C to about 60 °C (e.g., 50 °C) for 1-8 hours or more. The reaction can be carried out neat without additional solvent.

[0403] Compositions and uses thereof

[0404] In some embodiments, the fatty olefin metathesis product prepared according to the methods described herein is a pheromone. Accordingly, the pheromones prepared herein can be formulated for use as an insect control composition. The pheromone composition can comprise a carrier and / or be contained in a dispenser. The carrier can be, but is not limited to, an inert liquid or solid.

[0405] Examples of solid carriers include, but are not limited to, fillers such as kaolin, bentonite, dolomite, calcium carbonate, talc, magnesium oxide powder, Fuller's earth, wax, gypsum, diatomite, rubber, plastic, silica, and china clay. Examples of liquid carriers include, but are not limited to, water; alcohols, such as ethanol, butanol, or ethylene glycol, and their ethers or esters, such as methyl ethylene 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 alkyl naphthalene; mineral or vegetable oils; aliphatic chlorinated hydrocarbons such as trichloroethane or dichloromethane; aromatic chlorinated hydrocarbons, such as chlorobenzene; water-soluble or strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone; liquefied gases; and mixtures thereof. Bait or feeding stimulants can also be added to the carrier.

[0406] The pheromone composition can be formulated to be slowly released into the atmosphere, and / or to be protected from degradation upon release. For example, the pheromone composition can be contained in a carrier such as microcapsules, biodegradable foils, and solid paraffin-based matrices.

[0407] The pheromone composition can contain other pheromones or attractants, provided that the other compounds do not substantially interfere with the activity of the composition. The pheromone composition can also include a pesticide. Examples of suitable pesticides include, but are not limited to, buprofezin, pyriproxyfen, flonicamid, acetamiprid, dinotefuran, clothianidin, acephate, malathion, phosalone, chlorpyrifos, profenofos, dibutyl phthalate, bifenthrin, chlorpyrifos, cyfluthrin, diazinon, pyrethrin, fenpropathrin, hydroprene, saponin or oil and mixtures thereof.

[0408] The pheromone composition can be used in conjunction with a dispenser to release 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, a bubble cap with a permeable barrier reservoir through which the pheromone can be slowly released, a pad made of rubber, plastic, leather, cotton, cotton wool, wood or wooden articles impregnated with the pheromone composition, a bead, a tube stick, a spiral or a ball. For example, a polyvinyl chloride sheet, pellet, granule, rope or spiral or a rubber septum from which the pheromone composition evaporates. The skilled person will be able to select a suitable carrier and / or dispenser for the desired mode of application, storage, transport or handling.

[0409] 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 present application and formulated as described above. For example, the methods of the present application can be used to prepare the Spodoptera frugiperda sex pheromone, which is (Z)-tetradec-9-en-1-yl acetate. The Spodoptera frugiperda sex pheromone can be used in conjunction with a sustained pheromone release device having a polymeric container containing the Spodoptera frugiperda sex pheromone and a mixture of fatty acid esters (e.g., sebacate, laurate, palmitate, stearate, or arachidate) or fatty alcohols (e.g., undecanol, dodecanol, tridecanol, tridecenol, tetradecanol, tetradecenol, tetradecadienol, pentadecanol, pentadecenol, hexadecanol, hexadecenol, hexadecadienol, octadecenol, and octadecadienol). The polymeric container can be a tube, ampoule, or pouch made from a polyolefin or a copolymer containing an olefinic component. Sex pheromones for other pests such as the cotton bollworm (Helicoverpa armigera), the oriental fruit moth (Grapholita molesta), and the leafrollers (Tortricidae) can be used in such sustained pheromone release devices. Sex pheromones generally include one or more fatty acetic 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 fatty aldehyde compounds having 10 to 16 carbon atoms (e.g., 7-hexadecenal, 11-hexadecenal, 13-octadecenal, etc.).

[0410] Pheromones prepared according to the methods of the present application and compositions containing pheromones can be used to control the behavior and / or growth of insects in a variety of environments. For example, pheromones can be used to attract or repel male or female insects to or from a particular target area. Pheromones can be used to attract insects away from a vulnerable crop area. Pheromones can also be used to attract insects as part of an insect monitoring, mass trapping, luring / attracting and killing or mating disruption strategy, for example.

[0411] Mass trapping includes placing a high density of traps in a protected crop area in order to repel a large portion of the insects before the crop is damaged. Luring / attracting and killing techniques are similar, except that once the insects are attracted to the bait, they are affected by a killing agent. When the killing agent is a pesticide, the dispenser can also contain a feeding stimulant that lures or induces the insects to ingest an effective amount of the pesticide.

[0412] Those skilled in the art will appreciate that various different traps can be used. Suitable examples of such traps include water traps, sticky traps, and one-way traps. There are many varieties of sticky traps. One example of a sticky trap is a paperboard structure that is triangular or wedge shaped in cross section with an inner surface coated with a non-drying adhesive. Insects contact the adhesive surface and are captured. Water traps include a dish of water and detergent to capture insects. The detergent breaks the surface tension of the water, causing insects attracted to the dish to drown in the water. One-way traps allow an insect to enter the trap but prevent it from leaving. The traps of the present invention can be brightly colored to provide additional attraction to insects.

[0413] The traps are arranged in areas of insect infestation (or potential infestation). Typically, the traps are placed on or near a tree or large plant and the pheromone attracts insects into the trap. The insects can then be captured, immobilized, and / or killed in the trap, for example, by a killing agent present in the trap.

[0414] Pheromones prepared according to the methods of the present invention can also be used to interrupt mating. Strategies for mating interruption include interference, masking trails, and false trail following. Continuous exposure of insects to high concentrations of pheromone can prevent male insects from responding to normal levels of pheromone released by female insects. Masking trails uses pheromone to disrupt the trail of pheromone released by females. False trail following presents males with many false trails by placing many spots of pheromone at high concentrations. When released in sufficiently high amounts, male insects cannot find the natural source of sex pheromone (female insects) and mating does not occur.

[0415] Insect populations can be investigated or monitored by counting the number of insects in a target area (e.g., the number of insects captured in a trap). Inspectors can provide information about the life stage of the population. Knowing where the insects are, how many there are, and their life stage allows for intelligent decisions about where and when to use pesticides or other treatments. For example, finding a high insect population can require the use of a method to remove the insects. Early warning of infestations in new habitats can allow action to be taken before the population becomes unmanageable. Conversely, finding a low insect population can allow population monitoring to continue. Insect populations can be monitored on a regular basis so that insects are controlled only when they reach a certain threshold. This provides for economic and efficient control of insects and reduces the environmental impact of using pesticides.

[0416] It will be apparent to those skilled in the art that the amount of pheromone or pheromone composition used for a particular application can vary depending on several factors, such as the type and level of infestation; the type of composition used; the concentration of active ingredient; the manner in which the composition is provided, e.g., the type of dispenser used; the type of location to be treated; the length of time the method is used; and environmental factors such as temperature, wind speed and direction, rainfall, and humidity. Those skilled in the art will be able to determine an effective amount of pheromone or pheromone composition in a given application.

[0417] IV. Examples

[0418] Example 1. Synthesis of oleyl alcohol

[0419] Due to the extreme conditions required by the heterogeneous catalyst (i.e., copper chromite) used in those processes, commercial oleyl alcohol contains isomerization-derived impurities (i.e., elaidyl alcohol). High purity oleyl alcohol can optionally be prepared using homogeneous catalysts (e.g., [Ru-SNS] or [Ru-PNP]) and milder conditions (see Figure 1 ).

[0420] In a typical preparation, methyl oleate is combined 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]) in a reactor. The reactor is then heated to 30-60 °C and pressurized with hydrogen gas to 5-30 bar. When the reaction is complete, the reactor is depressurized, and the contents are washed with water or an aqueous solution (i.e., aqueous hydrochloric acid) to remove reaction byproducts. If desired, the product can be further purified by methods such as distillation. Oleyl alcohol produced using Ru-SNS and Ru-PNP provides >98% Z-selectivity and <1.0% over-reduction of double bonds.

