Polyol-derived compounds

Abstract

To provide polyalcohols with a high BHB unit or acetoacetate concentration per polyalcohol unit and preparation processes thereof.SOLUTION: There is provided a compound of formula 1, wherein A is derived from an organic polyol with at least 4 hydroxyl groups (A is referred to as the first organic polyol A), X is -C(H)(OH)- or -C(H)(OR1)-, R1 is selected from linear or branched C1-12 alkyl, C3-8 cycloalkyl, linear or branched C2-12 hydroxyalkyl, linear or branched C1-12 carboxyalkyl, and phenyl, and y is from 1 to the number of hydroxyl groups of the initial organic polyol A, and wherein the first organic polyol A is selected from linear or branched C2-12 alkyl substituted with at least four hydroxyl groups, or C3-8 cycloalkyl substituted with at least four hydroxyl groups.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to polyol-derived compounds and processes for their preparation. [Background technology]

[0002] Acetoacetylated polyalcohols and the beta-hydroxybutyrate (BHB) esters of polyalcohols prepared therefrom are useful compounds with a wide range of uses, for example, as parenteral nutritional supplements or for the treatment of certain diseases.

[0003] US2019 / 117612A1 relates to the field of migraine and its comprehensive symptom management using 3-hydroxybutyric acid glyceride.

[0004] US2018 / 193300A1 relates to a method for treating mild to moderate non-penetrating closed traumatic brain injury and mild to moderate traumatic brain injury with surgical intervention using 3-hydroxybutyric acid glyceride.

[0005] Acetoacetylated polyalcohols and beta-hydroxybutyrate (BHB) esters of polyalcohols are typically prepared by coupling a polyalcohol, such as glycerol, with a protected beta-hydroxybutyrate or acetoacetate ester. Both methods suffer from poor atom economy and generate significant waste.

[0006] Furthermore, polyalcohol BHB esters typically have a low BHB content per polyalcohol unit. However, to increase BHB delivery efficiency, a higher BHB content per polyalcohol unit is expected to be desirable. Furthermore, protecting the BHB units in polyalcohol BHB esters allows for the delivery of additional BHB precursors, which are hydrolyzed and oxidized to BHB in the body, further increasing BHB delivery efficiency. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] US2019 / 117612 A1 [Patent Document 2] US2018 / 193300 A1 Summary of the Invention [Problem to be solved by the invention]

[0008] Thus, there is a need to provide polyalcohols having high concentrations of BHB units or acetoacetate per polyalcohol unit. Additionally, there is a need to provide BHB esters of polyalcohols in which the BHB units are further functionalized or protected.

[0009] There is a further need for optimized processes for the synthesis of such acetoacetylated polyalcohols and beta-hydroxybutyrate (BHB) esters of polyalcohols having a high content of BHB units or acetoacetate per polyalcohol unit. There is a further need for optimized processes for the synthesis of BHB esters of polyalcohols in which the BHB units are further functionalized or protected. [Means for solving the problem]

[0010] The inventors have surprisingly found that the process according to the invention by reacting diketene with a polyol or a β-hydroxyl butyric acid ester of a polyol produces beta-hydroxybutyric acid. We have found that this process provides an excellent method for producing stable, neutral analogs of acids. The reaction of a polyol or a β-hydroxybutyric acid ester of a polyol with diketene, followed by hydrogenation and optional esterification, allows for easy access to the desired product. The use of asymmetric hydrogenation provides access to enantiomerically pure derivatives. Furthermore, the process according to the present invention allows for the synthesis of polyalcohols with high BHB unit or acetoacetate concentrations per polyalcohol unit.

[0011] Thus, the present invention provides a compound of formula 1

[0012] [ka]

[0013] (In the formula, A is derived from an organic polyol having at least four hydroxyl groups; X is -C(H)(OH)- or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial organic polyol A. to provide.

[0014] In another aspect, the present invention provides a compound of formula 9

[0015] [ka]

[0016] (In the formula, z is 0 or 1, A is derived from an organic polyol having at least three hydroxyl groups; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial polyol A. to provide.

[0017] In another aspect, the present invention provides a compound of formula 9

[0018] [ka]

[0019] (In the formula, z is 0 or more, A is derived from an organic polyol having at least three hydroxyl groups, provided that the organic polyol is not erythritol; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial polyol A. to provide.

[0020] In another aspect, the present invention provides a compound of formula 1

[0021] [ka]

[0022] (In the formula, A is derived from an organic polyol having at least four hydroxyl groups; X is -C(H)(OH)- or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial organic polyol A. 1. A process for preparing (i) reacting an organic polyol of formula 2 with diketene 3 to form a compound of formula 4

[0023] [ka]

[0024] To form; and (iia) reacting a compound of formula 4 with hydrogen in the presence of a catalyst to form a compound of formula 5

[0025] [ka]

[0026] To form and optionally, (iib) Compound 5 was mixed with compound LG-R 1 wherein LG is a leaving group to produce a compound of formula 6

[0027] [ka]

[0028] To form The present invention provides a process including:

[0029] In another aspect, the present invention provides a compound of formula 9

[0030] [ka]

[0031] (In the formula, z is 0 or more, A is derived from an organic polyol having at least three hydroxyl groups; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial organic polyol A. 1. A process for preparing (i) reacting a compound of formula 10 with diketene 3 to give a compound of formula 11

[0032] [ka]

[0033] To form and optionally, (iia) reacting a compound of formula 11 with hydrogen in the presence of a catalyst to produce a compound of formula 12

[0034] [ka]

[0035] To form and optionally, (iib) The compound of formula 12 is reacted with the compound LG-R 1 wherein LG is a leaving group to produce a compound of formula 13

[0036] [ka]

[0037] To form The present invention provides a process including: DETAILED DESCRIPTION OF THE INVENTION

[0038] The present invention will be described in more detail below.

[0039] definition To facilitate understanding of the present invention, definitions of numerous terms used throughout the present invention are provided below.

[0040] According to the present invention, the term "linear or branched chain C 1~12"Alkyl" refers to a straight or branched chain saturated hydrocarbon group having 1 to 12 carbon atoms, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, examples of which include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2- dimethylpropyl, hexyl, 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.

[0041] According to the present invention, the term "C 3~8 "Cycloalkyl" refers to a monocyclic saturated hydrocarbon group having 3 to 8 carbon ring members, e.g., 2, 3, 4, 5, 6, 7, or 8 carbon ring members, examples of which include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0042] According to the present invention, the term "linear or branched chain C 2~12"Hydroxyalkyl" refers to a straight or branched chain saturated hydrocarbon group having 2 to 12 carbon atoms, e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, in which at least one hydrogen atom has been replaced with a hydroxy group, including, for example, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxyisopropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 1-hydroxypentyl, 2-hydroxypentyl, 3-hydroxypentyl, 4-hydroxypentyl, 5-hydroxypentyl, 1-hydroxyhexyl, 2-hydroxyhexyl, 3-hydroxyhexyl, 4-hydroxyhexyl, 5-hydroxyhexyl, and 6-hydroxyhexyl.

[0043] According to the present invention, the term "linear or branched chain C 1~12 "Carboxyalkyl" refers to a straight or branched chain saturated hydrocarbon group having 1 to 12 carbon atoms as defined above, in which at least one hydrogen atom is replaced by a carboxy group, such as, for example, carboxymethyl, 1-carboxyethyl, 2-carboxyethyl, 1-methyl-2-carboxyethyl, 1-carboxypropyl, 2-carboxypropyl, 3-carboxypropyl, 1-methyl-2-carboxypropyl, 1-methyl-3-carboxypropyl, 1,1-dimethyl-2-carboxypropyl, 1,1-dimethyl-3-carboxypropyl, 1,2-dimethyl-3-carboxypropyl. Examples of carboxybutyl include 2,2-dimethyl-3-carboxypropyl, 1-carboxybutyl, 2-carboxybutyl, 3-carboxybutyl, 4-carboxybutyl, 1-methyl-4-carboxybutyl, 2-methyl-4-carboxybutyl, 3-methyl-4-carboxybutyl, 1,1-dimethyl-4-carboxybutyl, 1,2-dimethyl-4-carboxybutyl, 1,3-dimethyl-4-carboxybutyl, 2,2-dimethyl-4-carboxybutyl, 2,3-dimethyl-4-carboxybutyl, 3,3-dimethyl-4-carboxybutyl, 5-carboxypentyl, and 6-carboxyhexyl.

[0044] According to the present invention, the term "carboxyphenyl" refers to a phenol group in which at least one hydrogen atom has been replaced by a carboxy group, such as o / m / p-carboxyphenol, examples of which include carboxymethyl, 1-carboxyethyl, 2-carboxyethyl, 1-methyl-2-carboxyethyl, 1-carboxypropyl, 2-carboxypropyl, 3-carboxypropyl, 1-methyl-2-carboxypropyl, 1-methyl-3-carboxypropyl, 1,1-dimethyl-2-carboxypropyl, 1,1-dimethyl-3-carboxypropyl, 1,2-dimethyl-3-carboxypropyl, 2,2-dimethyl-3 and esters of one or more carboxy functional groups such as 1,1-dimethyl-4-carboxybutyl, 1,2-dimethyl-4-carboxybutyl, 1,3-dimethyl-4-carboxybutyl, 2,2-dimethyl-4-carboxybutyl, 2,3-dimethyl-4-carboxybutyl, 3,3-dimethyl-4-carboxybutyl, 5-carboxypentyl, and 6-carboxyhexyl.

[0045] According to the present invention, the term "linear or branched chain saturated or unsaturated C 1~24 "Alkanoyl" refers to the group -C(O)-R-, where R is a straight or branched chain saturated or unsaturated C 1~24 Examples include alkanoyls derived from fatty acids, such as medium-chain fatty acids such as caproic, caprylic, capric, and lauric acids; hexadecatrienoic acid, α-linolenic acid, stearidonic acid, eicosatrienoic acid, eicosatetraenoic acid, eicosapentaenoic acid, heneicosapentaenoic acid, docosapentaenoic acid, clupanodonic acid, docosahexaenoic acid, tetracosapentaenoic acid, and tetracosahexaenoic acid. alkanoyl groups derived from omega-3 fatty acids such as hydroxybenzoic acid; and omega-6 fatty acids such as linoleic acid, gamma-linolenic acid, calendic acid, eicosadienoic acid, dihomogamma-linolenic acid, arachidonic acid, docosadienoic acid, adrenic acid, osbondoic acid, tetracosatetraenoic acid, and tetracosapentaenoic acid.

[0046] According to the present invention, the term "organic polyol" refers to a linear, branched, or cyclic organic compound having 2 to 18 carbon atoms and at least three hydroxyl groups, or at least four hydroxyl groups. As such, the organic polyol can have 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms. In one embodiment, only one hydroxyl group is attached to one carbon atom. In one embodiment, the organic polyol contains only carbon, hydrogen, and oxygen atoms.

[0047] According to the present invention, the term "at least three hydroxyl groups" means that each compound has three or more hydroxyl groups. In one embodiment, "at least three hydroxyl groups" includes 3 to 18 hydroxyl groups, for example, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 hydroxyl groups. In one embodiment, "at least three hydroxyl groups" includes 3 to 12 hydroxyl groups, for example, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 hydroxyl groups. In one embodiment, "at least three hydroxyl groups" includes 3 to 9 hydroxyl groups, for example, 3, 4, 5, 6, 7, 8, or 9 hydroxyl groups. In one embodiment, "at least three hydroxyl groups" includes 3 to 6 hydroxyl groups, for example, 3, 4, 5, or 6 hydroxyl groups.

[0048] According to the present invention, the term "at least four hydroxyl groups" means that each compound has four or more hydroxyl groups. In one embodiment, "at least four hydroxyl groups" includes 4 to 18 hydroxyl groups, for example, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 hydroxyl groups. In one embodiment, "at least four hydroxyl groups" includes 4 to 12 hydroxyl groups, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12 hydroxyl groups. In one embodiment, "at least four hydroxyl groups" includes 4 to 9 hydroxyl groups, for example, 4, 5, 6, 7, 8, or 9 hydroxyl groups. In one embodiment, "at least four hydroxyl groups" includes 4 to 6 hydroxyl groups, for example, 4, 5, or 6 hydroxyl groups.

[0049] According to the present invention, the term "leaving group" or "LG" refers to a group that leaves with an electron pair in a heterolytic bond cleavage. Exemplary leaving groups include halides (e.g., F, Cl, Br, or I), sulfonates (e.g., tosylates (TsO), and the like). - )), pentafluorophenolate, N-hydroxysuccinimide, N,N-dicyclohexylurea, 1-hydroxybenzotriazole, 1-(3-(dimethylamino)propyl)-3-ethylurea, hydroxyl groups, ammonia groups and tertiary amines, thioesters, nitrate esters, phosphate esters, acetoacetate esters, and carboxylic acid esters. In one embodiment, LG is acetoacetate ester, F, Cl, Br, I, or TsO.

[0050] Linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, phenyl, carboxyphenyl, and straight or branched chain saturated or unsaturated C 1~24 Arcano It will be understood that the yl may be optionally further substituted. Exemplary substituents include hydroxy, straight or branched chain C 1~12 Alkyl, C 3~8 Examples include cycloalkyl, carboxy groups, halogens, and phenyl.

[0051] Unless expressly stated otherwise, compounds and functional groups that can exist as different stereoisomers or in different conformations and configurations will be understood to encompass all stereoisomers, conformations, and configurations. For example, the term "inositol" shall be understood to include all stereoisomers and conformations, such as myo-, scyllo-, muco-, D-chiro-, neo-inositol, L-chiro-, allo-, epi-, and cis-inositol. For example, the term "hexanetriol" shall be understood to include all hexane isomers containing three hydroxyl groups, such as 1,1,1-hexanetriol, 1,1,2-hexanetriol, 1,2,2-hexanetriol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2,5-hexanetriol, 1,2,6-hexanetriol, 1,3,5-hexanetriol, 1,3,6-hexanetriol, 2,3,4-hexanetriol, 2,3,5-hexanetriol, and the like.

[0052] A, R, R as described herein 1 The meanings and preferred meanings for X, , and LG apply to all compounds and processes, including precursors of the compounds, in all of the process steps detailed herein.