[0421] Example 2. Synthesis of oleyl acetate

[0422] Condition A: A round bottom flask equipped with a magnetic stir bar is charged with oleyl alcohol (1 molar equivalent), dichloromethane, and NEt3(3 molar equivalents). The flask is placed under an inert atmosphere and cooled with an external ice bath. Acetic anhydride (2 molar equivalents) is added dropwise to the flask, followed by a catalytic amount of 4-dimethylaminopyridine. The reaction mixture is slowly warmed to room temperature overnight. After 16 hours, the reaction is quenched with water, and the organic layer is washed with saturated aqueous ammonium chloride. After additional washing with saturated aqueous sodium bicarbonate and aqueous sodium chloride, the resulting organic layer is dried using anhydrous magnesium sulfate. The magnesium sulfate is removed by filtration, and all volatile components are removed in vacuo to yield a yellow to colorless oil in >95% yield.

[0423] Condition B: A round bottom flask equipped with a magnetic stir bar is charged with oleyl alcohol (1 molar equivalent) and a catalytic amount of anhydrous sodium acetate. The flask is placed under an inert atmosphere and heated to 60 °C with stirring. Acetic anhydride (1.2 molar equivalents) is added at a rate such that the reaction temperature does not exceed 60 °C. After 16 hours, the reaction mixture is cooled to ambient temperature and quenched with water. The organic layer is washed with water and then dried using anhydrous magnesium sulfate. The magnesium sulfate is removed by filtration to yield a yellow to colorless oil in >95% yield.

[0424] The Z:E ratio of the oleyl acetate obtained from these procedures is as low as 80:20 and is typically no higher than 95:5, depending on the commercial source of the oleyl alcohol.

[0425] Example 3. Synthesis of Z-internal olefins for metathesis reactions

[0426] 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., a tungsten catalyst or a ruthenium catalyst). Ethylene produced during the metathesis reaction is purged with an inert gas, such as nitrogen or argon. Alternatively, ethylene can be removed by applying an appropriate vacuum to remove ethylene while leaving the starting materials in the reaction system.

[0427] To a reactor containing a reflux condenser and optional inert gas inlet is added 1.0 mol of terminal olefin (water < 100 ppm; peroxide value (PV) < 0.1 meq / Kg) and degassed with inert gas for 15 minutes. When a tungsten catalyst is used, a saturated ester such as methyl decanoate (1000-5000 mol ppm relative to internal olefin) is added. Triethylaluminum (TEAl; 1000 to 3000 mol ppm relative to moles of terminal olefin) is added and stirred for 1 h to 24 h (e.g., 4 h to 8 h). When a ruthenium catalyst is used, it is effective to pretreat the starting materials by filtration through a plug of activated alumina to obtain water < 100 ppm and PV < 0.1 meq / Kg.

[0428] The cis-selective catalyst is added in one portion (3-50 mol ppm relative to moles of terminal olefin) and stirring is initiated. An inert gas purge is initiated at a flow rate of 15 to 30 L / h / Kg. Alternatively, vacuum assistance can be used to remove ethylene, with a typical pressure of 400 Torr to 30 Torr. The starting materials are maintained in the reactor by use of a reflux condenser. The metathesis reaction is run for 1 to 30 h, typically 4 to 8 h.

[0429] A tungsten catalyst was deactivated with 3000 to 5000 mol ppm of alcohol (e.g., methanol, ethanol, isopropanol, oleyl alcohol, etc.) relative to the moles of terminal olefin. The judicious choice of alcohol allows for the recycling of starting materials and intermediates. The addition of alcohol deactivates the metathesis catalyst and decomposes excess triethylaluminum. For the ruthenium catalyst, tetraethylenepentamine (TEPA; 100 moles, excess relative to catalyst) was added and heated to reflux for 1 hour. For both catalysts, typical reaction yields were 50% to 70% with >97% Z-selectivity.

[0430] Synthesis of Z5-decene. The synthesis of Z5-decene involves the self-metathesis of pure 1-hexene using a Z-selective catalyst. The produced ethylene is removed from the reaction by vacuum. Efficient removal of ethylene contributes to high yield and high Z-selectivity. To a 250 mL round bottom three neck flask containing a reflux condenser, inert gas inlet, and magnetic stir bar was added 40.8 g (0.49 mol) of 1-hexene (water concentration < 50 ppm and peroxide value (PV) < 0.1 meq / Kg). The material was degassed with nitrogen for 15 to 30 minutes while warming to 50 °C. The ruthenium catalyst 1 (2.6 mg, 3.92 x 10 -6 moles, 8 ppm per double bond) was added in one portion. The top of the reflux condenser was connected to a septum pump and vacuum was applied. The vacuum was controlled to 160 Torr to 90 Torr.

[0431]

[0432] After 7 hours, GC analysis showed a 75.9% yield of Z5-decene and 99% Z-selectivity. TEPA (100 molar equivalents relative to catalyst) was added to quench the ruthenium catalyst. The reaction mixture was vacuum distilled at 170 Torr, Bpt 114 °C, to isolate Z5-decene (24.2 g, 0.17 mol) in 71.4% isolated yield and 99% Z-selectivity. See Table 1, Example 3-14.

[0433] Table 1. Synthesis of Z5-decene using ruthenium catalyst 1

[0434]

[0435] In additional experiments outlined in Table 1, 1-hexene was reacted with ruthenium catalyst 1 from 20 °C to 60 °C to give Z5-decene in 60% to 80% yield and 99% Z-selectivity. Ruthenium catalyst 1 is air and moisture tolerant and is particularly advantageous for easy handling during the manufacture of fine chemicals such as insect pheromones. Ruthenium catalyst 1 was found to consistently provide improved Z:E ratios as well as increased yields, e.g., 10% higher yields, compared to other cis-selective catalysts. These advantages allow for a uniquely economical manufacturing process.

[0436] Synthesis of Z5-decene. 1-hexene reacted with catalyst 2 from 20 °C to 40 °C to give Z5-decene in 60-70% yield and >97% Z-selectivity. See Table 2 and Table 3.

[0437]

[0438] Synthesis of Z3-hexene. 1-butene reacted with catalyst 1 or catalyst 2 from -10 °C to 10 °C to give Z3-hexene, the reaction was worked up when Z-selectivity dropped to 97% or after 24 hours. Over 35% yield was obtained.

[0439] Synthesis of Z4-octene. 1-pentene reacted with catalyst 1 or catalyst 2 from 15 °C to 30 °C to give Z4-octene, the reaction was worked up when Z-selectivity dropped to 97% or after 24 hours. Over 50% yield was obtained.

[0440] Synthesis of Z3-hexene and Z5-decene. As a technique to increase the efficiency of 1-butene, 1-hexene saturated with 1-butene reacted with catalyst 1 or catalyst 2 from 10 °C to 40 °C to give Z5-decene, Z3-octene, and Z3-hexene, the reaction was worked up when Z-selectivity dropped to 97% or after 24 hours. Over 60% yield was obtained for the sum of Z5-decene, Z3-octene, and Z3-hexene based on the 1-hexene and 1-butene used.

[0441]

[0442] Synthesis of Z7-tetradecene. 1-octene reacted with catalyst 1 or catalyst 2 from 15 °C to 30 °C to give Z7-tetradecene, the reaction was worked up when Z-selectivity dropped to 97% or after 24 hours. Over 50% yield was obtained.

[0443] Synthesis of Z9-octadecene. 1-decene reacted with catalyst 1 or catalyst 2 from 15 °C to 30 °C to give Z9-octadecene, the reaction was worked up when Z-selectivity dropped to 97% or after 24 hours. Over 60% yield was obtained.

[0444] 9-decene acid methyl ester (9-DAME) self-metathesis to Z9-octadecene-dioic acid 1,18-dimethyl ester (ODDA). 9-DAME reacted with catalyst 1 or catalyst 2 from 20 °C to 40 °C and under <1 Torr vacuum to give ODDA, the reaction was worked up when Z-selectivity dropped to 97% or after 24 hours. ODDA was purified by wiped film evaporation.

[0445] 9-decenyl acetate self-metathesis to Z9-octadecene-diyl 1,18-diacetate (ODDAc2). 9-decenyl acetate is reacted with Catalyst 1 or Catalyst 2 from 20 °C to 40 °C and under <1 Torr vacuum to give ODDAc2, which is worked up when the Z-selectivity drops to 97% or after 24 hours. ODDAc2 is purified by wiped film evaporation.

[0446] 8-nonenyl acetate self-metathesis to Z8-hexadecene-diyl 1,16-diacetate (HDDAc2). 8-nonenyl acetate is reacted with Catalyst 1 or Catalyst 2 from 20 °C to 40 °C and under <1 Torr vacuum to give HDDAc2, which is worked up when the Z-selectivity drops to 97% or after 24 hours. HDDAc2 is purified by wiped film evaporation.

[0447] 7-octenyl acetate self-metathesis to Z7-tetradecene-diyl 1,14-diacetate (TDDAc2). 7-octenyl acetate is reacted with Catalyst 1 or Catalyst 2 from 20 °C to 40 °C and under <1 Torr vacuum to give Z7-tetradecene-diyl 1,14-diacetate TDDAc2, which is worked up when the Z-selectivity drops to 97% or after 24 hours. TDDAc2 is purified by wiped film evaporation.

[0448] 9-decenal acetal self-metathesis 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, propylene glycol acetal) is reacted with Catalyst 1 or Catalyst 2 from 20 °C to 40 °C and under <1 Torr vacuum to give ODDA(acetal)2, which is worked up when the Z-selectivity drops to 97% or after 24 hours. ODDA(acetal)2 is purified by wiped film evaporation.

[0449] Example 4. Cross-metathesis of oleyl acetate with (Z)-dec-5-ene

[0450] Commercially available oleyl acetate (Z9-18Ac) is a low cost commodity feedstock used to produce Z9 pheromones such as Z9-12Ac and Z9-14Ac. However, due to the nature of the hydrogenation and distillation used to make oleyl acetate, a significant amount (about 20%) of cis / trans isomerization occurs, resulting in the formation of trans-oleyl alcohol (E9-18Ac). Thus, metathesis products prepared from the available material were expected to contain a significant amount of E-alkene impurities. However, as described in detail below, it has now been found that surprisingly high Z-content (>99%) is obtained in the product when the metathesis reaction is carried out with catalysts such as Catalyst 3, Catalyst 4, and Catalyst 5.

[0451] AsFigure 2 As shown, 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 resulted in the formation of (Z)-tetradec-9-en-1-yl acetate (Z9-14Ac) and metathesis byproducts.

[0452] General procedure for cross-metathesis screening reactions. A vial was charged with olefinic starting materials (i.e., OA and (Z)-dec-5-ene) and a magnetic stir bar under an inert atmosphere. A stock solution of the metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) was prepared in dichloromethane. The desired 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 (about 30 °C). The reaction was typically stirred for 2 hours prior to the addition of an excess of tris(hydroxymethyl)phosphine relative to the amount of metathesis catalyst 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:

[0453] OA % Conversion (area %)

[0454]

[0455] Z9-14Ac GC Yield (area %)

[0456]

[0457] Z-Selectivity for Z9-14Ac (area %)

[0458]

[0459] Pretreatment of oleyl acetate to maximize catalyst efficiency. Using the general procedure for cross-metathesis described above, 0.5 mmol of oleyl acetate (either pretreated or unpretreated), 1.5 mmol of (Z)-dec-5-ene, and either 0.113 µmol or 0.038 µmol of Catalyst 3 or Catalyst 4 were combined. Pretreated oleyl acetate was purified by storage on an alumina bed or by reaction with homogeneous isopropyl magnesium aluminum (MgAl2(O-i-Pr)8). In the case of pretreatment using MgAl2(O-i-Pr)8, the reagent and oleyl acetate starting materials were mixed and stored at ambient temperature for about 20 hours before the screening reaction was performed without removing the pretreated reagent. The reactions were analyzed using GC, and the effect of oleyl acetate pretreatment on catalyst efficiency is presented in Table 4.

[0460] Table 4

[0461]

[0462] As described below, triethylaluminum (TEAl) can also be used for pretreatment.

[0463] Optimization of magnesium isopropoxide aluminum pretreatment conditions. Using the general procedure for cross-metathesis described above, 0.5 mmol of oleyl acetate (pretreated with MgAl2(O-i-Pr)8or untreated) was combined with 1.5 mmol of (Z)-dec-5-ene and 0.113 μmol or 0.038 μmol of catalyst 3 or catalyst 4. Prior to conducting the screening reactions, the pretreated oleyl acetate was purified by reaction with homogeneous MgAl2(O-i-Pr)8, where the MgAl2(O-i-Pr)8and oleyl acetate stock were mixed and stored at ambient temperature for about 1, 2, 4, 8, or 20 days without removal of the pretreatment reagent. The results of GC analysis of these pretreatment optimization screening reactions are listed in Table 5.

[0464] Table 5

[0465]

[0466] Kinetic study of product E / Z isomerization reactions of cross-metathesis reactions 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 at 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 GC analysis of these E / Z isomerization screening reactions are shown in Table 6.

[0467] Table 6

[0468]

[0469]

[0470] Preparative scale cross-metathesis of oleyl acetate and (Z)-dec-5-ene. In an argon-filled glovebox, a 3 liter round bottom flask 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 previously treated with activated alumina. Ruthenium catalyst 3 (0.375 g, 0.442 mmol) was added to the flask and the reaction was stirred at ambient temperature. After 5 hours, the contents of the flask were transferred to a 5 liter jacketed flask. Tris(hydroxymethyl)phosphine (30 mL of a 1 M isopropyl alcohol solution, 68 equivalents) was added and the contents were stirred at 60 °C for 18 hours. The reaction mixture was then washed with 1 liter of water twice. The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered through a medium frit funnel to give a light yellow liquid. The mixture was purified by fractional vacuum distillation at <0.1 torr. A 183 g main fraction was collected at a head temperature of 89-100 °C that was found to be 85% pure Z9-14Ac (0.63 mol, 43% molar yield based on oleyl acetate) by GC analysis.

[0471] Example 5. Cross-metathesis of oleyl acetate with (Z)-hex-3-ene

[0472] As shown in Scheme 5, Figure 3 Cross-metathesis of oleyl acetate (Z9-18Ac or “OA”) with (Z)-hex-3-ene in the presence of catalyst 3 results in the formation of (Z)-dodec-9-en-1-yl acetate (Z9-12Ac) and a metathesis byproduct (not shown).

[0473] A flask with a stir bar was charged with (Z)-hex-3-ene (3 mol) and oleyl acetate (1 mol), both of which had been previously treated for purification. The desired amount of catalyst 3 needed to reach equilibrium conversion was added to the flask and the reaction was stirred at ambient temperature. When the reaction was complete, the catalyst was deactivated by the addition of tris(hydroxymethyl)phosphine and heating the contents with stirring. The reaction mixture was then washed with water and the organic layer was separated. The organic layer was dried and then purified by fractional vacuum distillation to give pure (Z)-dodec-9-en-1-yl acetate (Z9-12Ac).

[0474] Example 6. Investigation of starting material composition for cross-metathesis of oleyl acetate with (Z)-dec-5-ene

[0475] Z9-14 Ac (Z9-tetradecenyl acetate) was synthesized from oleyl acetate and Z5-decene. Oleyl alcohol (Jarchem or BASF) was acetylated with acetic anhydride and catalytic amount of sodium acetate, worked up, and purified by wiped film evaporation. The Z:E ratio of oleyl acetate was as low as 80:20, typically no higher than 95:5. To a 2L round bottom three neck flask containing an inert gas inlet and magnetic stir bar was added oleyl acetate (310 g, 1.0 mol) and Z5-decene (700 g, 5.0 mol), both <100 ppm water concentration and <0.1 meq / Kg PV. The reaction mixture was degassed with nitrogen for 30 minutes. Magnesium aluminum isopropoxide (CAS # 69207-83-6) (10 g, 1 wt%) was added and the reaction was stirred at 45 °C for 24 h. Ruthenium metathesis catalyst 4 (304 mg, 0.4 mmol; 50 mol ppm relative to moles 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 mole excess relative to catalyst) was added and heated to 120 °C for 1 hour. The reaction was cooled to 45 °C, excess 250 mL 1M HC1 and TEPA-catalyst complex was removed. Sodium bicarbonate (200 mL, saturated in water) was added, mixed, and the aqueous phase was removed.