[0053] As used herein, the term "comprising" means "including." and "consisting of" are intended to encompass both "and" and "consisting of" and both meanings of embodiments of the invention are specifically intended and individually disclosed.

[0054] As used herein, the articles "a" and "b" preceding an element or component are used interchangeably. "An" is intended to be open-ended regarding the number of instances (i.e., occurrences) of an element or component. Thus, "a" or "an" means one or more. or at least one, and the singular forms of elements or components also include the plural, unless the number is clearly implied to be singular.

[0055] As used herein, the term "about" modifying the amount of a substance, ingredient, component, or parameter employed refers to variations in the quantity that may occur, for example, through typical measuring and handling procedures, such as those for handling liquids used to make concentrates or solutions. Additionally, variations may arise due to unintentional errors in measuring procedures, differences in the manufacture, source, or purity of components employed in carrying out the method, etc. In one embodiment, the term "about" means within 10% of the reported numerical value. In a more specific embodiment, the term "about" means within 5% of the reported numerical value.

[0056] As outlined above, the subject of the present invention is a compound of formula 1

[0057] [ka]

[0058] (In the formula, A is derived from an organic polyol having at least four hydroxyl groups; X is -C(H)(OH)- or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial organic polyol A. The purpose is to provide

[0059] In one embodiment, the present invention provides a compound of formula 1

[0060] [ka]

[0061] (In the formula, A is derived from an organic polyol having at least four hydroxyl groups; X is -C(H)(OH)- or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 4 to the number of hydroxyl groups in the initial organic polyol A. to provide.

[0062] In one embodiment, the organic polyol is a linear, branched, or cyclic organic compound having from 2 to 18 carbon atoms and having at least four hydroxyl groups.

[0063] In one embodiment, the organic polyol is a linear or branched C substituted with at least four hydroxyl groups. 2~12 C substituted with alkyl or at least four hydroxyl groups 3~8 cycloalkyl.

[0064] Preferably, a linear or branched C substituted with at least four hydroxyl groups 2~12 The alkyl is selected from the group consisting of pentaerythritol, butane tetrol, pentane tetrol, hexane tetrol, and hexane pentol.

[0065] Preferably, C substituted with at least four hydroxyl groups 3~8 The cycloalkyl is selected from the group consisting of cyclopentane tetrol, cyclopentane pentol, cyclohexane tetrol, cyclohexane pentol, and cyclohexane hexol.

[0066] In one embodiment, the organic polyol is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids.

[0067] Monosaccharides generally have the chemical formula C n H 2n O n Monosaccharides are the number of carbon atoms they contain (CHO) x They can be classified by the x in the formula: triose (x=3), tetrose (x=4), pentose (x=5), hexose (x=6) and heptose (x=7).

[0068] In one embodiment, the monosaccharide is selected from pentose, hexose, and heptose. Preferably, the monosaccharide is selected from aldopentoses, ketopentoses, aldohexoses, and ketohexoses.

[0069] In one embodiment, the monosaccharide is ribose, arabinose, xylose, lyxose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, n-acetyl-d-glucosamine, glucosamine, N-acetyl-D-galactosamine, fucose, rhamnose, chinovose, fructose, 2-deoxy-D-glucose, fluorodeoxyglucose, or methylglucose. The sugar is selected from the group consisting of glycerol, 6-deoxyfructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, mannoheptulose, L-glycero-D-mannoheptose, and combinations thereof.

[0070] Sugar alcohols (also called polyhydric alcohols, polyalcohols, alditols, or glycitols) are organic compounds derived from sugars that typically contain one hydroxyl group (—OH) attached to each carbon atom.

[0071] In one embodiment, the sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof.

[0072] Sugar acids are generally monosaccharides with a carboxyl group at one or both ends of the carbon chain. Major classes of sugar acids include aldonic acids, ulosonic acids, uronic acids, and aldaric acids. In aldonic acids, the aldehyde group (-CHO) located at the first end (position 1) of the aldose is oxidized. In ulosonic acids, the -CH2(OH) group at the first end of a 2-ketose is oxidized to produce an α-keto acid. In uronic acids, the -CH2(OH) group at the terminus of an aldose or ketose is oxidized. In aldaric acids, both ends of the aldose (-CHO and -CH2(OH)) are oxidized.

[0073] In one embodiment, the sugar acid is selected from aldonic acid, ulosonic acid, uronic acid, and aldaric acid. Preferably, the sugar acid is xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galactosyl acid, hydroxybenzoic ... It is selected from the group consisting of turonic acid, iduronic acid, mucic acid, saccharinic acid, and combinations thereof.

[0074] In one embodiment, the organic polyol is selected from the group consisting of sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, and pentaerythritol. Preferably, the organic polyol is erythritol.

[0075] In one embodiment, y is from 2 to the number of hydroxyl groups in the initial organic polyol A. In one embodiment, y is from 3 to the number of hydroxyl groups in the initial organic polyol A. Preferably, y is from 4 to the number of hydroxyl groups in the initial organic polyol A. Thus, depending on the number of hydroxyl groups in the initial organic polyol A, y may be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In one embodiment, y is 2. In one embodiment, y is 3. In one embodiment, y is 4. In one embodiment, y is 5. In one embodiment, y is 6. In one embodiment, y is 7. In one embodiment, y is 8 In one embodiment, y is 9. In one embodiment, y is 10.

[0076] In one embodiment, in the compound of Formula 1, y is equal to the number of hydroxyl groups in the initial polyol A.

[0077] In one embodiment, the residue in the compound of formula 1

[0078] [ka]

[0079] may be the same or may be independently different for each occurrence.

[0080] In one embodiment, in the compound of Formula 1, all of the β-hydroxyl butyrate ester units are in either the D or L configuration. In another embodiment, all of the β-hydroxyl butyrate ester units are present in the compound of Formula 1 as a non-racemic mixture of the D and L configurations.

[0081] In one embodiment, the compound of Formula 1 contains more β-hydroxyl butyrate units in the D configuration than β-hydroxyl butyrate units in the L configuration. Preferably, all of the β-hydroxyl butyrate units are in the D configuration.

[0082] In one embodiment, in the compound of Formula 1, all of the β-hydroxyl butyrate ester units are in either the R or S configuration. In another embodiment, all of the β-hydroxyl butyrate ester units are present in the compound of Formula 1 as a non-racemic mixture of the R and S configurations.

[0083] In one embodiment, the compound of Formula 1 contains more β-hydroxyl butyrate units in the R configuration than β-hydroxyl butyrate units in the S configuration. Preferably, all of the β-hydroxyl butyrate units are in the R configuration.

[0084] In one embodiment, X is —C(H)(OH)—.

[0085] In one embodiment, the compound of formula 1 is selected from the group consisting of:

[0086] [ka]

[0087] [ka]

[0088] In another aspect, the present invention provides a compound of formula 1

[0089] [ka]

[0090] (In the formula, A is derived from an organic polyol having at least four hydroxyl groups; X is -C(H)(OH)- or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial organic polyol A. 1. A process for preparing (i) reacting an organic polyol of formula 2 with diketene 3 to form a compound of formula 4

[0091] [ka]

[0092] To form; and (iia) reacting a compound of formula 4 with hydrogen in the presence of a catalyst to form a compound of formula 5

[0093] [ka]

[0094] To form and optionally, (iib) The compound of formula 5 is reacted with the compound LG-R 1 wherein LG is a leaving group to produce a compound of formula 6

[0095] [ka]

[0096] To form The present invention provides a process including:

[0097] The present inventors have surprisingly discovered that the process for preparing compounds of Formula 1 according to the present invention achieves significantly improved atom economy and cost-effectiveness per acetoacetate unit when diketene 3 is employed directly in the reaction. For applications where a high ratio of BHB units or their derivatives to polyol is desirable, more BHB units or BHB derivative units per polyol core are advantageous. Furthermore, terminal BHB units may be further reacted, e.g., to form BHB esters. The process according to the present invention achieves a high BHB unit content per polyol unit. Furthermore, the process according to the present invention provides BHB ester polyols in which the BHB units are further functionalized or protected, e.g., with esters or ethers.

[0098] In one embodiment, the present invention provides a compound of formula 1

[0099] [ka]

[0100] (In the formula, A is derived from an organic polyol having at least four hydroxyl groups; X is -C(H)(OH)- or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24selected from alkanoyl, phenyl, and carboxyphenyl; y is from 4 to the number of hydroxyl groups in the initial organic polyol A. 1. A process for preparing (i) reacting an organic polyol of formula 2 with diketene 3 to form a compound of formula 4

[0101] [ka]

[0102] To form; and (iia) reacting a compound of formula 4 with hydrogen in the presence of a catalyst to form a compound of formula 5

[0103] [ka]

[0104] To form and optionally (iib) The compound of formula 5 is reacted with the compound LG-R 1 wherein LG is a leaving group to produce a compound of formula 6

[0105] [ka]

[0106] To form The present invention provides a process including:

[0107] In one embodiment, the organic polyol is a linear, branched, or cyclic organic compound having from 2 to 18 carbon atoms and having at least four hydroxyl groups.

[0108] In one embodiment, the organic polyol is a linear or branched C substituted with at least four hydroxyl groups. 2~12C substituted with alkyl or at least four hydroxyl groups 3~8 cycloalkyl.

[0109] Preferably, a linear or branched C substituted with at least four hydroxyl groups 2~12 The alkyl is selected from the group consisting of pentaerythritol, butane tetrol, pentane tetrol, hexane tetrol, and hexane pentol.

[0110] Preferably, C substituted with at least four hydroxyl groups 3~8 The cycloalkyl is selected from the group consisting of cyclopentane tetrol, cyclopentane pentol, cyclohexane tetrol, cyclohexane pentol, and cyclohexane hexol.

[0111] In one embodiment, the organic polyol is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids.

[0112] Monosaccharides generally have the chemical formula C n H 2n O n Monosaccharides are the number of carbon atoms they contain (CHO) x They can be classified by the x in the formula: triose (x=3), tetrose (x=4), pentose (x=5), hexose (x=6) and heptose (x=7).

[0113] In one embodiment, the monosaccharides are selected from pentoses, hexoses, and heptoses. Preferably, the monosaccharides are selected from aldopentoses, ketopentoses, aldohexoses, and ketohexoses.

[0114] In one embodiment, the monosaccharide is selected from the group consisting of ribose, arabinose, xylose, lyxose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, n-acetyl-d-glucosamine, glucosamine, N-acetyl-D-galactosamine, fucose, rhamnose, synovose, fructose, 2-deoxy-D-glucose, fluorodeoxyglucose, 6-deoxyfructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, mannoheptulose, L-glycero-D-mannoheptose, and combinations thereof.

[0115] Sugar alcohols (also called polyhydric alcohols, polyalcohols, alditols, or glycitols) are organic compounds derived from sugars that typically contain one hydroxyl group (—OH) attached to each carbon atom.

[0116] In one embodiment, the sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof.

[0117] Sugar acids are generally monosaccharides with a carboxyl group at one or both ends of the carbon chain. Major classes of sugar acids include aldonic acids, urosonic acids, uronic acids, and These include aldaric acids. In aldonic acids, the aldehyde group (-CHO) located at the first terminus (position 1) of an aldose is oxidized. In urosonic acids, the -CH2(OH) group at the first terminus of a 2-ketose is oxidized to produce an α-keto acid. In uronic acids, the -CH2(OH) group at the terminus of an aldose or ketose is oxidized. In aldaric acids, both termini of the aldose (-CHO and -CH2(OH)) are oxidized.

[0118] In one embodiment, the sugar acid is selected from aldonic acid, ulosonic acid, uronic acid, and aldaric acid. Preferably, the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof.

[0119] In one embodiment, the organic polyol is selected from the group consisting of sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, and pentaerythritol. Preferably, the organic polyol is erythritol.

[0120] In one embodiment, y is from 2 to the number of hydroxyl groups in the initial organic polyol A. In one embodiment, y is from 3 to the number of hydroxyl groups in the initial organic polyol A. Preferably, y is from 4 to the number of hydroxyl groups in the initial organic polyol A. Thus, depending on the number of hydroxyl groups in the initial organic polyol A, y may be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In one embodiment, y is 2. In one embodiment, y is 3. In one embodiment, y is 4. In one embodiment, y is 5. In one embodiment, y is 6. In one embodiment, y is 7. In one embodiment, y is 8. In one embodiment, y is 9. In one embodiment, y is 10.

[0121] In one embodiment, in the compound of Formula 1, y is equal to the number of hydroxyl groups in the initial polyol A.

[0122] In one embodiment, the residue in the compound of formula 1

[0123] [ka]

[0124] may be the same or may be independently different for each occurrence.

[0125] In one embodiment, in the compound of Formula 1, all of the β-hydroxyl butyrate ester units are in either the D or L configuration. In another embodiment, all of the β-hydroxyl butyrate ester units are present in the compound of Formula 1 as a non-racemic mixture of the D and L configurations.

[0126] In one embodiment, the compound of Formula 1 contains more β-hydroxyl butyrate units in the D configuration than β-hydroxyl butyrate units in the L configuration. Preferably, all of the β-hydroxyl butyrate units are in the D configuration.

[0127] In one embodiment, in the compound of Formula 1, all of the β-hydroxyl butyrate ester units are in either the R or S configuration. In another embodiment, all of the β-hydroxyl butyrate ester units are present in the compound of Formula 1 as a non-racemic mixture of the R and S configurations.

[0128] In one embodiment, the compound of Formula 1 contains more β-hydroxyl butyrate units in the R configuration than β-hydroxyl butyrate units in the S configuration. Preferably, all of the β-hydroxyl butyrate units are in the R configuration.

[0129] In one embodiment, X is —C(H)(OH)—.