[0476] The crude reaction mixture was purified by vacuum distillation using a fractional distillation column containing a minimum of 8 theoretical plates. Z5-decene and Z5-tetradecene were removed under 160 torr vacuum. The product Z9-14 Ac (203 g, 0.8 mol, Bpt 105 °C to 110 °C at 0.2 torr) was provided by ruthenium catalyst 4 with good yield and excellent selectivity. The product was isolated with 99.4% Z-selectivity and 95% purity. The major impurity was Z9-octadecene (3%). This can be minimized by adding more equivalents of Z5-decene in the metathesis reaction and by employing refined distillation conditions. In addition, ruthenium catalyst 4 is a crystalline material that does not tend to generate static charge making it particularly advantageous for handling during manufacturing.

[0477] The effect of bond geometry in non-functionalized olefins such as Z5-decene was also investigated. Oleyl acetate was reacted with a mixture of 5-decene isomers having different E / Z ratios. The isomer mixture was prepared by mixing Z5-decene (95% Z) and a thermodynamic mixture of 5-decene isomers (E / Z = 81.5% / 18.5%) in different ratios. The results are shown in Table 7 below. It is notable that even when the decene starting material was about 60% E5-decene, Z selectivity close to 95% was observed.

[0478] Table 7

[0479]

[0480]

[0481] a Yields were calculated by GC area %.

[0482] Example 7. Synthesis of Jojoba Oil Acetate

[0483] In a round-bottom flask, commercial jojoba oil (3.5 kg) was reduced at about 0° C. using 1.2 molar equivalents of sodium bis(2-methoxyethoxy)aluminum hydride in toluene. The reaction mixture was quenched with aqueous sulfuric acid solution and then washed with water. The crude jojoba alcohol was then acetylated at 75-95° C. using excess acetic anhydride and a catalytic amount of anhydrous sodium acetate in toluene. After post-treatment, the final molar yield of jojoba acetate was >85%. GC analysis showed that the composition of the final product was 5.2 area % (Z)-octadec-9-ene-1-yl acetate, 55.6 area % (Z)-eicos-11-ene-1-yl acetate, 30.4 area % (Z)-docosahexadec-13-ene-1-yl acetate, 6.17 area % (Z)-tetracos-15-ene-1-yl acetate, and 2.6 area % unidentified.

[0484] Example 8. Cross-metathesis of jojoba acetate with (Z)-hex-3-ene

[0485] like Figure 4 As shown, cross-metathesis of a mixture of jojoba acetates ("JOAs") prepared from commercial jojoba oil with (Z)-hex-3-ene in the presence of Catalyst 3, Catalyst 4, or Catalyst 5 results in the formation of (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 byproducts.

[0486] General procedure for cross-metathesis screening reactions. A flask was charged with the olefinic starting material (i.e., jojoba oil acetate and 2 to 4 molar excess of (Z)-hex-3-ene) and a magnetic stir bar under an inert atmosphere. A stock solution of catalyst 3 or catalyst 4 was prepared in dichloromethane. The desired amount of catalyst solution was added to the flask containing the jojoba oil acetate (JOAs) 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 relative to the amount of metathesis catalyst added before an excess of tris(hydroxymethyl)phosphine 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 equations:

[0487]

[0488]

[0489]

[0490] Cross-metathesis of jojoba oil acetate and varying amounts of (Z)-hex-3-ene. Using the general procedure for cross-metathesis described above, 100 mmol of prepared JOAs and 2 or 4 molar equivalents of (Z)-hex-3-ene were combined with 75 ppm (mol) / double bond of catalyst 3 for 1 hour to examine the effect of substrate loading on reaction yield and selectivity. The reaction was analyzed using GC, the results of which are shown in Table 8.

[0491] Table 8

[0492]

[0493] Cross-metathesis of jojoba oil acetate and (Z)-hex-3-ene with catalyst 3 or catalyst 4. Using the general procedure for cross-metathesis described above, 100 mmol of prepared JOAs and 300 mmol of (Z)-hex-3-ene were combined with 2000, 300, or 150 ppm (mol) / double bond of catalyst 3 or catalyst 4 to examine the effect of catalyst on reaction yield and selectivity. The reaction was analyzed using GC, the results of which are shown in Table 9.

[0494] Table 9

[0495]

[0496] Cross metathesis of jojoba oil acetate and (Z)-hex-3-ene with varying amounts of catalyst. Using the general procedure for cross metathesis described above, 100 mmol of prepared JOAs and 300 mmol of (Z)-hex-3-ene were combined with 2000, 300, or 150 ppm (mol) / double bond of catalyst 3 to examine the effect of catalyst loading on reaction yield and selectivity. Reactions were analyzed using GC, and the results are shown in Table 10.

[0497] Table 10

[0498]

[0499] Example 9. Cross metathesis of jojoba oil with (Z)-hex-3-ene

[0500] As shown below Figure 5 , cross metathesis of commercial jojoba oil (i.e., a mixture of fatty acids) with (Z)-hex-3-ene in the presence of catalyst 4 or catalyst 6 resulted in the formation of cross-metathesized jojoba oil fatty acids and metathesis byproducts (not shown). The cross-metathesized jojoba oil fatty acids were then reduced to the corresponding cross-metathesized jojoba alcohol (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).

[0501] Jojoba oil and (Z)-hex-3-ene were cross metathesized with catalyst 4 or catalyst 6. Using the general procedure for cross metathesis described above, commercial jojoba oil (“JO”) (50 mmol) and (Z)-hex-3-ene (300 mmol) were cross metathesized using either metathesis catalyst 4 or metathesis catalyst 6. The reactions were run at ambient temperature for 2 hours. Prior to GC analysis, a sample of the cross-metathesized JO (i.e., a mixture of cross-metathesized jojoba oil fatty acids) was reduced using sodium bis(2-methoxyethoxy)aluminum hydride according to the procedure described in Example 7, “Synthesis of jojoba oil acetate.” The resulting cross-metathesized 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 was analyzed using the following equation, and the results are shown in Table 11.

[0502] Jojoba alcohol (“JO Alc.”) % Conversion (area %)

[0503]

[0504] Z-selectivity of Z11-14OH (area %)

[0505]

[0506] Table 11

[0507]

[0508]

[0509] Example 10. Synthesis of functionalized olefin products for agricultural applications

[0510] General cross-metathesis reaction conditions using ruthenium stereo- retaining metathesis catalysts. To a reactor with inert gas inlet is added 1.0 mol of functionalized internal olefin (e.g., oleyl acetate) and 3 to 6 molar equivalents of non-functionalized Z-internal olefin (e.g., Z5-decene), both with <100 ppm water and <0.1 meq / Kg PV. The internal olefin is degassed with inert gas for 15 minutes. Triethylaluminum (1000 to 3000 mol ppm relative to moles of internal olefin) is added and stirred for 1 to 24 hours. Alternatively, pre-treatment to achieve <100 ppm and <0.1 meq / Kg PV is effective by filtering the starting materials through a plug of activated alumina. The ruthenium stereo-retaining metathesis catalyst, e.g., Catalyst 3, Catalyst 4, Catalyst 5, etc. (3 to 50 ppm / internal double bond) is added in one portion and stirring is initiated. The reaction is typically run at 20 °C to 60 °C. TEPA (100 molar excess relative to catalyst) is added and heated to reflux for 1 hour to deactivate the catalyst. Typical reaction yields are 50% to 85% with >97% Z-selectivity for both catalysts. Purification and isolation is accomplished by fractional vacuum distillation through a packed bed.

[0511] Synthesis of Z9-14Ac from ODDAc2 and Z5-decene. ODDAc2 (1 mol) and Z5-decene (4 to 8 mol Z5-decene / mol ODDAc2) are stirred, degassed with nitrogen for 15 minutes and treated with triethylaluminum. A ruthenium stereo-retaining 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 fractional vacuum packed bed distillation to yield Z9-14Ac with >97% Z-selectivity.

[0512] Synthesis of Z9-12Ac 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 to 6 mol of Z3-hexene per mol of oleyl acetate) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium 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 fractional vacuum packed bed distillation with >97% Z-selectivity. The level of impurities such as Z9-octadecene is kept at <3%.

[0513] Synthesis of Z9-12Ac from ODDAc2 and Z3-decene. ODDAc2 (1 mol) and Z3-decene (4 to 8 mol of Z3-decene per mol of ODDAc2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum for 1 to 8 hours. A ruthenium 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 fractional vacuum packed bed distillation to yield Z9-12Ac with >97% Z-selectivity.

[0514] 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 to 6 mol of Z3-octene per mol of oleyl acetate) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium 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 fractional vacuum packed bed distillation. Both Z9-14Ac and Z9-12Ac are isolated with >95% purity and >97% Z-selectivity. The level of impurities such as Z9-octadecene is kept at <3%.

[0515] Synthesis of Z9-14Ac and Z9-12Ac from ODDAc2 and Z3-octene. ODDAc2 (1 mol) and Z3-octene (4 to 8 mol of Z3-octene per mol of ODDAc2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium 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 fractional vacuum packed bed distillation. Both Z9-14Ac and Z9-12Ac are isolated with >95% purity and >97% Z-selectivity.

[0516] Synthesis of Z8-12Ac from HDDAc2 and Z4-octene. Stir HDDAc2 (1 mol) and Z4-octene (3 to 6 mol Z4-octene / mol HDDAc2), degas with nitrogen for 15 minutes and treat with triethylaluminum. Add a ruthenium metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) and monitor the reaction by GC analysis. Isolate Z8-12Ac by fractional vacuum packed bed distillation with >95% purity and >97% Z-selectivity.

[0517] Synthesis of Z7-12Ac from TDDAc2 and Z5-decene. Stir TDDAc2 (1 mol) and Z5-decene (3 to 6 mol Z5-decene / mol TDDAc2), degas with nitrogen for 15 minutes and treat with triethylaluminum. Add a ruthenium metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) and monitor the reaction by GC analysis. Isolate Z7-12Ac by fractional vacuum packed bed distillation with >95% purity and >97% Z-selectivity.

[0518] Synthesis of Z9-16Ac from oleyl acetate and Z7-tetradecene. Convert oleyl alcohol to oleyl acetate and purify as described above. Stir oleyl acetate (1 mol) and Z7-tetradecene (4 to 8 mol Z7-tetradecene / mol oleyl acetate), degas with nitrogen for 15 minutes and treat with triethylaluminum. Add a ruthenium metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) and monitor the reaction by GC analysis. Isolate Z9-16Ac by fractional vacuum packed bed distillation with >95% purity and >97% Z-selectivity. The level of impurities (e.g., Z9-octadecene) is kept at <1%.

[0519] Synthesis of Z9-16Ac from ODDAc2 and Z7-tetradecene. Stir ODDAc2 (1 mol) and Z7-tetradecene (4 to 8 mol Z7-tetradecene / mol ODDAc2), degas with nitrogen for 15 minutes and treat with triethylaluminum. Add a ruthenium metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) and monitor the reaction by GC analysis. Isolate Z9-16Ac by fractional vacuum packed bed distillation with >95% purity and >97% Z-selectivity.

[0520] Synthesis of Z9-16 acetal from ODDA(acetal)2 and Z7-tetradecene (Z9-16 acetal is Z9-hexadecene aldehyde acetal). Stir ODDA(acetal)2 (1 mol) and Z7-tetradecene (4 to 8 mol Z7-tetradecene / mol ODDA(acetal)2), degas with nitrogen for 15 minutes and treat with triethylaluminum. Add a ruthenium stereo-retentive metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) and monitor the reaction by GC analysis. Isolate Z9-16 acetal by fractional vacuum packed bed distillation to >90% purity and >95% Z-selectivity.

[0521] Synthesis of Z9-18 Ac from ODDAc2 and Z9-octadecene (Z9-18 Ac is Z9-octadecenyl acetate). Stir ODDAc2 (1 mol) and Z9-octadecene (4 to 8 mol Z9-octadecene / mol ODDAc2), degas with nitrogen for 15 minutes and treat with triethylaluminum. Add a ruthenium stereo-retentive metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) and monitor the reaction by GC analysis. Isolate Z9-18c by fractional vacuum packed bed distillation to >95% purity and >97% Z-selectivity.

[0522] Synthesis of Z9-18 acetal from ODDA(acetal)2 and Z9-octadecene (Z9-18 acetal is Z9-octadecene aldehyde acetal). Stir ODDA(acetal)2 (1 mol) and Z9-octadecene (4-8 mol Z9-octadecene / mol ODDAc2), degas with nitrogen for 15 minutes and treat with triethylaluminum. Add a ruthenium stereo-retentive metathesis catalyst (e.g., Catalyst 3, Catalyst 4, or Catalyst 5) and monitor the reaction by GC analysis. Isolate Z9-18 acetal by fractional vacuum packed bed distillation to >90% purity and >95% Z-selectivity.

[0523] Synthesis of jojoba acetate by jojoba oil reduction and acetylation to jojoba acetate. Dilute jojoba oil (Greenchem) with an equal volume of anhydrous toluene, 1.5 molar equivalents of sodium bis dihydroaluminate relative to 1 mol jojoba ester. After reduction is complete, carefully dilute the reaction with sulfuric acid until the aqueous phase has a pH < 1 and wash with brine. Isolate the organic phase and make it anhydrous by azeotropic removal of water. Acetylate the anhydrous jojobanol as described above for oleyl acetate. Jojoba acetate is purified by wiped film evaporation at ~80% yield. Jojoba acetate composition is ~5% Z9-18 Ac, ~55% Z11-20 Ac, ~35% Z13-22 Ac, and ~5% Z15-24 Ac.

[0524] Z9-12Ac, Z11-14Ac (Z11-tetradecenyl acetate), and Z13-16Ac (Z13-hexadecenyl acetate) are synthesized from jojoba acetate and Z3-hexene. Jojoba acetate (1 mol) and Z3-hexene (4 to 8 mol of Z3-hexene per mol of jojoba acetate) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium 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 fractional vacuum packed bed distillation. Z9-12Ac, Z11-14Ac, and Z13-16Ac are isolated in >95% purity and >97% Z-selectivity.

[0525] Z9-14Ac, Z11-16Ac (Z11-hexadecenyl acetate), and Z13-18Ac (Z13-hexadecenyl acetate) are synthesized from jojoba acetate and Z5-decene. Jojoba acetate (1 mol) and Z5-decene (4 to 8 mol of Z5-decene per mol of jojoba acetate) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium 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 fractional vacuum packed bed distillation. Z9-14Ac, Z11-16Ac, and Z13-18Ac are isolated in >95% purity and >97% Z-selectivity.

[0526] Jojoba acetal is synthesized by jojoba oil reduction, oxidation, and acetal formation into jojoba acetal. Jojobanol is prepared as described above. Jojobanal is oxidized to an aldehyde (e.g., by Stahl oxidation, Swern oxidation, tetrapropylammonium perruthenate (TPAP) oxidation, etc.) using anhydrous jojobanol. Jojobanal 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 wiped film evaporation in ~70% isolated yield. Jojoba acetal composition is ~5% Z9-18 acetal, ~55% Z11-20 acetal, ~35% Z13-22 acetal, and ~5% Z15-24 acetal.

[0527] Z9-14 acetal (Z9-tetradecenyl aldehyde acetal), Z11-16 acetal (Z11-hexadecenyl aldehyde acetal), and Z13-18 acetal (Z13-octadecenyl aldehyde acetal) from jojoba acetal and Z5-decene. Jojoba acetal (1 mol) and Z5-decene (4 to 8 mol of Z5-decene per mol of jojoba acetal) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium 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 fractional vacuum packed bed distillation. Z9-14 acetal, Z11-16 acetal, and Z13-18 acetal are isolated in >80% purity and >90% Z-selectivity.