[0130] In one embodiment, the compound of formula 1 is selected from the group consisting of:

[0131] [ka]

[0132] [ka]

[0133] In one embodiment, the reaction step (i) is carried out in the presence of an organic amine catalyst. Suitable organic amine catalysts include tertiary amines. Preferably, the organic amine catalyst is 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0134] In step (iia), the compound of formula 4 reacts with hydrogen in the presence of a catalyst to form a compound of formula 5. In one embodiment, reacting step (iia) is carried out in the presence of a metal-based catalyst. Preferably, the metal-based catalyst is a Ni-based catalyst, a Pd-based catalyst, a Pt-based catalyst, a Ru-based catalyst, a Co-based catalyst, an Ir-based catalyst, or a Rh-based catalyst.

[0135] In one embodiment, reacting step (iia) is carried out in the presence of a chiral ligand capable of forming a complex with the metal-based catalyst. Preferred chiral ligands are 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), 1,1'-bi-2-naphthol (BINOL), 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane (DIOP), 2,2',5,5'-tetramethyl-4,4'-bis-(diphenylphosphino)-3,3'-bithiophene (tetraMe-BITIOP), bis(diphenylphosphino)-7,8-dihydro-6H -dibenzo[f,h][1,5]dioxonine (C3-TunePhos), 4,4'-bis(bis(3,5-dimethylphenyl)phosphino)-2,2',6,6'-tetramethoxy-3,3'-bipyridine (Xyl-p-PHOS), (6,6'-dimethoxybiphenyl-2,2'-diyl)-bis-(diphenylphosphine) (MeO-BIPHEP), and 1,2-bis[(2-methoxyphenyl)phenylphosphino]ethane (DIPAMP).

[0136] Preferably, the reaction step (iia) is carried out in the presence of a Ru-based catalyst. A preferred Ru-based catalyst is a ruthenium oxide catalyst, such as RuO. Further preferred Ru-based catalysts include Ru / C, RuAlO, Ru(OAc)(BINAP), Ru(Cl)(BINAP), C-[(S,S)-teth-MtsDpenRuCl], [(R)-BinapRuCl(p-cymene)]Cl, and [chloro(R)-C-TunePhos)(p-cymene)ruthenium(II)] chloride.

[0137] In one embodiment, compound 5 is further esterified at at least one hydroxyl group of the terminal β-hydroxyl butyrate unit with an omega fatty acid, a medium chain fatty acid, or a combination thereof. In this situation, R in the compound of formula 6 1It will be understood that LG-R is a fatty acid residue obtained from a fatty acid as detailed herein. This is preferably carried out in reaction step (iib). In this case, LG-R 1 is used, where R 1 is a fatty acid residue, LG is a leaving group that replaces the hydroxyl group in the carboxylic acid function, i.e., LG-C(O)-R-, where R is a straight or branched chain saturated or unsaturated C 1~24 It is an alkyl residue, e.g., LG-R 1 may be a fatty acid halide, such as caproic acid chloride, caprylic acid chloride, capric acid chloride, or lauric acid chloride.

[0138] In one embodiment, omega-3 fatty acid is omega-3 fatty acid, omega-6 fatty acid, omega-3,6 fatty acid or their combination.In one embodiment, omega-3 fatty acid is selected from the group consisting of hexadecatrienoic acid, α-linolenic acid, stearidonic acid, eicosatrienoic acid, eicosatetraenoic acid, eicosapentaenoic acid, heneicosapentaenoic acid, docosapentaenoic acid, clupanodonic acid, docosahexaenoic acid, tetracosapentaenoic acid and tetracosahexaenoic acid.In one embodiment, omega-6 fatty acid is selected from the group consisting of linoleic acid, gamma-linolenic acid, calendic acid, eicosadienoic acid, dihomogammalinolenic acid, arachidonic acid, docosadienoic acid, adrenic acid, osbondoic acid, tetracosatetraenoic acid and tetracosapentaenoic acid.

[0139] In one embodiment, the medium chain fatty acids are selected from the group consisting of caproic acid, caprylic acid, capric acid, lauric acid, and combinations thereof.

[0140] In one embodiment, LG-R 1 is a fatty acid halide of any one of the fatty acids detailed herein.

[0141] Compound 5 may be esterified with only one omega or medium chain fatty acid, Or it may be esterified with any combination of omega fatty acids and / or medium chain fatty acids.

[0142] Depending on the type of organic polyol, the process for preparing the compound of formula 1 can be carried out in an organic solvent or without a solvent. Specifically, for liquid organic polyols or organic polyols with a low melting point (typically <120°C), an organic solvent is not required, and the process can be carried out without a solvent. Thus, in one embodiment, the process for preparing the compound of formula 1 is carried out without a solvent. In another embodiment, the process for preparing the compound of formula 1 is carried out in an organic solvent.

[0143] Suitable organic solvents include ethyl acetate, diethyl ether, MTBE, tetrahydrofuran, n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, DMF, DMSO, acetone, acetonitrile, toluene, chloroform, 1,4-dioxane, or o / m / p-xylene. Preferably, the organic solvent is ethyl acetate.

[0144] In one embodiment, in the process for preparing a compound of Formula 1, reaction step (i) is carried out at a temperature of 20 to 100° C. Preferably, reaction step (i) is carried out at a temperature of 40 to 70° C. Additionally, the reaction temperature of reaction step (i) may be maintained at 40 to 70° C. after the addition of diketene 3 is complete.

[0145] In one embodiment, in the process for preparing a compound of Formula 1, reacting step (i) is carried out at a temperature of 0 to 100° C. Preferably, reacting step (i) is carried out at a temperature of 15 to 70° C. Additionally, the reaction temperature of reacting step (i) may be maintained at 20 to 70° C. after the addition of diketene 3 is complete.

[0146] In one embodiment, during reaction step (i), diketene 3 is added slowly, for example dropwise, to the reaction mixture over a period of 1 to 6 hours to avoid the formation of by-products.

[0147] In one embodiment, during reaction step (i), diketene 3 is added slowly, for example dropwise, to the reaction mixture over a period of 1 to 10 hours to avoid the formation of by-products.

[0148] In one embodiment, reacting step (iia) is carried out in a closed vessel under hydrogen pressure. Preferably, reacting step (iia) is carried out at a hydrogen pressure of from 5 to 30 bar, even more preferably at a hydrogen pressure of from 10 to 20 bar.

[0149] In one embodiment, reacting step (iia) is carried out at a temperature of 20 to 90° C. In one embodiment, reacting step (iia) is carried out at a temperature of 30 to 90° C. Preferably, reacting step (iia) is carried out at a temperature of 50 to 70° C., more preferably, reacting step (iia) is carried out at a temperature of about 60° C.

[0150] In one embodiment, the reaction step (iia) is stirred at 800 to 1200 rpm to ensure sufficient hydrogen diffusion into the reaction mixture.

[0151] In another aspect, the present invention provides a compound of formula 9

[0152] [ka]

[0153] (In the formula, z is 0 or more, A is derived from an organic polyol having at least three hydroxyl groups; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial polyol A. to provide.

[0154] In one embodiment, the present invention provides a compound of formula 9

[0155] [ka]

[0156] (In the formula, z is 0 or more, A is derived from an organic polyol having at least three hydroxyl groups; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 3 to the number of hydroxyl groups in the initial polyol A. to provide.

[0157] In one embodiment, z is 0 to 100, for example, 0 to 95, 0 to 90, 0 to 85, 0 to 80, 0 to 75, 0 to 70, 0 to 65, 0 to 60, 0 to 55, 0 to 50, 0 to 45, 0 to 40, 0 to 35, 0 to 30, 0 to 25, or 0 to 20. In one embodiment, z is 0 to 20, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. In one embodiment, z is 0 to 20, for example, 0 to 19, 0 to 18, 0 to 17, 0 to 16, 0 to 15, 0 to 14, 0 to 13, 0 to 12, 0 to 11, 0 to 10, 0 to 9, 0 to 8, 0 to 7, 0 to 6, 0 to 5, 0 to 4, 0 to 3, 0 to 2, 1, or 0. Preferably, z is 0 or 1.

[0158] In one embodiment, the organic polyol is a linear, branched, or cyclic organic compound having at least three hydroxyl groups and having from 2 to 18 carbon atoms.

[0159] In one embodiment, the organic polyol is a linear or branched C substituted with at least three hydroxyl groups. 2~12 C substituted with alkyl or at least three hydroxyl groups 3~8 cycloalkyl.

[0160] Preferably, a linear or branched C substituted with at least three hydroxyl groups 2~12 The alkyl is selected from the group consisting of glycerol, trimethylolpropane, butanetriol, 2-methyl-propanetriol, pentanetriol, 3-methyl-pentanetriol, hexanetriol, pentaerythritol, butanetetrol, pentanetetrol, hexanetetrol, hexanepentol, and combinations thereof.

[0161] In one embodiment, C substituted with at least three hydroxyl groups 3~8The cycloalkyl is selected from the group consisting of cyclopentanetriol, cyclohexanetriol, cyclopentanetetrol, cyclohexanetetrol, and combinations thereof.

[0162] In one embodiment, the organic polyol is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids.

[0163] In one embodiment, the monosaccharides are preferably selected from tetroses, pentoses, hexoses, and heptoses, and the monosaccharides are selected from aldotetroses, ketotetroses, aldopentoses, ketopentoses, aldohexoses, ketohexoses, aldoheptoses, and ketoheptoses.

[0164] Preferably, the monosaccharide is erythrose, threose, erythrulose, ribose, arabinose, xylose, lyxose, deoxyribose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, n-acetyl-d-glucosamine, glucosamine, N-acetyl-D-galactosamine, fucose, rhamnose, synovose, fructose, 2-deoxy-D- The sugar is selected from the group consisting of glucose, fluorodeoxyglucose, 6-deoxyfructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, mannoheptulose, L-glycero-D-mannoheptose, and combinations thereof.

[0165] Preferably, the sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof.

[0166] Preferably, the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof.

[0167] In one embodiment, the organic polyol is selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, pentaerythritol, and trimethylolpropane. Preferably, the organic polyol is erythritol.

[0168] In one embodiment, y is from 2 to the number of hydroxyl groups in the initial organic polyol A. In one embodiment, y is from 3 to the number of hydroxyl groups in the initial organic polyol A. In one embodiment, y is from 4 to the number of hydroxyl groups in the initial organic polyol A. Thus, depending on the number of hydroxyl groups in the initial organic polyol A, y may be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In one embodiment, y is 2. In one embodiment, y is 3. In one embodiment, y is 4. In one embodiment, y is 5. In one embodiment, y is 6. In one embodiment, y is 7. In one embodiment, y is 8. In one embodiment, y is 9. In one embodiment, y is 10.

[0169] In one embodiment, in the compound of Formula 9, y is equal to the number of hydroxyl groups in the initial polyol A.

[0170] In one embodiment, the residue in the compound of formula 9

[0171] [ka]

[0172] may be the same or may be independently different for each occurrence.

[0173] In one embodiment, in the compound of Formula 9, all of the β-hydroxyl butyrate ester units are in either the D or L configuration. In another embodiment, all of the β-hydroxyl butyrate ester units are present in the compound of Formula 9 as a non-racemic mixture of the D and L configurations.

[0174] In one embodiment, the compound of formula 9 contains more β-hydroxyl butyrate units in the D configuration than β-hydroxyl butyrate units in the L configuration. Preferably, all of the β-hydroxyl butyrate units are in the D configuration.

[0175] In one embodiment, in the compound of Formula 9, all of the β-hydroxyl butyrate ester units are in either the R or S configuration. In another embodiment, all of the β-hydroxyl butyrate ester units are present in the compound of Formula 9 as a non-racemic mixture of the R and S configurations.

[0176] In one embodiment, the compound of Formula 9 contains more β-hydroxyl butyrate units in the R configuration than β-hydroxyl butyrate units in the S configuration. Preferably, all of the β-hydroxyl butyrate units are in the R configuration.

[0177] In one embodiment, X is -C(O)-. In one embodiment, X is -C(H)(OH)-.

[0178] In one embodiment, the compound of formula 9 is selected from the group consisting of:

[0179] [ka]

[0180] In another aspect, the present invention provides a compound of formula 9

[0181] [ka]

[0182] (In the formula, z is 0 or more, A is derived from an organic polyol having at least three hydroxyl groups; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial organic polyol A. 1. A process for preparing (i) reacting a compound of formula 10 with diketene 3 to give a compound of formula 11

[0183] [ka]

[0184] To form and optionally (iia) reacting a compound of formula 11 with hydrogen in the presence of a catalyst to produce a compound of formula 12

[0185] [ka]

[0186] To form and optionally (iib) The compound of formula 12 is reacted with the compound LG-R 1wherein LG is a leaving group to produce a compound of formula 13

[0187] [ka]

[0188] To form The present invention provides a process including:

[0189] In one embodiment, the present invention provides a compound of formula 9

[0190] [ka]

[0191] (In the formula, z is 0 or more, A is derived from an organic polyol having at least three hydroxyl groups; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 Alkanoyl, phenyl, and carbo selected from phenyl, y is from 3 to the number of hydroxyl groups in the initial organic polyol A. 1. A process for preparing (i) reacting a compound of formula 10 with diketene 3 to give a compound of formula 11

[0192] [ka]

[0193] To form and optionally (iia) reacting a compound of formula 11 with hydrogen in the presence of a catalyst to produce a compound of formula 12

[0194] [ka]

[0195] To form and optionally (iib) The compound of formula 12 is reacted with the compound LG-R 1 wherein LG is a leaving group to produce a compound of formula 13

[0196] [ka]

[0197] To form The present invention provides a process including:

[0198] The inventors have surprisingly found that the process according to the present invention for preparing a compound of formula 9 achieves significantly improved atom economy and cost-effectiveness per acetoacetate unit when a compound according to formula 10 is reacted with diketene 3 to form a compound of formula 11. For applications where a high ratio of acetoacetate and / or BHB units or derivatives thereof relative to the polyol is desirable, more acetoacetate and / or BHB units per polyol core is advantageous. Furthermore, the inventors have surprisingly found that the process of hydrogenating compound 11 to compound 12 followed by reaction of the resulting compound with diketene 3 can be repeated. This ultimately results in a dendrimer having multiple BHB units of a desired length. The terminal acetoacetate and / or BHB units may be further reacted, e.g., to obtain BHB esters. Thus, the process according to the present invention achieves a high BHB unit content per polyol unit. Additionally, the process according to the present invention provides BHB ester polyols in which the BHB units are further functionalized or protected, for example, by esters or ethers.