[0528] V. Exemplary Embodiments

[0529] Exemplary embodiments provided in accordance with the presently disclosed subject matter include, but are not limited to, the claims and the following embodiments:

[0530] 1. A method for synthesizing a Z-enriched fatty olefin metathesis product, the method comprising contacting an olefin metathesis reaction partner with an internal olefin in the presence of a Group 8 transition metal metathesis catalyst to form the Z-enriched fatty olefin metathesis product, wherein:

[0531] the fatty olefin metathesis product is an acylated enol or enal acetal,

[0532] the olefin metathesis reaction partner comprises a mixture of Z-olefins and E-olefins in a starting Z:E ratio,

[0533] the fatty olefin metathesis product comprises a mixture of Z-olefins and E-olefins in a product Z:E ratio, and

[0534] the product Z:E ratio is higher than the starting Z:E ratio.

[0535] 2. The method of embodiment 1, wherein:

[0536] the fatty olefin metathesis product is an acylated enol of Formula I:

[0537]

[0538] the metathesis reaction partner is a compound of Formula III

[0539]

[0540] the internal olefin is a compound of Formula IV

[0541]

[0542] R 1 selected from H and C 1-6 alkyl;

[0543] R 2 selected from C 1-18 alkyl and C 2-18 alkenyl;

[0544] R 3 is C 1-18 alkyl;

[0545] the subscript y is an integer from 0 to 17;

[0546] the subscript z is an integer from 0 to 17; and

[0547] the Group 8 transition metal metathesis catalyst is a Z-selective Group 8 transition metal catalyst.

[0548] 3. The method of either of embodiments 1 or 2, wherein the metathesis catalyst is a Z- selective ruthenium catalyst or a Z-selective osmium catalyst.

[0549] 4. The method of any of embodiments 1 to 3, wherein the fatty olefin metathesis product is at least 97% Z.

[0550] 5. The method of any of embodiments 1 to 3, wherein the fatty olefin metathesis product is greater than 98% Z.

[0551] 6. The method of any of embodiments 1 to 3, wherein the fatty olefin metathesis product is greater than 99% Z.

[0552] 7. The method of any of embodiments 1 to 6, wherein the metathesis reaction partner is about 1% E to about 50% E.

[0553] 8. The method of any of embodiments 2 to 7, wherein the synthesis of the fatty olefin metathesis product comprises forming the olefin metathesis reaction partner of formula III by contacting an acylating agent with an enol according to formula II

[0554]

[0555] 9. The method of embodiment 8, wherein the acylating agent is acetic anhydride.

[0556] 10. The method of either of embodiments 8 or 9, wherein the synthesis of the fatty olefin metathesis reaction partner comprises forming the enol of formula II by reducing an unsaturated fatty carboxyl derivative according to formula Ila

[0557]

[0558] wherein R 4 is selected from H and C 1-8 alkyl.

[0559] 11. The method of embodiment 10, wherein forming the enol of Formula II comprises contacting the unsaturated fatty carboxyl derivative with a base in the presence of a hydrogenation catalyst and hydrogen gas.

[0560] 12. The method of embodiment 10, wherein forming the enol of Formula II comprises contacting the unsaturated fatty carboxyl derivative with a reducing agent.

[0561] 13. The method of embodiment 12, wherein the reducing agent is sodium bis(2- methoxyethoxy)aluminum hydride.

[0562] 14. The method of any one of embodiments 8 to 13, wherein the enol of Formula II is about 1% E to about 50% E.

[0563] 15. The method of embodiment 1, wherein:

[0564] the fatty olefin metathesis product is an enal hemiacetal of Formula VI:

[0565]

[0566] the metathesis reaction partner is a compound of Formula VII:

[0567]

[0568] the internal olefin is a compound of Formula IV

[0569]

[0570] R 1 is C 1-6 alkyl;

[0571] R 2 is selected from C 1-18 alkyl and C 2-18 alkenyl;

[0572] R 3 is C 1-18 alkyl;

[0573] the subscript y is an integer from 0 to 17;

[0574] the subscript z is an integer from 0 to 17; and

[0575] the Group 8 transition metal metathesis catalyst is a Z-selective Group 8 transition metal catalyst.

[0576] 16. The method of embodiment 15, further comprising converting the metathesis product to an enal of Formula VIII: 2

[0577] 2 2 2

[0578] 217. The method of any one of embodiments 1 to 16, wherein the synthesis of the fatty olefin metathesis product comprises forming the internal olefin by contacting a terminal olefin with a metathesis catalyst to form an internal olefin. 2

[0579] 218. The method of embodiment 20, wherein the internal olefin is a compound of Formula Via: 2

[0580] 2 2and 2

[0581] 2the terminal olefin is a compound of Formula IVb: 2

[0582] 2 2 2

[0583] 219. The method of embodiment 17 or 18, wherein the metathesis catalyst used to form the internal olefin is a Z-selective ruthenium catalyst or a Z-selective tungsten catalyst. 2

[0584] 220. A method for synthesizing a fatty olefin metathesis product according to Formula I: 2

[0585] 2 2 2

[0586] 2the method comprising contacting an acylating agent with an enol according to Formula II 2

[0587] 2 2 2

[0588] 2to form an olefin metathesis reaction partner according to Formula III 2

[0589] 2 2and 2

[0590] 2contacting the olefin metathesis reaction partner with an internal olefin according to Formula IV 2

[0591] 2 2 2

[0592] 2in the presence of a Z-selective ruthenium catalyst or a Z-selective osmium catalyst 2

[0593] 2R 1 2is selected from H and C 1-6 2alkyl; 2

[0594] 2R 2 2is selected from C 1-18 2alkyl and C 2-18 2alkenyl;

[0595] R 3 is C 1-18 alkyl;

[0596] the subscript y is an integer from 0 to 17;

[0597] the subscript z is an integer from 0 to 17; and

[0598] the fatty olefin metathesis product is at least 97% Z.

[0599] 21. The method of embodiment 20, wherein the acylating agent is acetic anhydride.

[0600] 22. The method of embodiment 20 or 21, wherein the enol of Formula II is about 1% E to about 50% E.

[0601] 23. A method for synthesizing a fatty olefin metathesis product according to Formula I:

[0602]

[0603] the method comprising reducing an unsaturated fatty carboxyl derivative according to Formula Ha

[0604]

[0605] to form an enol according to Formula II

[0606]

[0607] contacting an acylating agent with the enol to form an olefin metathesis reaction partner according to Formula III

[0608] and

[0609] contacting the olefin metathesis reaction partner with an internal olefin according to Formula IV in the presence of a Z-selective ruthenium catalyst or a Z-selective osmium catalyst

[0610]

[0611] to form the fatty olefin metathesis product; wherein:

[0612] R 1 is selected from H and C 1-6 alkyl;

[0613] R 2 is selected from C 1-18 alkyl and C 2-18 alkenyl;

[0614] R 3 is C1-18 alkyl;

[0615] R 4 selected from H and C 1-8 alkyl;

[0616] the subscript y is an integer from 0 to 17;

[0617] the subscript z is an integer from 0 to 17; and

[0618] the fatty olefin metathesis product is at least 97% Z.

[0619] 24. The method of embodiment 23, wherein reducing the unsaturated fatty carboxyl derivative of Formula Ila to form the enol of Formula II comprises contacting the unsaturated fatty carboxyl derivative with a base in the presence of a hydrogenation catalyst and hydrogen gas.

[0620] 25. The method of embodiment 23, wherein reducing the unsaturated fatty carboxyl derivative of Formula Ila to form the enol of Formula II comprises contacting the unsaturated fatty carboxyl derivative with a reducing agent.

[0621] 26. The method of embodiment 25, wherein the reducing agent is sodium bis(2- methoxyethoxy)aluminum hydride.

[0622] 27. The method of any one of embodiments 23 to 26, wherein the acylating agent is acetic anhydride.

[0623] 28. The method of any one of embodiments 23 to 27, wherein the enol of Formula II is about 1% E to about 50% E.