[0199] In one embodiment, z is 0 to 100, for example, 0 to 95, 0 to 90, 0 to 85, 0 to 80, 0 to 75, 0 to 70, 0 to 65, 0 to 60, 0 to 55, 0 to 50, 0 to 45, 0 to 40, 0 to 35, 0 to 30, 0 to 25, or 0 to 20. In one embodiment, z is 0 to 20, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. In one embodiment, z is 0 to 20, for example, 0 to 19, 0 to 18, 0 to 17, 0 to 16, 0 to 15, 0 to 14, 0 to 13, 0 to 12, 0 to 11, 0 to 10, 0 to 9, 0 to 8, 0 to 7, 0 to 6, 0 to 5, 0 to 4, 0 to 3, 0 to 2, 1, or 0. Preferably, z is 0 or 1.

[0200] In one embodiment, the organic polyol is a linear, branched, or cyclic organic compound having from 2 to 18 carbon atoms and having at least three hydroxyl groups.

[0201] In one embodiment, the organic polyol is a linear or branched C substituted with at least three hydroxyl groups. 2~12 C substituted with alkyl or at least three hydroxyl groups 3~8 cycloalkyl.

[0202] Preferably, a linear or branched C substituted with at least three hydroxyl groups 2~12 The alkyl is selected from the group consisting of glycerol, trimethylolpropane, butanetriol, 2-methyl-propanetriol, pentanetriol, 3-methyl-pentanetriol, hexanetriol, pentaerythritol, butanetetrol, pentanetetrol, hexanetetrol, hexanepentol, and combinations thereof.

[0203] In one embodiment, C substituted with at least three hydroxyl groups 3~8 The cycloalkyl is selected from the group consisting of cyclopentanetriol, cyclohexanetriol, cyclopentanetetrol, cyclohexanetetrol, and combinations thereof.

[0204] In one embodiment, the organic polyol is selected from the group consisting of a monosaccharide, a sugar alcohol, and a sugar acid.

[0205] In one embodiment, the monosaccharides are preferably selected from tetroses, pentoses, hexoses, and heptoses, and the monosaccharides are selected from aldotetroses, ketotetroses, aldopentoses, ketopentoses, aldohexoses, ketohexoses, aldoheptoses, and ketoheptoses.

[0206] Preferably, the monosaccharide is erythrose, threose, erythrulose, ribose, arabinose, xylose, lyxose, deoxyribose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, n-acetyl-d-glucosamine, glucosamine, N-acetyl-D-galactosamine, fucose, rhamnose, synovose, fructose, 2-deoxy-D- The sugar is selected from the group consisting of glucose, fluorodeoxyglucose, 6-deoxyfructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, mannoheptulose, L-glycero-D-mannoheptose, and combinations thereof.

[0207] Preferably, the sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof.

[0208] Preferably, the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof.

[0209] In one embodiment, the organic polyol is selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, pentaerythritol, and trimethylolpropane. Preferably, the organic polyol is erythritol.

[0210] In one embodiment, y is from 2 to the number of hydroxyl groups in the initial organic polyol A. In one embodiment, y is from 3 to the number of hydroxyl groups in the initial organic polyol A. In one embodiment, y is from 4 to the number of hydroxyl groups in the initial organic polyol A. Thus, depending on the number of hydroxyl groups in the initial organic polyol A, y may be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In one embodiment, y is 2. In one embodiment, y is 3. In one embodiment, y is 4. In one embodiment, y is 5. In one embodiment, y is 6. In one embodiment, y is 7. In one embodiment, y is 8. In one embodiment, y is 9. In one embodiment, y is 10.

[0211] In one embodiment, in the compound of Formula 9, y is equal to the number of hydroxyl groups in the initial polyol A.

[0212] In one embodiment, the residue in the compound of formula 9

[0213] [ka]

[0214] may be the same or may be independently different for each occurrence.

[0215] In one embodiment, in the compound of Formula 9, all of the β-hydroxyl butyrate ester units are in either the D or L configuration. In another embodiment, all of the β-hydroxyl butyrate ester units are present in the compound of Formula 9 as a non-racemic mixture of the D and L configurations.

[0216] In one embodiment, the compound of formula 9 contains more β-hydroxyl butyrate units in the D configuration than β-hydroxyl butyrate units in the L configuration. Preferably, all of the β-hydroxyl butyrate units are in the D configuration.

[0217] In one embodiment, in the compound of Formula 9, all β-hydroxyl butyrate esters are The positions are either in the R or S configuration. In another embodiment, all of the β-hydroxyl butyrate units are present in the compound of formula 9 as a non-racemic mixture of the R and S configurations.

[0218] In one embodiment, the compound of Formula 9 contains more β-hydroxyl butyrate units in the R configuration than β-hydroxyl butyrate units in the S configuration. Preferably, all of the β-hydroxyl butyrate units are in the R configuration.

[0219] In one embodiment, X is -C(O)-. In one embodiment, X is -C(H)(OH)-.

[0220] In one embodiment, the compound of formula 9 is selected from the group consisting of:

[0221] [ka]

[0222] In one embodiment, the reaction step (i) is carried out in the presence of an organic amine catalyst. Suitable organic amine catalysts include tertiary amines. Preferably, the organic amine catalyst is 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0223] In step (iia), the compound of formula 11 reacts with hydrogen in the presence of a catalyst to form a compound of formula 12. In one embodiment, reacting step (iia) is carried out in the presence of a metal-based catalyst. Preferably, the metal-based catalyst is a Ni-based catalyst, a Pd-based catalyst, a Pt-based catalyst, a Ru-based catalyst, a Co-based catalyst, an Ir-based catalyst, or a Rh-based catalyst.

[0224] In one embodiment, reacting step (iia) comprises forming a complex with a metal-based catalyst. The reaction is carried out in the presence of a chiral ligand. Preferred chiral ligands are 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), 1,1'-bi-2-naphthol (BINOL), 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane (DIOP), 2,2',5,5'-tetramethyl-4,4'-bis-(diphenylphosphino)-3,3'-bithiophene (tetraMe-BITIOP), bis(diphenylphosphino)-7,8-dihydro-6H -dibenzo[f,h][1,5]dioxonine (C3-TunePhos), 4,4'-bis(bis(3,5-dimethylphenyl)phosphino)-2,2',6,6'-tetramethoxy-3,3'-bipyridine (Xyl-p-PHOS), (6,6'-dimethoxybiphenyl-2,2'-diyl)-bis-(diphenylphosphine) (MeO-BIPHEP), and 1,2-bis[(2-methoxyphenyl)phenylphosphino]ethane (DIPAMP).

[0225] Preferably, the reaction step (iia) is carried out in the presence of a Ru-based catalyst. Preferred Ru-based catalysts are any ruthenium oxide catalysts, such as RuO. Further preferred Ru-based catalysts include Ru / C, RuAlO, Ru(OAc)(BINAP), Ru(Cl)(BINAP), C-[(S,S)-teth-MtsDpenRuCl], [(R)-BinapRuCl(p-cymene)]Cl, and [chloro(R)-C-TunePhos)(p-cymene)ruthenium(II)] chloride.

[0226] In one embodiment, compound 12 is further esterified at at least one hydroxyl group of the terminal β-hydroxyl butyrate unit with an omega fatty acid, a medium chain fatty acid, or a combination thereof. In this situation, R in the compound of formula 13 1 It will be understood that LG-R is a fatty acid residue obtained from a fatty acid as detailed herein. This is preferably carried out in reaction step (iib). In this case, LG-R 1 is used, where R 1 is a fatty acid residue, LG is a leaving group that replaces the hydroxyl group in the carboxylic acid function, i.e., LG-C(O)-R-, where R is a straight or branched chain saturated or unsaturated C 1~24 It is an alkyl residue, e.g., LG-R 1 may be a fatty acid halide, such as caproic acid chloride, caprylic acid chloride, capric acid chloride, or lauric acid chloride.

[0227] In one embodiment, omega-3 fatty acid is omega-3 fatty acid, omega-6 fatty acid, omega-3,6 fatty acid or their combination.In one embodiment, omega-3 fatty acid is selected from the group consisting of hexadecatrienoic acid, α-linolenic acid, stearidonic acid, eicosatrienoic acid, eicosatetraenoic acid, eicosapentaenoic acid, heneicosapentaenoic acid, docosapentaenoic acid, clupanodonic acid, docosahexaenoic acid, tetracosapentaenoic acid and tetracosahexaenoic acid.In one embodiment, omega-6 fatty acid is selected from the group consisting of linoleic acid, gamma-linolenic acid, calendic acid, eicosadienoic acid, dihomogammalinolenic acid, arachidonic acid, docosadienoic acid, adrenic acid, osbondoic acid, tetracosatetraenoic acid and tetracosapentaenoic acid.

[0228] In one embodiment, the medium chain fatty acids are selected from the group consisting of caproic acid, caprylic acid, capric acid, lauric acid, and combinations thereof.

[0229] In one embodiment, LG-R 1 is a fatty acid halide of any one of the fatty acids detailed herein.

[0230] Compound 12 may be esterified with only one omega fatty acid or medium chain fatty acid, or with any combination of omega fatty acids and / or medium chain fatty acids. good.

[0231] Depending on the type of organic polyol, the process for preparing the compound of formula 9 can be carried out in an organic solvent or without a solvent. Specifically, for liquid organic polyols or organic polyols with a low melting point (typically <120°C), an organic solvent is not required, and the process can be carried out without a solvent. Thus, in one embodiment, the process for preparing the compound of formula 9 is carried out without a solvent. In another embodiment, the process for preparing the compound of formula 9 is carried out in an organic solvent.

[0232] Suitable organic solvents include ethyl acetate, diethyl ether, MTBE, tetrahydrofuran, n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, DMF, DMSO, acetone, t-butyl alcohol, acetonitrile, toluene, chloroform, 1,4-dioxane, methanol, ethanol, or o / m / p-xylene. Preferably, the organic solvent is ethyl acetate.

[0233] In one embodiment, in the process for preparing the compound of Formula 9, reaction step (i) is carried out at a temperature of 20 to 100° C. Preferably, reaction step (i) is carried out at a temperature of 40 to 70° C. Additionally, the reaction temperature of reaction step (i) may be maintained at 40 to 70° C. after the addition of diketene 3 is complete.

[0234] In one embodiment, in the process for preparing the compound of Formula 9, reaction step (i) is carried out at a temperature of 0 to 100° C. Preferably, reaction step (i) is carried out at a temperature of 15 to 70° C. Additionally, the reaction temperature of reaction step (i) may be maintained at 20 to 70° C. after the addition of diketene 3 is complete.

[0235] In one embodiment, during reaction step (i), diketene 3 is added to the reaction mixture slowly, for example dropwise, over a period of 1 to 6 hours to avoid the formation of by-products.

[0236] In one embodiment, during reaction step (i), diketene 3 is added slowly, for example dropwise, to the reaction mixture over a period of 1 to 10 hours to avoid the formation of by-products.

[0237] In one embodiment, reacting step (iia) is carried out in a closed vessel under hydrogen pressure. Preferably, reacting step (iia) is carried out at a hydrogen pressure of from 5 to 30 bar, even more preferably at a hydrogen pressure of from 10 to 20 bar.

[0238] In one embodiment, reacting step (iia) is carried out at a temperature of 20 to 90° C. In one embodiment, reacting step (iia) is carried out at a temperature of 30 to 90° C. Preferably, reacting step (iia) is carried out at a temperature of 50 to 70° C., more preferably, reacting step (iia) is carried out at a temperature of about 60° C.

[0239] In one embodiment, the reaction step (iia) is stirred at 800 to 1200 rpm to ensure sufficient hydrogen diffusion into the reaction mixture.

[0240] In another aspect, the present invention provides a compound of formula 9

[0241] [ka]

[0242] (In the formula, z is 0 or 1, A is derived from an organic polyol having at least three hydroxyl groups; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial polyol A. to provide.

[0243] In one embodiment, the present invention provides a compound of formula 9

[0244] [ka]

[0245] (In the formula, z is 0 or 1, A is derived from an organic polyol having at least three hydroxyl groups; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 3 to the number of hydroxyl groups in the initial polyol A. to provide.

[0246] In one embodiment, the organic polyol is a linear, branched, or cyclic organic compound having from 2 to 18 carbon atoms and having at least three hydroxyl groups.

[0247] In one embodiment, the organic polyol is a linear or branched C substituted with at least three hydroxyl groups. 2~12 C substituted with alkyl or at least three hydroxyl groups 3~8 cycloalkyl.

[0248] Preferably, a linear or branched C substituted with at least three hydroxyl groups 2~12 Alkyl is glycerol, trimethylolpropane, butanetriol, 2-methyl-propanetriol, pentanetriol, 3-methyl-pentanetriol, hexanetriol, pentaerythritol, butanetetrol, pentanetetrol, hexa The hydroxybenzoate is selected from the group consisting of pentetrol, hexanepentol, and combinations thereof.

[0249] In one embodiment, C substituted with at least three hydroxyl groups 3~8 The cycloalkyl is selected from the group consisting of cyclopentanetriol, cyclohexanetriol, cyclopentanetetrol, cyclohexanetetrol, and combinations thereof.

[0250] In one embodiment, the organic polyol is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids.

[0251] In one embodiment, the monosaccharides are preferably selected from tetroses, pentoses, hexoses, and heptoses, and the monosaccharides are selected from aldotetroses, ketotetroses, aldopentoses, ketopentoses, aldohexoses, ketohexoses, aldoheptoses, and ketoheptoses.

[0252] Preferably, the monosaccharide is erythrose, threose, erythrulose, ribose, arabinose, xylose, lyxose, deoxyribose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, n-acetyl-d-glucosamine, glucosamine, N-acetyl-D-galactosamine, fucose, rhamnose, synovose, fructose, 2-deoxy-D- The sugar is selected from the group consisting of glucose, fluorodeoxyglucose, 6-deoxyfructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, mannoheptulose, L-glycero-D-mannoheptose, and combinations thereof.

[0253] Preferably, the sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof.

[0254] Preferably, the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof.

[0255] In one embodiment, the organic polyol is selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, pentaerythritol, and trimethylolpropane. Preferably, the organic polyol is erythritol.

[0256] In one embodiment, y is from 2 to the number of hydroxyl groups in the initial organic polyol A. In one embodiment, y is from 3 to the number of hydroxyl groups in the initial organic polyol A. In one embodiment, y is from 4 to the number of hydroxyl groups in the initial organic polyol A. Thus, depending on the number of hydroxyl groups in the initial organic polyol A, y may be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In one embodiment, y is 2. In one embodiment, y is 3. In one embodiment, y is 4. In one embodiment, y is 5. In one embodiment, y is 6. In one embodiment, y is 7. In one embodiment, y is 8. In one embodiment, y is 9. In one embodiment, y is 10.

[0257] In one embodiment, in the compound of Formula 9, y is equal to the number of hydroxyl groups in the initial polyol A.

[0258] In one embodiment, the residue in the compound of formula 9

[0259] [ka]

[0260] may be the same or may be independently different for each occurrence.

[0261] In one embodiment, in the compound of Formula 9, all of the β-hydroxyl butyrate ester units are in either the D or L configuration. In another embodiment, all of the β-hydroxyl butyrate ester units are present in the compound of Formula 9 as a non-racemic mixture of the D and L configurations.

[0262] In one embodiment, the compound of formula 9 contains more β-hydroxyl butyrate units in the D configuration than β-hydroxyl butyrate units in the L configuration. Preferably, all of the β-hydroxyl butyrate units are in the D configuration.

[0263] In one embodiment, in the compound of Formula 9, all of the β-hydroxyl butyrate ester units are in either the R or S configuration. In another embodiment, all of the β-hydroxyl butyrate ester units are present in the compound of Formula 9 as a non-racemic mixture of the R and S configurations.

[0264] In one embodiment, the compound of Formula 9 contains more β-hydroxyl butyrate units in the R configuration than β-hydroxyl butyrate units in the S configuration. Preferably, all of the β-hydroxyl butyrate units are in the R configuration.

[0265] In one embodiment, X is -C(O)-. In one embodiment, X is -C(H)(OH)-.

[0266] In one embodiment, the compound of formula 9 is selected from the group consisting of:

[0267] [ka]

[0268] In another aspect, the present invention provides a compound of formula 9

[0269] [ka]

[0270] (In the formula, z is 0 or more, A is derived from an organic polyol having at least three hydroxyl groups, provided that the organic polyol is not erythritol; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial polyol A. to provide.

[0271] In one embodiment, the present invention provides a compound of formula 9

[0272] [ka]

[0273] (In the formula, z is 0 or more, A is derived from an organic polyol having at least three hydroxyl groups, provided that the organic polyol is not erythritol; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 3 to the number of hydroxyl groups in the initial polyol A. to provide.

[0274] In one embodiment, z is 0 to 100, for example, 0 to 95, 0 to 90, 0 to 85, 0 to 80, 0 to 75, 0 to 70, 0 to 65, 0 to 60, 0 to 55, 0 to 50, 0 to 45, 0 to 40, 0 to 35, 0 to 30, 0 to 25, or 0 to 20. In one embodiment, z is 0 to 20, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. In one embodiment, z is 0 to 20, for example, 0 to 19, 0 to 18, 0 to 17, 0 to 16, 0 to 15, 0 to 14, 0 to 13, 0 to 12, 0 to 11, 0 to 10, 0 to 9, 0 to 8, 0 to 7, 0 to 6, 0 to 5, 0 to 4, 0 to 3, 0 to 2, 1, or 0. Preferably, z is 0 or 1.

[0275] In one embodiment, the organic polyol is a linear, branched, or cyclic organic compound having at least three hydroxyl groups and having from 2 to 18 carbon atoms.

[0276] In one embodiment, the organic polyol is a linear or branched C substituted with at least three hydroxyl groups. 2~12 C substituted with alkyl or at least three hydroxyl groups 3~8 cycloalkyl.

[0277] Preferably, a linear or branched C substituted with at least three hydroxyl groups 2~12 The alkyl is selected from the group consisting of glycerol, trimethylolpropane, butanetriol, 2-methyl-propanetriol, pentanetriol, 3-methyl-pentanetriol, hexanetriol, pentaerythritol, butanetetrol, pentanetetrol, hexanetetrol, hexanepentol, and combinations thereof.

[0278] In one embodiment, C substituted with at least three hydroxyl groups 3~8 The cycloalkyl is selected from the group consisting of cyclopentanetriol, cyclohexanetriol, cyclopentanetetrol, cyclohexanetetrol, and combinations thereof.

[0279] In one embodiment, the organic polyol is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids.

[0280] In one embodiment, the monosaccharides are preferably tetroses, pentoses, hexoses, and heptose, and the monosaccharide is selected from aldotetrose, ketotetrose, aldopentose, ketopentose, aldohexose, ketohexose, aldoheptose and ketoheptose.

[0281] Preferably, the monosaccharide is erythrose, threose, erythrulose, ribose, arabinose, xylose, lyxose, deoxyribose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, n-acetyl-d-glucosamine, glucosamine, N-acetyl-D-galactosamine, fucose, rhamnose, synovose, fructose, 2-deoxy-D- The sugar is selected from the group consisting of glucose, fluorodeoxyglucose, 6-deoxyfructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, mannoheptulose, L-glycero-D-mannoheptose, and combinations thereof.

[0282] Preferably, the sugar alcohol is selected from the group consisting of threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof.

[0283] Preferably, the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof.

[0284] In one embodiment, the organic polyol is selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, maltitol, glucose, glucitol, ribulose, pentaerythritol, and trimethylolpropane.

[0285] In one embodiment, y is from 2 to the number of hydroxyl groups in the initial organic polyol A. In one embodiment, y is from 3 to the number of hydroxyl groups in the initial organic polyol A. In one embodiment, y is from 4 to the number of hydroxyl groups in the initial organic polyol A. Thus, depending on the number of hydroxyl groups in the initial organic polyol A, y may be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In one embodiment, y is 2. In one embodiment, y is 3. In one embodiment, y is 4. In one embodiment, y is 5. In one embodiment, y is 6. In one embodiment, y is 7. In one embodiment, y is 8. In one embodiment, y is 9. In one embodiment, y is 10.

[0286] In one embodiment, in the compound of Formula 9, y is equal to the number of hydroxyl groups in the initial polyol A.

[0287] In one embodiment, the residue in the compound of formula 9

[0288] [ka]

[0289] may be the same or may be independently different for each occurrence.

[0290] In one embodiment, in the compound of Formula 9, all of the β-hydroxyl butyrate ester units are in either the D or L configuration. In another embodiment, all of the β-hydroxyl butyrate ester units are present in the compound of Formula 9 as a non-racemic mixture of the D and L configurations.

[0291] In one embodiment, the compound of formula 9 contains more β-hydroxyl butyrate units in the D configuration than β-hydroxyl butyrate units in the L configuration. Preferably, all of the β-hydroxyl butyrate units are in the D configuration.

[0292] In one embodiment, in the compound of Formula 9, all of the β-hydroxyl butyrate ester units are in either the R or S configuration. In another embodiment, all of the β-hydroxyl butyrate ester units are present in the compound of Formula 9 as a non-racemic mixture of the R and S configurations.

[0293] In one embodiment, the compound of Formula 9 contains more β-hydroxyl butyrate units in the R configuration than β-hydroxyl butyrate units in the S configuration. Preferably, all of the β-hydroxyl butyrate units are in the R configuration.

[0294] In one embodiment, X is -C(O)-. In one embodiment, X is -C(H)(OH)-.

[0295] In one embodiment, the compound of formula 9 is selected from the group consisting of:

[0296] [ka]

[0297] The following numbered paragraphs further define preferred embodiments of the present invention.

[0298] 1. Compound of Formula 1

[0299] [ka]

[0300] (In the formula, A is derived from an organic polyol having at least four hydroxyl groups; X is -C(H)(OH)- or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial organic polyol A).

[0301] 2. The organic polyol is a linear or branched C substituted with at least four hydroxyl groups. 2~12 C substituted with alkyl or at least four hydroxyl groups 3~8 Item 1. The compound according to item 1, wherein the aryl group is selected from cycloalkyl.

[0302] 3. Linear or branched chain C substituted with at least four hydroxyl groups 2~12 Archi 3. The compound according to item 2, wherein the tetraol is selected from the group consisting of pentaerythritol, butane tetrol, pentane tetrol, hexane tetrol, and hexane pentol.

[0303] 4. C substituted with at least four hydroxyl groups 3~8 4. The compound according to item 2 or 3, wherein the cycloalkyl is selected from the group consisting of cyclopentane tetrol, cyclopentane pentol, cyclohexane tetrol, cyclohexane pentol, and cyclohexane hexol.

[0304] 5. The compound according to item 1, wherein the organic polyol is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids.

[0305] 6. The compound according to item 5, wherein the monosaccharide is selected from pentoses, hexoses, and heptoses, preferably the monosaccharide is selected from aldopentoses, ketopentoses, aldohexoses, ketohexoses, aldoheptoses, and ketoheptoses.

[0306] 7. Monosaccharides include ribose, arabinose, xylose, lyxose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, N-acetyl-D-glucosamine, glucosamine, N-acetyl-D-galactosamine, fucose, rhamnose, synovose, fructose, 2-deoxy-D-glucose, fluorodeoxyglucose, 6-deoxy-D-glucose, and 2-deoxy-D-glucose. 7. The compound according to item 5 or 6, wherein the compound is selected from the group consisting of dihydroxyfructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, mannoheptulose, L-glycero-D-mannoheptose, and combinations thereof.

[0307] 8. The compound according to any one of items 5 to 7, wherein the sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof.

[0308] 9. The compound according to any one of items 5 to 8, wherein the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof.

[0309] 10. The compound according to any one of items 1 to 9, wherein the organic polyol is selected from the group consisting of sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, and pentaerythritol, preferably the organic polyol is erythritol.

[0310] 11. The compound is

[0311] [ka]

[0312] [ka]

[0313] 11. The compound according to any one of items 1 to 10, selected from the group consisting of:

[0314] 12. The compound according to any one of items 1 to 11, wherein all β-hydroxyl butyrate ester units are either in the D-configuration or in the L-configuration, or all β-hydroxyl butyrate ester units are present as a non-racemic mixture of the D- and L-configurations.

[0315] 13. The compound according to any one of items 1 to 12, wherein the compound contains more β-hydroxyl butyrate units in the D configuration than β-hydroxyl butyrate units in the L configuration, preferably all β-hydroxyl butyrate units are in the D configuration.

[0316] 14. Compound of Formula 9

[0317] [ka]

[0318] (In the formula, z is 0 or more, A is derived from an organic polyol having at least three hydroxyl groups; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial polyol A).

[0319] 15. The compound according to item 14, wherein z is 0 to 100, for example, 0 to 95, 0 to 90, 0 to 85, 0 to 80, 0 to 75, 0 to 70, 0 to 65, 0 to 60, 0 to 55, 0 to 50, 0 to 45, 0 to 40, 0 to 35, 0 to 30, 0 to 25, or 0 to 20, preferably z is 0 to 20, for example, 0 to 19, for example, 0 to 18, for example, 0 to 17, for example, 0 to 16, for example, 0 to 15, for example, 0 to 14, for example, 0 to 13, for example, 0 to 12, for example, 0 to 11, for example, 0 to 10, for example, 0 to 9, for example, 0 to 8, for example, 0 to 7, for example, 0 to 6, for example, 0 to 5, for example, 0 to 4, for example, 0 to 3, for example, 0 to 2, more preferably z is 0 or 1.

[0320] 16. The organic polyol is a linear or branched C substituted with at least three hydroxyl groups. 2~12 C substituted with alkyl or at least three hydroxyl groups 3~8 16. The compound according to item 14 or 15, selected from cycloalkyl.

[0321] 17. Linear or branched chain C substituted with at least three hydroxyl groups 2~12 Item 17. The compound according to item 16, wherein the alkyl is selected from the group consisting of glycerol, trimethylolpropane, butanetriol, 2-methyl-propanetriol, pentanetriol, 3-methyl-pentanetriol, hexanetriol, pentaerythritol, butanetetrol, pentanetetrol, hexanetetrol, hexanepentol, and combinations thereof.

[0322] 18. C substituted with at least three hydroxyl groups 3~818. The compound according to item 16 or 17, wherein the cycloalkyl is selected from the group consisting of cyclopentanetriol, cyclohexanetriol, cyclopentanetetrol, cyclohexanetetrol, and combinations thereof.

[0323] 19. The compound according to item 14 or 15, wherein the organic polyol is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids.

[0324] 20. The compound according to item 19, wherein the monosaccharide is preferably selected from tetrose, pentose, hexose, and heptose, and the monosaccharide is selected from aldotetrose, ketotetrose, aldopentose, ketopentose, aldohexose, ketohexose, aldoheptose, and ketoheptose.

[0325] 21. Monosaccharides include erythrose, threose, erythrulose, ribose, arabinose, xylose, lyxose, deoxyribose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, n-acetyl-d-glucosamine, glucosamine, N-acetyl-D-galactosamine, fucose, rhamnose, synovose, fructose, 2-deoxy-D-glucose, fluorodeoxyglucose, 6-deoxyfructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, and mannosaccharides. 21. The compound according to item 19 or 20, selected from the group consisting of heptulose, L-glycero-D-mannoheptose, and combinations thereof.

[0326] 22. The compound according to any one of items 19 to 21, wherein the sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof.

[0327] 23. The compound according to any one of items 19 to 22, wherein the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof.

[0328] 24. The compound according to any one of items 14 to 23, wherein the organic polyol is selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, pentaerythritol, and trimethylolpropane, preferably the organic polyol is erythritol.

[0329] 25. A compound is

[0330] [ka]

[0331] 25. The compound according to any one of items 14 to 24, selected from the group consisting of:

[0332] 26. The compound according to any one of items 14 to 25, wherein all of the β-hydroxyl butyrate ester units are either in the D-configuration or in the L-configuration, or all of the β-hydroxyl butyrate ester units are present as a non-racemic mixture of the D- and L-configurations.