[0624] 29. The method of any one of embodiments 2 to 28, wherein R 1 is C 1-3 alkyl, R 2 is C 1-12 alkyl, R 3 is C 1-12 alkyl, y is an integer from 5 to 15, and z is an integer from 0 to 7.

[0625] 30. The method of any one of embodiments 10, 11, 23, and 24, wherein R 1 is C 1-3 alkyl, R 2 is C 1-12 alkyl, R 3 is C 1-12 alkyl, R 4 is C 1-3 alkyl, y is 7, and z is an integer from 1 to 5.

[0626] 31. The method of any one of embodiments 10, 12, 23, and 25, wherein R 1 is C 1-3 alkyl, R 2 is C 1-12 alkyl, R 3 is C 1-12 alkyl, R 4 is H, y is an integer from 5 to 15, and z is an integer from 1 to 5.

[0627] 32. The method of any one of embodiments 2 to 7, wherein:

[0628] the metathesis reaction partner according to Formula III is a fatty C 12 - C 30 alkene acetic ester;

[0629] the internal olefin according to Formula IV is a C4-C 20 internal olefin; and

[0630] the fatty olefin metathesis product according to Formula I is a C8-C 28 (Z)-unsaturated fatty ester acetic ester.

[0631] 33. The method of any one of embodiments 2 to 7 and 32, wherein:

[0632] the olefin metathesis reaction partner according to Formula III is (Z)-octadec-9- en-1-yl acetate;

[0633] the internal olefin according to Formula IV is (Z)-dec-5-ene; and

[0634] the fatty olefin metathesis product according to Formula I is (Z)-tetradec-9- en-1-yl acetate.

[0635] 34. The method of any one of embodiments 2 to 7 and 32, wherein:

[0636] the olefin metathesis reaction partner according to Formula III is (Z)-octadec-9- en-1-yl acetate;

[0637] the internal olefin according to Formula IV is (Z)-hex-3-ene; and

[0638] the fatty olefin metathesis product according to Formula I is (Z)-dodec-9-en-1- yl acetate.

[0639] 35. The method of any one of embodiments 2 to 7 and 32, wherein:

[0640] the olefin metathesis reaction partner according to Formula III is (Z)-eicosa-11-en-1-yl acetate;

[0641] the internal olefin according to Formula IV is (Z)-hex-3-ene; and

[0642] the fatty olefin metathesis product according to Formula I is (Z)-tetradec-11-en-1-yl acetate.

[0643] 36. The method of any one of embodiments 8 to 31, wherein:

[0644] the enol according to Formula II is C 10 - C 28 fatty enol;

[0645] the olefin metathesis reaction partner according to Formula III is the C 10 - C 28 fatty enol acetate;

[0646] the internal olefin according to Formula IV is C4-C 20 internal olefin; and

[0647] the fatty olefin metathesis product according to Formula I is C8-C 28 (Z)-unsaturated fatty ester acetate.

[0648] 37. The method of any one of embodiments 10 to 36, wherein:

[0649] the enol according to Formula II is (Z)-octadec-9-en-1-ol;

[0650] the olefin metathesis reaction partner according to Formula III is (Z)-octadec-9-en-1-yl acetate;

[0651] the internal olefin according to Formula IV is (Z)-dec-5-ene; and

[0652] the fatty olefin metathesis product according to Formula I is (Z)-tetradec-9-en-1-yl acetate.

[0653] 38. The method of any one of embodiments 10 to 36, wherein:

[0654] the enol according to Formula II is (Z)-octadec-9-en-1-ol;

[0655] the olefin metathesis reaction partner according to Formula III is (Z)-octadec-9-en-1-yl acetate;

[0656] the internal olefin according to Formula IV is (Z)-hex-3-ene; and

[0657] the fatty olefin metathesis product according to Formula I is (Z)-dodec-9-en-1-yl acetate.

[0658] 39. The method of any one of embodiments 10 to 36, wherein:

[0659] the enol according to Formula II is (Z)-eicosa-11-en-1-ol;

[0660] the olefin metathesis reaction partner according to Formula III is (Z)-eicosa-11-en-1-yl acetate;

[0661] the internal olefin according to Formula IV is (Z)-hex-3-ene; and

[0662] the fatty olefin metathesis product according to Formula I is (Z)-tetradec-11-en-1-yl acetate.

[0663] 40. The method of any one of embodiments 1 to 38, wherein synthesis of the fatty olefin metathesis product comprises contacting the olefin metathesis reaction partner with a pretreatment reagent prior to contacting with the internal olefin.

[0664] 41. The method of embodiment 40, wherein the pretreatment reagent is selected from the group consisting of aluminum oxide, triethylaluminum, and magnesium aluminum isopropoxide.

[0665] 42. The method of any one of embodiments 10 to 12 and 23 to 25, wherein the unsaturated fatty carboxyl derivative is derived from a natural oil.

[0666] 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, grape seed oil, olive oil, palm oil, peanut oil, hemp oil, macadamia oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil, jojoba oil, mustard oil, oilseed rape oil, borage oil, castor oil, and combinations thereof.

[0667] 44. The method of embodiment 42 or 43, further comprising distilling the unsaturated fatty carboxyl derivative according to Formula Ila, the enol according to Formula II, or the olefin metathesis reaction partner of Formula III to remove plant-based impurities prior to metathesis.

[0668] 45. The method of embodiment 44, wherein the plant-based impurities comprise one or more proteins.

[0669] 46. The method of any one of embodiments 2 to 45, wherein the Z-selective metathesis catalyst has a structure according to Formula V:

[0670]

[0671] wherein:

[0672] M is selected from ruthenium and osmium;

[0673] X and Y are independently selected from S and O;

[0674] Z is selected from O, S(=0), N, and halogen;

[0675] the subscript m and the subscript n are each independently an integer selected from 0, 1, 2, 3, and 4;

[0676] each R a is independently selected from halogen, Ci-C6alkyl, alkoxy, aryl, and heteroaryl; or one R a forms, together with an adjacent R a , an unsubstituted or substituted bicyclic ring, or an unsubstituted or substituted polycyclic ring;

[0677] each R b is independently selected from halogen, Ci-C6alkyl, alkoxy, aryl, and heteroaryl; or one R b forms, together with an adjacent R b , an unsubstituted or substituted bicyclic ring, or an unsubstituted or substituted polycyclic ring;

[0678] R c is selected from hydrogen and Ci-C6alkyl;

[0679] each R d , R e , R f , and R g is independently selected from hydrogen and Ci-C6alkyl;

[0680] R 12 and R 13 are independently selected from 2,4,6-triisopropylphenyl, 2,6-diisopropylphenyl, 2,6-diamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert- butylphenyl, and 2,6-di-tert-butylphenyl;

[0681] each R 14 is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl, and phenyl; and

[0682] R 15 is selected from hydrogen, halogen, and Ci-C6alkyl, or R 15 and one R 14together form a bond.

[0683] 47. The method of embodiment 46, wherein:

[0684] M is ruthenium;

[0685] X and Y are S;

[0686] Z is selected from O and S(=0);

[0687] the subscript m is 2;

[0688] the subscript n is 0;

[0689] each R a is independently selected from halogen, Ci-C6alkyl, and aryl;

[0690] R c is hydrogen;

[0691] each R d , R e , R f , and R g is hydrogen; and

[0692] each R 14 is independently selected from methyl, isopropyl, benzyl, and tert-butyl.

[0693] 48. The method of embodiment 46 or 47, wherein the metathesis catalyst is selected from:

[0694]

[0695] While the foregoing has been described in some detail for purposes of clarity and the understanding, it will be appreciated that certain changes and modifications can be practiced within the scope of appended claims. All publications, patents, patent applications and sequence registry numbers cited herein are hereby incorporated by reference in their entirety for all purposes.