[0333] 27. The compound according to any one of items 14 to 26, wherein the compound contains more β-hydroxyl butyrate ester units in the D configuration than β-hydroxyl butyrate ester units in the L configuration, preferably all β-hydroxyl butyrate ester units are in the D configuration.

[0334] 28. The compound according to any one of items 1 to 27, wherein y is from 3 to the number of hydroxyl groups in the initial polyol A, or y is from 4 to the number of hydroxyl groups in the initial polyol A, or y is equal to the number of hydroxyl groups in the initial polyol A.

[0335] 29. Compound of Formula 1

[0336] [ka]

[0337] (In the formula, A is derived from an organic polyol having at least four hydroxyl groups; X is -C(H)(OH)- or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial organic polyol A. 1. A process for preparing (i) reacting an organic polyol of formula 2 with diketene 3 to form a compound of formula 4

[0338] [ka]

[0339] To form; and (iia) reacting a compound of formula 4 with hydrogen in the presence of a catalyst to form a compound of formula 5

[0340] [ka]

[0341] To form and optionally, (iib) The compound of formula 5 is reacted with the compound LG-R 1 wherein LG is a leaving group to produce a compound of formula 6

[0342] [ka]

[0343] To form The above process, comprising:

[0344] 30. The organic polyol is a linear or branched C substituted with at least four hydroxyl groups. 2~12 C substituted with alkyl or at least four hydroxyl groups 3~8 30. The process according to item 29, wherein the alkyl is selected from cycloalkyl.

[0345] 31. Linear or branched chain C substituted with at least four hydroxyl groups 2~12 31. The process of claim 30, wherein the alkyl is selected from the group consisting of pentaerythritol, butane tetrol, pentane tetrol, hexane tetrol, and hexane pentol.

[0346] 32. C substituted with at least four hydroxyl groups 3~832. The process of claim 30 or 31, wherein the cycloalkyl is selected from the group consisting of cyclopentane tetrol, cyclopentane pentol, cyclohexane tetrol, cyclohexane pentol, and cyclohexane hexol.

[0347] 33. The process according to item 29, wherein the organic polyol is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids.

[0348] 34. The process according to item 33, wherein the monosaccharide is selected from pentoses, hexoses, and heptoses, preferably the monosaccharide is selected from aldopentoses, ketopentoses, aldohexoses, ketohexoses, aldoheptoses, and ketoheptoses.

[0349] 35. Monosaccharides include ribose, arabinose, xylose, lyxose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, N-acetyl-D-glucosamine, glucosamine, N-acetyl-D-galactosamine, fucose, rhamnose, synovose, fructose, 2-deoxy-D-glucose, fluorodeoxyglucose, 6-deoxyglucose, and 2-deoxy-D-glucose. 35. The process of claim 33 or 34, wherein the sugar is selected from the group consisting of cyclofructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, mannoheptulose, L-glycero-D-mannoheptulose, and combinations thereof.

[0350] 36. The process according to any one of items 34 to 35, wherein the sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof.

[0351] 37. Sugar acids include xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, and ketodeoxy 37. The process of any one of items 33 to 36, wherein the hydroxyl group is selected from the group consisting of thioctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof.

[0352] 38. The process according to any one of items 29 to 37, wherein the organic polyol is selected from the group consisting of sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, and pentaerythritol, preferably the organic polyol is erythritol.

[0353] 39. A compound is

[0354] [ka]

[0355] [ka]

[0356] 39. The process according to any one of items 29 to 38, selected from the group consisting of:

[0357] 40. Compound of Formula 9

[0358] [ka]

[0359] (In the formula, z is 0 or more, A is derived from an organic polyol having at least three hydroxyl groups; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial organic polyol A. 1. A process for preparing (i) reacting a compound of formula 10 with diketene 3 to give a compound of formula 11

[0360] [ka]

[0361] To form and optionally, (iia) reacting a compound of formula 11 with hydrogen in the presence of a catalyst to produce a compound of formula 12

[0362] [ka]

[0363] To form and optionally, (iib) The compound of formula 12 is reacted with the compound LG-R 1 wherein LG is a leaving group to produce a compound of formula 13

[0364] [ka]

[0365] To form The above process, comprising:

[0366] 41. The process according to item 40, wherein z is 0 to 100, for example, 0 to 95, 0 to 90, 0 to 85, 0 to 80, 0 to 75, 0 to 70, 0 to 65, 0 to 60, 0 to 55, 0 to 50, 0 to 45, 0 to 40, 0 to 35, 0 to 30, 0 to 25, or 0 to 20, preferably z is 0 to 20, for example, 0 to 19, for example, 0 to 18, for example, 0 to 17, for example, 0 to 16, for example, 0 to 15, for example, 0 to 14, for example, 0 to 13, such as 0 to 12, for example, 0 to 11, for example, 0 to 10, for example, 0 to 9, for example, 0 to 8, such as, for example, 0 to 7, for example, 0 to 6, for example, 0 to 5, for example, 0 to 4, for example, 0 to 3, for example, 0 to 2, more preferably z is 0 or 1.

[0367] 42. The organic polyol is a linear or branched C substituted with at least three hydroxyl groups. 2~12 C substituted with alkyl or at least three hydroxyl groups 3~8 42. The process according to item 40 or 41, wherein the alkyl is selected from cycloalkyl.

[0368] 43. Linear or branched chain C substituted with at least three hydroxyl groups 2~12 Item 43. The process of item 42, wherein the alkyl is selected from the group consisting of glycerol, trimethylolpropane, butanetriol, 2-methyl-propanetriol, pentanetriol, 3-methyl-pentanetriol, hexanetriol, pentaerythritol, butanetetrol, pentanetetrol, hexanetetrol, hexanepentol, and combinations thereof.

[0369] 44. C substituted with at least three hydroxyl groups 3~8 44. The process of claim 42 or 43, wherein the cycloalkyl is selected from the group consisting of cyclopentanetriol, cyclohexanetriol, cyclopentanetetrol, cyclohexanetetrol, and combinations thereof.

[0370] 45. The process according to item 40 or 41, wherein the organic polyol is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids.

[0371] 46. ​​The process according to item 45, wherein the monosaccharide is selected from tetrose, pentose, hexose, and heptose, preferably the monosaccharide is selected from aldotetrose, ketotetrose, aldopentose, ketopentose, aldohexose, ketohexose, aldoheptose, and ketoheptose.

[0372] 47. Monosaccharides include erythrose, threose, erythrulose, ribose, arabinose, xylose, lyxose, deoxyribose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, n-acetyl-d-glucosamine, glucosamine, N-acetyl-d-galactosamine, fucose, rhamnose, synovose, fructose, 2-deoxy-d-glucose, fluoro 47. The process of claim 45 or 46, wherein the sugar is selected from the group consisting of deoxyglucose, 6-deoxyfructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, mannoheptulose, L-glycero-D-mannoheptose, and combinations thereof.

[0373] 48. The process according to any one of items 45 to 47, wherein the sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof.

[0374] 49. The process according to any one of items 45 to 48, wherein the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof.

[0375] 50. The process according to any one of items 40 to 49, wherein the organic polyol is selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, pentaerythritol, and trimethylolpropane, preferably the organic polyol is erythritol.

[0376] 51. The compound is

[0377] [ka]

[0378] 51. The process according to any one of items 40 to 50, selected from the group consisting of:

[0379] 52. The process according to any one of items 29 to 51, wherein the reacting step (i) is carried out in the presence of an organic amine catalyst.

[0380] 53. The process according to item 52, wherein the organic amine catalyst is a tertiary amine.

[0381] 54. The process according to item 53, wherein the organic amine catalyst is DABCO.

[0382] 55. The process according to any one of items 29 to 54, wherein reacting step (iia) is carried out in the presence of a metal-based catalyst, preferably a Ni-based catalyst, a Pd-based catalyst, a Pt-based catalyst, a Ru-based catalyst, a Co-based catalyst, an Ir-based catalyst, or a Rh-based catalyst.

[0383] 56. The process according to any one of items 29 to 55, wherein reacting step (iia) is carried out in the presence of a Ru-based catalyst, preferably the Ru-based catalyst is selected from a ruthenium oxide catalyst, Ru / C, RuAl2O3, RuO2, Ru(OAc)2(BINAP), Ru(Cl)2(BINAP), C3-[(S,S)-teth-MtsDpenRuCl], [(R)-BinapRuCl(p-cymene)]Cl, and [chloro(R)-C3-TunePhos)(p-cymene)ruthenium(II)] chloride.

[0384] 57. The reaction step (iia) comprises reacting a chiral compound capable of forming a complex with a metal-based catalyst. The reaction is carried out in the presence of a chiral ligand, preferably, the chiral ligand is 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), 1,1'-bi-2-naphthol (BINOL), 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane (DIOP), 2,2',5,5'-tetramethyl-4,4'-bis-(diphenylphosphino)-3,3'-bithiophene (tetraMe-BITIOP), bis(diphenylphosphino)-7,8-dihydro-6H-dibenzyl 57. The process of any one of items 29 to 56, wherein the aryl group is selected from the group consisting of benzo[f,h][1,5]dioxonine (C3-TunePhos), 4,4'-bis(bis(3,5-dimethylphenyl)phosphino)-2,2',6,6'-tetramethoxy-3,3'-bipyridine (Xyl-p-PHOS), (6,6'-dimethoxybiphenyl-2,2'-diyl)-bis-(diphenylphosphine) (MeO-BIPHEP), and 1,2-bis[(2-methoxyphenyl)phenylphosphino]ethane (DIPAMP).

[0385] 58. The process of any one of items 29 to 56, wherein all of the β-hydroxyl butyrate ester units are either in the D configuration or the L configuration, or all of the β-hydroxyl butyrate ester units are present as a non-racemic mixture of the D and L configurations.

[0386] 59. The process according to any one of items 29 to 58, wherein the compound contains more β-hydroxyl butyrate ester units in the D configuration than β-hydroxyl butyrate ester units in the L configuration, preferably all β-hydroxyl butyrate ester units are in the D configuration.

[0387] 60. The process according to any one of items 29 to 59, wherein compound 5 or 12 is further esterified at at least one hydroxyl group of the terminal β-hydroxyl butyrate ester unit with an omega fatty acid, a medium chain fatty acid, or a combination thereof, preferably wherein the omega fatty acid is an omega 3 fatty acid, an omega 6 fatty acid, an omega 3,6 fatty acid, or a combination thereof, and / or the medium chain fatty acid is selected from the group consisting of caproic acid, caprylic acid, capric acid, lauric acid, and a combination thereof.

[0388] 61. The process of any one of items 29 to 60, wherein y is from 3 to the number of hydroxyl groups in the initial polyol A, or y is from 4 to the number of hydroxyl groups in the initial polyol A, or y is equal to the number of hydroxyl groups in the initial polyol A.

[0389] 62. Compound of Formula 9

[0390] [ka]

[0391] (In the formula, z is 0 or 1, A is derived from an organic polyol having at least three hydroxyl groups; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial polyol A).

[0392] 63. The organic polyol is a linear or branched C substituted with at least three hydroxyl groups. 2~12 C substituted with alkyl or at least three hydroxyl groups 3~8 63. The compound according to item 62, selected from cycloalkyl.

[0393] 64. Linear or branched chain C substituted with at least three hydroxyl groups 2~12 64. The compound according to item 63, wherein the alkyl is selected from the group consisting of glycerol, trimethylolpropane, butanetriol, 2-methyl-propanetriol, pentanetriol, 3-methyl-pentanetriol, hexanetriol, pentaerythritol, butanetetrol, pentanetetrol, hexanetetrol, hexanepentol, and combinations thereof.

[0394] 65. C substituted with at least three hydroxyl groups 3~8 65. The compound according to item 63 or 64, wherein the cycloalkyl is selected from the group consisting of cyclopentanetriol, cyclohexanetriol, cyclopentanetetrol, cyclohexanetetrol, and combinations thereof.

[0395] 66. The compound according to item 62, wherein the organic polyol is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids.

[0396] 67. The compound according to item 66, wherein the monosaccharide is preferably selected from tetrose, pentose, hexose, and heptose, and the monosaccharide is selected from aldotetrose, ketotetrose, aldopentose, ketopentose, aldohexose, ketohexose, aldoheptose, and ketoheptose.

[0397] 68. Monosaccharides include erythrose, threose, erythrulose, ribose, arabinose, xylose, lyxose, deoxyribose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, n-acetyl-d-glucosamine, glucosamine, N-acetyl-d-galactosamine, fucose, rhamnose, synovose, fructose, 2-deoxy-d-glucose, fluoro 68. The compound according to item 66 or 67, selected from the group consisting of deoxyglucose, 6-deoxyfructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, mannoheptulose, L-glycero-D-mannoheptose, and combinations thereof.

[0398] 69. The compound according to any one of items 66 to 68, wherein the sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof.

[0399] 70. The compound according to any one of items 66 to 69, wherein the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof.

[0400] 71. The organic polyol is selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, pentaerythritol, and trimethylolpropane, preferably an organic 71. The compound according to any one of items 62 to 70, wherein the polyol is erythritol.

[0401] 72. The compound is

[0402] [ka]

[0403] 72. The compound according to any one of items 62 to 71, selected from the group consisting of:

[0404] 73. The compound according to any one of items 62 to 72, wherein all β-hydroxyl butyrate ester units are either in the D-configuration or in the L-configuration, or all β-hydroxyl butyrate ester units are present as a non-racemic mixture of the D- and L-configurations.

[0405] 74. The compound according to any one of items 62 to 73, wherein the compound contains more β-hydroxyl butyrate ester units in the D configuration than β-hydroxyl butyrate ester units in the L configuration, preferably all β-hydroxyl butyrate ester units are in the D configuration.

[0406] 75. The compound according to any one of items 62 to 74, wherein y is from 3 to the number of hydroxyl groups in the initial polyol A, or y is from 4 to the number of hydroxyl groups in the initial polyol A, or y is equal to the number of hydroxyl groups in the initial polyol A.

[0407] 76. Compound of Formula 9

[0408] [ka]

[0409] (In the formula, z is 0 or more, A is derived from an organic polyol having at least three hydroxyl groups, provided that the organic polyol is not erythritol; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial polyol A).

[0410] 77. The compound according to item 76, wherein z is 0 to 100, for example, 0 to 95, 0 to 90, 0 to 85, 0 to 80, 0 to 75, 0 to 70, 0 to 65, 0 to 60, 0 to 55, 0 to 50, 0 to 45, 0 to 40, 0 to 35, 0 to 30, 0 to 25, or 0 to 20, preferably z is 0 to 20, for example, 0 to 19, for example, 0 to 18, for example, 0 to 17, for example, 0 to 16, for example, 0 to 15, for example, 0 to 14, for example, 0 to 13, for example, 0 to 12, for example, 0 to 11, for example, 0 to 10, for example, 0 to 9, for example, 0 to 8, for example, 0 to 7, for example, 0 to 6, for example, 0 to 5, for example, 0 to 4, for example, 0 to 3, for example, 0 to 2, more preferably z is 0 or 1.

[0411] 78. The organic polyol is a linear or branched C substituted with at least three hydroxyl groups. 2~12 C substituted with alkyl or at least three hydroxyl groups 3~8 78. The compound according to item 76 or 77, selected from cycloalkyl.

[0412] 79. Linear or branched C substituted with at least three hydroxyl groups 2~1279. The compound according to item 78, wherein the alkyl is selected from the group consisting of glycerol, trimethylolpropane, butanetriol, 2-methyl-propanetriol, pentanetriol, 3-methyl-pentanetriol, hexanetriol, pentaerythritol, butanetetrol, pentanetetrol, hexanetetrol, hexanepentol, and combinations thereof.

[0413] 80. C substituted with at least three hydroxyl groups 3~8 80. The compound according to item 78 or 79, wherein the cycloalkyl is selected from the group consisting of cyclopentanetriol, cyclohexanetriol, cyclopentanetetrol, cyclohexanetetrol, and combinations thereof.

[0414] 81. The compound according to item 76 or 77, wherein the organic polyol is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids.

[0415] 82. The compound according to item 81, wherein the monosaccharide is preferably selected from tetrose, pentose, hexose, and heptose, and the monosaccharide is selected from aldotetrose, ketotetrose, aldopentose, ketopentose, aldohexose, ketohexose, aldoheptose, and ketoheptose.

[0416] 83. Monosaccharides include erythrose, threose, erythrulose, ribose, arabinose, xylose, lyxose, deoxyribose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, n-acetyl-d-glucosamine, glucosamine, N-acetyl-d-galactosamine, fucose, rhamnose, synovose, fructose, 2-deoxy-d-glucose, fluoro 83. The compound according to item 81 or 82, selected from the group consisting of deoxyglucose, 6-deoxyfructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, mannoheptulose, L-glycero-D-mannoheptose, and combinations thereof.

[0417] 84. The compound according to any one of items 81 to 83, wherein the sugar alcohol is selected from the group consisting of threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof.

[0418] 85. The compound according to any one of items 81 to 84, wherein the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof.

[0419] 86. The compound according to any one of items 76 to 85, wherein the organic polyol is selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, maltitol, glucose, glucitol, ribulose, pentaerythritol, and trimethylolpropane.

[0420] 87. The compound is

[0421] [ka]

[0422] 87. The compound according to any one of items 76 to 86, selected from the group consisting of:

[0423] 88. The compound according to any one of items 76 to 87, wherein all β-hydroxyl butyrate ester units are either in the D configuration or in the L configuration, or all β-hydroxyl butyrate ester units are present as a non-racemic mixture of the D and L configurations.

[0424] 89. The compound according to any one of items 76 to 88, wherein the compound contains more β-hydroxyl butyrate ester units in the D configuration than β-hydroxyl butyrate ester units in the L configuration, preferably all β-hydroxyl butyrate ester units are in the D configuration.

[0425] 90. The compound according to any one of items 76 to 89, wherein y is from 3 to the number of hydroxyl groups in the initial polyol A, or y is from 4 to the number of hydroxyl groups in the initial polyol A, or y is equal to the number of hydroxyl groups in the initial polyol A.

[0426] 91. The compound or process according to any one of items 1 to 90, wherein all β-hydroxyl butyrate ester units are in the R configuration.

[0427] It will be apparent to those skilled in the art that these embodiments and items merely depict examples of multiple possibilities. Therefore, the embodiments shown herein should not be understood to form limitations on these features and forms. Any possible combination and form of the described features can be selected according to the scope of the present invention. All embodiments and preferred embodiments described herein in relation to one particular form of the present invention (e.g., the preservative composition of the present invention) are applicable to all other forms of the present invention, e.g., the preservative composition of the present invention. This provision shall equally apply to any end-use formulation, use, or method for which it is used.

[0428] The present invention is further illustrated by the following examples. [Example]

[0429] Example 1:

[0430] [ka]

[0431] Propane-1,2,3-tolyltris(3-hydroxybutanoate) (180.0 g, 514 mmol, 1 equiv.) was introduced into a stirred-tank reactor. DABCO (70 mg, 0.7 mmol, 0.0013 equiv.) was added, and the mixture was stirred to obtain a homogeneous mixture. Then, diketene (129.6 g, 1.5 mol, 1 equiv. per hydroxyl group) was slowly added to the reaction mixture while cooling the reactor jacket to maintain an internal temperature of 40-70 °C. The feed rate was adjusted to maintain an internal temperature of 40-70 °C. After the addition was complete, the mixture was maintained at an internal temperature of 40-70 °C for an additional 30 min. Finally, the reaction mixture was cooled to room temperature and analyzed. The final product, propane-1,2,3-tolyltris(3-((3-oxobutanoyl)oxy)butanoate), was obtained in quantitative yield with a purity of 64%-a / a (by HPLC at 220 nm). 1 H NMR (400 MHz, DMSO-d6) δ ppm 1.05 - 1.10 (m, 9 H) 1.19 - 1.26 (m, 9 H) 2.24 - 2.38 (m, 6 H) 2.54 - 2.73 (m, 6 H) 3.91 - 4.01 (m, 3 H) 4.09 - 4.19 (m, 2 H) 4.20 - 4.32 (m, 2 H) 4.57 - 4.76 (m, 3 H) 5.05 - 5.15 (m, 3 H) 5.16 - 5.23 (m, 1 H).

[0432] Example 2:

[0433] [ka]

[0434] Sorbitol (800 g, 4.39 mol, 1 equiv.) was introduced into a stirred tank reactor and ethyl acetate (1.6 L, 2 rel. vol.) was added. To this suspension was added DABCO (0.64 g, 5.7 mmol, 0.0013 equiv.). Diketene (2.24 kg, 26.61 mol, 1 equiv. per hydroxyl group) was then added slowly to the reaction mixture while cooling the reactor jacket to maintain an internal temperature of 30-50°C. The feed rate was adjusted to maintain an internal temperature of 30-50°C. After the addition was complete, the chamber was cooled. The mixture was maintained at an internal temperature of 50°C for an additional 30 minutes before being cooled to room temperature. Water (800 mL, 1 relative volume) and sulfuric acid 96% w / w (4 g) were then added, and the mixture was stirred for 10 minutes. The aqueous phase was discarded, the solvent from the organic phase was evaporated, and the reaction mixture was analyzed. The final product (2R,3R,4R,5S)-hexane-1,2,3,4,5,6-hexylhexakis(3-oxobutanoate) was obtained in quantitative yield with a purity of 72% a / a (by HPLC at 220 nm). 1H NMR (400 MHz, DMSO-d6) δ ppm 2.11 - 2.28 (m, 18 H) 3.45 - 3.82 (m, 12 H) 4.10 - 4.35 (m, 3 H) 4.35 - 4.50 (m, 1 H) 4.98 - 5.15 (m, 1 H) 5.26 - 5.35 (m, 1 H) 5.35 - 5.44 (m, 1 H) 5.44 - 5.55 (m, 1H).

[0435] Example 3:

[0436] [ka]

[0437] Xylitol (50 g, 329 mmol, 1 equiv.) was introduced into a stirred-tank reactor, and to this suspension was added DABCO (0.37 g, 3, 0.01 equiv.). Diketene (143.7 g, 1.7 mol, 1.04 equiv. per hydroxyl group) was then added slowly to the reaction mixture while cooling the reactor jacket to maintain an internal temperature of 50–100 °C. The feed rate was adjusted to maintain an internal temperature of 50–100 °C. After the addition was complete, the mixture was maintained at an internal temperature of 100 °C for an additional 30 min. The reaction mixture was cooled to room temperature and analyzed. The final product, (2R,3R,4S)-pentane-1,2,3,4,5-pentylpentakis(3-oxobutanoate), was obtained in quantitative yield. 1H NMR (400 MHz, DMSO-d6) δ ppm 2.19 (s, 15 H) 3.49 - 3.79 (m, 10 H) 3.88 - 4.12 (m, 2 H) 4.23 - 4.37 (m, 2 H) 5.07 - 5.21 (m, 1 H) 5.29 - 5.41 (m, 1 H) 5.41 - 5.68 (m, 1 H).

[0438] Example 4:

[0439] [ka]

[0440] Mannitol (20 g, 110 mmol, 1 equiv.) was introduced into a stirred tank reactor, and acetone (100 ml, 5 rel. vol.) was added. To this suspension, DABCO (0.12 g, 1.1 mmol, 0.01 equiv.) was added. Diketene (57.2 g, 52.5 mmol, 1.03 equiv. per hydroxyl group) was then added slowly to the reaction mixture while cooling the reactor jacket to maintain reflux at 40 °C. The feed rate was adjusted to maintain reflux. After the addition was complete, the mixture was held at reflux for an additional 30 min, and the solvent was evaporated. Finally, the reaction mixture was cooled to room temperature, filtered, and analyzed. The final product, (2R,3R,4R,5R)-hexane-1,2,3,4,5,6-hexylhexakis(3-oxobutanoate), was isolated in 90% yield and 85.3% a / a purity (by HPLC at 220 nm). 1H NMR (400 MHz, DMSO-d6) δ ppm 2.17 - 2.23 (m, 18 H) 3.50 - 3.81 (m, 12 H) 4.11 - 4.30 (m, 2 H) 4.35 - 4.53 (m, 2 H) 5.04 - 5.25 (m, 2 H) 5.37 - 5.57 (m, 2 H).

[0441] Example 5:

[0442] [ka]

[0443] Erythritol (50 g, 555 mmol, 1 equiv.) was introduced into a stirred-tank reactor, and ethyl acetate (150 ml, 3 rel. vol.) was added. To this suspension, DABCO (82 mg, 0.72 mmol, 0.0013 equiv.) was added. Subsequently, diketene (195.9 g, 2.33 mol, 1.05 equiv. per hydroxyl group) was slowly added to the reaction mixture while cooling the reactor jacket to maintain an internal temperature of 50-65 °C. The feed rate was adjusted to maintain an internal temperature of 50-65 °C. After the addition was complete, the mixture was maintained at an internal temperature of 60 °C for an additional 30 min to allow the solvent to evaporate. Finally, the reaction mixture was cooled to room temperature and analyzed. The final product, (2R,3S)-butane-1,2,3,4-tetrayltetrakis(3-oxobutanoate), was isolated in quantitative yield. LC-MS: 459.14 [M+H] + , 1H NMR (400 MHz, DMSO-d6) δ ppm 2.19 (br s, 12 H) 3.63 (d, J=16.81 Hz, 8 H) 4.24 - 4.31 (m, 2 H) 4.31 - 4.56 (m, 2 H) 5.17 - 5.38 (m, 2 H).

[0444] Example 6:

[0445] [ka]

[0446] Pentaerythritol (40 g, 294 mmol, 1 equiv.) was introduced into a stirred-tank reactor, and acetone (150 ml, 2.5 rel. vol.) was added. To this suspension was added DABCO (333 mg, 2.9 mmol, 0.01 equiv.). Diketene (98.8 g, 1.17 mol, 1.0 equiv. per hydroxyl group) was then added slowly to the reaction mixture while cooling the reactor jacket to maintain an internal temperature of 30-40 °C. The feed rate was adjusted to maintain an internal temperature of 30-40 °C. After the addition was complete, the mixture was maintained at an internal temperature of 40 °C for an additional 30 min to allow the solvent to evaporate. Finally, the reaction mixture was cooled to room temperature and analyzed. The final product, 2,2-bis(((3-oxobutanoyl )oxy)methyl)propane-1,3-diylbis(3-oxobutanoate) was isolated in quantitative yield and 86.2% a / a purity (by HPLC at 220 nm). 1H NMR (400 MHz, DMSO-d6) δ ppm 2.12 - 2.25 (m, 12 H), 3.57 - 3.72 (m, 8 H), 4.07 - 4.30 (m, 8 H).

[0447] Example 7:

[0448] [ka]

[0449] Propane-1,2,3-tolyltris(3-hydroxybutanoate) (100 g, 175 mmol, 1 equiv.) was placed in an autoclave and ethyl acetate (400 ml, 4 rel. vol.) was added. The catalyst (RuO 2、 A 232 mg (1.7 mmol, 0.01 equiv.) HCl solution was added, and the atmosphere was exchanged by pressurizing the reactor three times with nitrogen followed by three times with hydrogen. The hydrogen pressure was adjusted to 10-20 bar, and the mixture was heated to 60 °C with stirring at 1000 rpm until no further hydrogen uptake was observed (approximately 12 h). The mixture was then cooled to room temperature, and the hydrogen atmosphere was exchanged with nitrogen. The reaction mixture was mixed with activated carbon and filtered through Celite. The solvent was evaporated from the filtrate, and the product was analyzed. The final product, propane-1,2,3-tolyltris(3-((3-hydroxybutanoyl)oxy)butanoate), was isolated in 87% yield and 58% a / a purity (by HPLC at 220 nm). 1H NMR (400 MHz, DMSO-d6) δ ppm 1.08 (dd, J=6.27, 1.38 Hz, 9 H) 1.21 (br d, J=6.27 Hz, 9 H) 2.24 - 2.38 (m, 6 H) 2.54 - 2.73 (m, 6 H) 3.91 - 4.01 (m, 3 H) 4.09 - 4.19 (m, 2 H) 4.20 - 4.32 (m, 2 H) 4.57 - 4.76 (m, 3 H) 5.05 - 5.15 (m, 3 H) 5.16 - 5.23 (m, 1 H).