Claims

1. A process for synthesizing a Z-enriched aliphatic olefin metathesis product, said process 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 said Z-enriched aliphatic olefin metathesis product, wherein: The fatty olefin metathesis product is an acylated enol or enal acetal, The olefin metathesis reaction partners include a starting Z:E A mixture of Z olefins and E olefins in a ratio, The fatty olefin metathesis product comprises a product Z:E A mixture of Z olefins and E olefins in a ratio, The product Z:E Ratios higher than the starting Z:E ratio; and wherein the Z-selective Group 8 transition metal metathesis catalyst has a structure according to Formula V: (V)， in: M is selected from ruthenium and osmium; X and Y are independently selected from S and O; Z is selected from S(=O), O, N and halogen; Subscript m is an integer selected from 2, 4, 3, 1 and 0; Subscript n is an integer selected from 0, 1, 2, 3 or 4; Each R a independently selected from halogen, C1-C6 alkyl, alkoxy, aryl and heteroaryl; or one R a With adjacent R a together to form an unsubstituted or substituted polycyclic ring; Each R b independently selected from halogen, C1-C6 alkyl, alkoxy, aryl and heteroaryl; or one R b With adjacent R b together to form an unsubstituted or substituted polycyclic ring; R c Selected from hydrogen and C1-C6 alkyl; Each R d 、R e 、R f and R g Independently selected from hydrogen and C1-C6 alkyl; R 12 and R 13 independently selected from 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diadamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl; Each R 14 independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl, phenyl, and hydrogen; and R 15 is selected from hydrogen, halogen and C1-C6 alkyl, or R 15 and an R 14 together to form a bond.

2. The method of claim 1, wherein the fatty olefin metathesis product is at least 97% to 99% Z .

3. The method of claim 1, wherein the fatty olefin metathesis product is greater than 99%. Z .

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

5. The method of claim 1, wherein: The fatty olefin metathesis product is an acylated enol of formula I: (I)， The metathesis reaction partner is a compound of formula III (III), The internal olefin is a compound of formula IV (IV); R 1 Selected from H and C 1-6 alkyl; R 2 Selected from C 1-18 Alkyl and C 2-18 alkenyl; R 3 It is C 1-18 alkyl; Subscript y is an integer from 0 to 17; and The subscript z is an integer from 0 to 17.

6. The method of claim 1, wherein: M is ruthenium; X and Y are S; Z is selected from S(=O) and O; The subscript m is 2; Subscript n is 0; Each R a Independently selected from halogen, C1-C6 alkyl and aryl; R c It is hydrogen; Each R d 、R e 、R f and R g is hydrogen; and Each R 14 Independently selected from methyl, isopropyl, benzyl and tert-butyl.

7. The method of claim 1 , wherein the Z-selective Group 8 transition metal metathesis catalyst is selected from the group consisting of: 、 and .

8. The method of claim 5, wherein the synthesis of the fatty olefin metathesis product comprises forming the olefin metathesis reaction partner of formula III by contacting an acylating agent with an enol according to formula II (II), where R 2 Selected from C 1-18 Alkyl and C 2-18 The subscript y is an integer from 0 to 17.

9. The method of claim 8, wherein the acylating agent is acetic anhydride.

10. The method of claim 8, wherein the synthesis of the fatty olefin metathesis reaction partner comprises forming an olefin of formula II by reducing an unsaturated fatty carboxyl derivative according to formula IIa. (IIa), where R 2 Selected from C 1-18 Alkyl and C 2-18 alkenyl, subscript y is an integer from 0 to 17, and R 4 Selected from H and C 1-8 alkyl.

11. The method of claim 10, wherein forming the enol of Formula II comprises contacting the unsaturated fatty carboxyl derivative with a base in the presence of a hydrogenation catalyst and hydrogen.

12. The method of claim 10, wherein forming the enol of Formula II comprises contacting the unsaturated fatty carboxyl derivative with a reducing agent.

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

14. The method of claim 10, wherein the unsaturated fatty carboxyl derivative is derived from a natural oil.

15. The method of claim 14, 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, sesame oil, macadamia oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil, jojoba oil, mustard oil, thrush oil, camellia oil, castor oil, and combinations thereof.

16. The method of claim 14, further comprising distilling the unsaturated fatty carboxyl derivative, the enol, or the olefin metathesis reaction partner prior to metathesis to remove plant-based impurities.

17. The method of claim 1, wherein: The aliphatic olefin metathesis product is an aldehyde acetal of formula VI: (WE) The metathesis reaction partner is a compound of formula VII: (VII), The internal olefin is a compound of formula IV (IV); R 1 It is C 1-6 alkyl; R 2 Selected from C 1-18 Alkyl and C 2-18 alkenyl; R 3 It is C 1-18 alkyl; Subscript y is an integer from 0 to 17; and The subscript z is an integer from 0 to 17.

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

19. The process of claim 18, wherein the internal olefin is a compound of formula VIa: (VIa); and The terminal olefin is a compound of formula IVb: (IVb), wherein the subscript z is an integer from 0 to 17.

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

21. The method of claim 5, wherein: The metathesis reaction partner according to formula III is a fatty acid C 12 -C 30 olefin acetates; The internal olefin according to formula IV is C4-C 20 internal olefins; and The fatty olefin metathesis product according to formula I is C8-C 28 ( Z )-unsaturated fatty ester acetate.

22. The method of claim 5, wherein: The olefin metathesis reaction partner according to formula III is ( Z )-octadec-9-en-1-yl acetate; The internal olefin according to formula IV is ( Z )-dec-5-ene; and The fatty olefin metathesis product according to formula I is ( Z )-tetradec-9-en-1-yl acetate.

23. The method of claim 5, wherein: The olefin metathesis reaction partner according to formula III is ( Z )-octadec-9-en-1-yl acetate; The internal olefin according to formula IV is ( Z )-hex-3-ene; and The fatty olefin metathesis product according to formula I is ( Z )-dodec-9-en-1-yl acetate.

24. The method of claim 5, wherein: The olefin metathesis reaction partner according to formula III is ( Z )-eicos-11-en-1-yl acetate; The internal olefin according to formula IV is ( Z )-hex-3-ene; and The fatty olefin metathesis product according to formula I is ( Z )-tetradec-11-en-1-yl acetate.

25. 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.

26. The method of claim 25, wherein the pretreatment agent is selected from the group consisting of alumina, triethylaluminum, and magnesium aluminum isopropoxide.

27. A process for synthesizing alkenals of formula VIII 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 include a starting Z:E A mixture of Z olefins and E olefins in a ratio, The fatty olefin metathesis product comprises a product Z:E A mixture of Z olefins and E olefins in a ratio, The product Z:E Ratios higher than the starting Z:E ratio; and wherein the Z-selective Group 8 transition metal metathesis catalyst has a structure according to Formula V: (V)， in: M is selected from ruthenium and osmium; X and Y are independently selected from S and O; Z is selected from S(=O), O, N and halogen; Subscript m is an integer selected from 2, 4, 3, 1 and 0; Subscript n is an integer selected from 0, 1, 2, 3 or 4; Each R a independently selected from halogen, C1-C6 alkyl, alkoxy, aryl and heteroaryl; or one R a With adjacent R a together to form an unsubstituted or substituted polycyclic ring; Each R b independently selected from halogen, C1-C6 alkyl, alkoxy, aryl and heteroaryl; or one R b With adjacent R b together to form an unsubstituted or substituted polycyclic ring; R c Selected from hydrogen and C1-C6 alkyl; Each R d 、R e 、R f and R g Independently selected from hydrogen and C1-C6 alkyl; R 12 and R 13 independently selected from 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diadamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl; Each R 14 independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl, phenyl, and hydrogen; and R 15 is selected from hydrogen, halogen and C1-C6 alkyl, or R 15 and an R 14 together to form a bond, The aliphatic olefin metathesis product is an aldehyde acetal of formula VI: (WE) The metathesis reaction partner is a compound of formula VII: (VII), The internal olefin is a compound of formula IV (IV); R 1 It is C 1-6 alkyl; R 2 Selected from C 1-18 Alkyl and C 2-18 alkenyl; R 3 It is C 1-18 alkyl; Subscript y is an integer from 0 to 17; and The subscript z is an integer from 0 to 17, The method further comprises converting the fatty olefin metathesis product into the alkenal of formula VIII: (VIII), wherein subscript z is an integer from 0 to 17, and subscript y is an integer from 0 to 17.

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