[0450] Example 8:

[0451] [ka]

[0452] (2R,3R,4R,5S)-Hexane-1,2,3,4,5,6-hexylhexakis(3-oxobutanoate) (1.2 kg, 1.75 mol, 1 equiv.) was placed in an autoclave and ethyl acetate (300 ml, 0.25 rel. vol.) was added. The catalyst (RuO, 2.33 g, 17.5 mmol, 0.01 equiv.) was then added, and the atmosphere was exchanged by pressurizing the reactor three times with nitrogen followed by three times with hydrogen. The hydrogen pressure was increased to 10 The pressure was adjusted to ∼20 bar, and the mixture was heated to 60 °C with stirring at 1000 rpm until no further hydrogen uptake was observed (18 h). Afterwards, the mixture was cooled to room temperature, and the hydrogen atmosphere was replaced with nitrogen. The reaction mixture was mixed with activated carbon and filtered through Celite. The solvent was evaporated from the filtrate, and the product was analyzed. The final product (2R,3R,4R,5S)-hexane-1,2,3,4,5,6-hexylhexakis(3-hydroxybutanoate) was isolated in 92% yield and 64%-a / a purity (by HPLC at 220 nm). HPLC-MS: 699.3 [M+H], 1H NMR (400 MHz, DMSO-d6) δ ppm 0.96 - 1.15 (m, 18 H) 2.17 - 2.49 (m, 12 H) 3.83 - 4.12 (m, 8 H) 4.12 - 4.49 (m, 2 H) 4.51 - 4.88 (m, 6 H) 4.91 - 5.10 (m, 1 H) 5.10 - 5.31 (m, 1 H) 5.31 - 5.37 (m, 1 H) 5.37 - 5.59 (m, 1 H).

[0453] Example 9:

[0454] [ka]

[0455] (2R,3R,4S)-Pentane-1,2,3,4,5-pentylpentakis(3-oxobutanoate) (100 g, 175 mmol, 1 equiv.) was placed in an autoclave and ethyl acetate (400 ml, 4 rel. vol.) was added. The catalyst (RuO 2、 A 232 mg (1.75 mmol, 0.01 equiv.) HCl solution was added, and the atmosphere was exchanged by pressurizing the reactor three times with nitrogen followed by three times with hydrogen. The hydrogen pressure was adjusted to 10-20 bar, and the mixture was heated to 60 °C with stirring at 1000 rpm until no further hydrogen uptake was observed (36 h). The mixture was then cooled to room temperature, and the hydrogen atmosphere was exchanged with nitrogen. The reaction mixture was mixed with activated carbon and filtered through Celite. The solvent was evaporated from the filtrate, and the product was analyzed. The final product, (2R,3R,4S)-pentane-1,2,3,4,5-pentylpentakis(3-hydroxybutanoate), was isolated in 87.8% yield. 1H NMR (400 MHz, DMSO-d6) δ ppm 0.95 - 1.13 (m, 15 H) 2.22 - 2.48 (m, 10 H) 3.82 - 4.12 (m, 7 H) 4.12 - 4.33 (m, 2 H) 4.57 - 4.79 (m, 5 H) 5.00 - 5.20 (m, 1 H) 5.21 - 5.36 (m, 1 H) 5.36 - 5.55 (m, 1 H).

[0456] Example 10:

[0457] [ka]

[0458] (2R,3R,4R,5R)-hexane-1,2,3,4,5,6-hexylhexakis(3-oxobutanoate) (100 g, 146 mmol, 1 equiv.) was autoclaved. The mixture was placed in a flask and ethyl acetate (200 ml, 2 rel. vol.) was added. Then the catalyst (RuO 2、A 194 mg (1.46 mmol, 0.01 equiv.) HCl solution was added, and the atmosphere was exchanged by pressurizing the reactor three times with nitrogen followed by three times with hydrogen. The hydrogen pressure was adjusted to 10-20 bar, and the mixture was heated to 60 °C with stirring at 1000 rpm until no further hydrogen uptake was observed (120 h). The mixture was then cooled to room temperature, and the hydrogen atmosphere was exchanged with nitrogen. The reaction mixture was mixed with activated carbon and filtered through Celite. The solvent was evaporated from the filtrate, and the product was analyzed. The final product, (2R,3R,4R,5R)-hexane-1,2,3,4,5,6-hexylhexakis(3-hydroxybutanoate), was isolated in 82.6% yield. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.02 - 1.16 (m, 18 H) 2.29 - 2.47 (m, 12 H) 3.92 - 4.02 (m, 6 H) 4.09 - 4.20 (m, 1 H) 4.21 - 4.45 (m, 3 H) 4.55 - 4.83 (m, 6 H) 4.91 - 5.26 (m, 3 H) 5.30 - 5.41 (m, 1 H).

[0459] Example 11:

[0460] [ka]

[0461] (2R,3S)-Butane-1,2,3,4-tetrayltetrakis(3-oxobutanoate) (200 g, 436 mmol, 1 equiv.) was placed in an autoclave and ethyl acetate (300 ml, 1.5 rel. vol.) was added. The catalyst (RuO 2、A 500 ml (581 mg, 4.4 mmol, 0.01 equiv.) HCl was added, and the atmosphere was exchanged by pressurizing the reactor three times with nitrogen, followed by three times with hydrogen. The hydrogen pressure was adjusted to 10-20 bar, and the mixture was heated to 60 °C with stirring at 1000 rpm until no further hydrogen uptake was observed (18 h). Afterwards, the mixture was cooled to room temperature, and the hydrogen atmosphere was exchanged with nitrogen. The reaction mixture was mixed with activated carbon and filtered through Celite. The solvent was evaporated from the filtrate, and the product was analyzed. The final product, (2R,3S)-butane-1,2,3,4-tetrayltetrakis(3-hydroxybutanoate), was isolated in 86.0% yield. LC-MS: 467.21 [M+H] + , 1H NMR (400 MHz, DMSO-d6) δ ppm 0.97 - 1.13 (m, 12 H) 2.21 - 2.45 (m, 8 H) 4.01 (s, 5 H) 4.07 - 4.23 (m, 2 H) 4.23 - 4.40 (m, 2 H) 4.54 - 4.77 (m, 4 H) 5.14 - 5.28 (m, 2 H).

[0462] Example 12:

[0463] [ka]

[0464] (2R,3S)-Butane-1,2,3,4-tetrayltetrakis(3-oxobutano The catalyst (RuO) (50 g, 106 mmol, 1 equiv.) was placed in an autoclave and ethyl acetate (300 ml, 1.5 rel. vol.) was added. 2、A 146 mg (1.1 mmol, 0.01 equiv.) HCl solution was added, and the atmosphere was exchanged by pressurizing the reactor three times with nitrogen followed by three times with hydrogen. The hydrogen pressure was adjusted to 10-20 bar, and the mixture was heated to 60 °C with stirring at 1000 rpm until no further hydrogen uptake was observed (36 h). The mixture was then cooled to room temperature, and the hydrogen atmosphere was exchanged with nitrogen. The reaction mixture was mixed with activated carbon and filtered through Celite. The solvent was evaporated from the filtrate, and the product was analyzed. The final product, 2,2-bis(((3-hydroxybutanoyl)oxy)methyl)propane-1,3-diylbis(3-hydroxybutanoate), was isolated in 81.4% yield. 1H NMR (400 MHz, DMSO-d6) δ ppm 0.85 (d, J=6.27 Hz, 12 H) 2.07-2.17 (m, 8 H) 3.66 - 3.79 (m, 4 H) 3.79 - 3.95 (m, 8 H) 4.32 - 4.63 (m, 4 H).

[0465] Example 13:

[0466] [ka]

[0467] (2R,3S)-Butane-1,2,3,4-tetrayltetrakis(3-oxobutanoate) (25 g, 54.5 mmol, 1 equiv.) was placed in an autoclave, and methanol (77 ml, 35 equiv.) was added. The catalyst ([RuCl((R)-BINAP)]NEt 3、(2N, 218 mg, 0.11 mmol, 0.002 equiv.) and H2SO4 (2N, 97 mg, 0.002 equiv.) were added, and the atmosphere was exchanged by pressurizing the reactor three times with nitrogen followed by three times with hydrogen. The hydrogen pressure was adjusted to 30 bar, and the mixture was heated to 60 °C with stirring at 600 rpm until no further hydrogen uptake was observed (5 days). Afterwards, the mixture was cooled to room temperature, and the hydrogen atmosphere was exchanged with nitrogen. The reaction mixture was mixed with activated carbon and filtered through Celite and silica. The solvent was evaporated from the filtrate, and the product was analyzed. The final product, (2R,3S)-butane-1,2,3,4-tetrayl(3R,3'R,3"R,3"'R)-tetrakis(3-hydroxybutanoate), was isolated as a brown liquid in quantitative yield (ee = 95.4%). 1H NMR (400 MHz, CDCl3) δ ppm 1.28 (m, 12 H), 2.50 (m, 8 H), 4.39 (m, 8 H), 5.25 (m, 2 H).

[0468] Example 14: Mesoerythritol (6 g, 0.05 mol, 1 equiv.) was charged to a stirred-tank reactor, and ethyl acetate (10.8 g, 2.5 equiv.) was added. To this suspension was added DABCO (7.2 mg, 0.0001 mol, 0.0013 equiv.). Diketene (4.1 g, 0.05 mol, 1 equiv.) was then added slowly to the reaction mixture over 8 hours while cooling the reactor jacket to maintain an internal temperature of 40 °C. The feed rate was adjusted to maintain an internal temperature of 40 °C. After the addition was complete, the mixture was maintained at an internal temperature of 40 °C overnight. The solvent was removed under reduced pressure to yield a mixture of isomers of mesoerythritol monoacetoacetate (7.2 g, 72%) as an off-white solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 2.18 (m, 3H), 3.39 (s, 5H), 4.35 (m, 2H), 4.48 (s, 2H).

[0469] Example 15: Mesoerythritol (6 g, 0.05 mol, 1 equiv.) was charged to a stirred-tank reactor, and ethyl acetate (10.8 g, 2.5 equiv.) was added. To this suspension was added DABCO (7.2 mg, 0.0001 mol, 0.0013 equiv.). Diketene (8.3 g, 0.1 mol, 2 equiv.) was then added slowly to the reaction mixture over 8 hours while cooling the reactor jacket to maintain an internal temperature of 40 °C. The feed rate was adjusted to maintain an internal temperature of 40 °C. After the addition was complete, the mixture was maintained at an internal temperature of 40 °C overnight. The solvent was removed under reduced pressure to yield a mixture of isomers of mesoerythritol diacetoacetate (13.4 g, 94%) as an orange solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 2.18 (m, 6H), 3.38 (m, 6H), 3.54 (m, 2H), 4.24 (m, 1H), 4.43 (m, 1H), 4.48 (s, 1H), 5.52 (m, 1H).

[0470] Example 16: Mesoerythritol (6 g, 0.05 mol, 1 equiv.) was charged to a stirred-tank reactor, and ethyl acetate (10.8 g, 2.5 equiv.) was added. To this suspension was added DABCO (7.2 mg, 0.0001 mol, 0.0013 equiv.). Diketene (12.4 g, 0.15 mol, 3 equiv.) was then added slowly to the reaction mixture over 8 hours while cooling the reactor jacket to maintain an internal temperature of 40 °C. The feed rate was adjusted to maintain an internal temperature of 40 °C. After the addition was complete, the mixture was maintained at an internal temperature of 40 °C overnight. The solvent was removed under reduced pressure to yield a mixture of isomers of mesoerythritol triacetoacetate (18.1 g, 99%) as a yellow suspension. 1H NMR (400 MHz, DMSO-d6) δ ppm 2.18 (m, 9H), 3.37 (m, 7H), 3.61 (m, 3H), 3.65(m, 3H), 4.23 (m, 1H), 4.35 (m, 2H), 5.25 (m, 1H).

[0471] Example 17: A mixture of mesoerythritol monoacetoacetate isomers (6.9 g, 0.03 mol, 1 eq., Example 14) was placed in an autoclave along with ethyl acetate (141 g, 41 eq.). RuO2 (0.08 g, 0.6 mmol, 0.02 eq.) was added, and the atmosphere was exchanged by pressurizing the reactor three times with nitrogen and then three times with hydrogen. The hydrogen pressure was adjusted to 20 bar, and the mixture was heated to 60 °C with stirring at 1000 rpm to observe possible hydrogen uptake (6 days). Afterwards, the mixture was cooled to room temperature, and the hydrogen atmosphere was exchanged with nitrogen. The reaction mixture was mixed with activated carbon and filtered through Celite. The solvent was evaporated from the filtrate, and the product was analyzed. The resulting mixture of mesoerythritol mono(3-hydroxybutanoate) isomers was isolated as a yellow oil (3.42 g, 49%). 1H NMR (400 MHz, DMSO-d6) δ ppm 1.09 (m, 3H), 2.36 (m, 2H), 3.36 (m, 3H), 3.94 (m, 3H), 4.30 (m, 3H).

[0472] Example 18: A mixture of isomers of mesoerythritol diacetoacetate (11.9 g, 0.04 mol, 1 equiv., Example 15) was placed in an autoclave along with ethyl acetate (141 g, 41 equiv.). Ru / C (5 wt %, 4 g, 2.0 mmol, 0.05 equiv.) was added, and the atmosphere was exchanged by pressurizing the reactor three times with nitrogen and then three times with hydrogen. The hydrogen pressure was adjusted to 10 bar, and the mixture was heated to 40 °C while stirring at 1000 rpm to observe possible hydrogen uptake (1 day). Afterwards, the mixture was cooled to room temperature, and the hydrogen atmosphere was exchanged with nitrogen. The reaction mixture was mixed with activated carbon and filtered through Celite. The solvent was evaporated from the filtrate, and the product was analyzed. The resulting mixture of isomers of mesoerythritol di(3-hydroxybutanoate) was isolated as a yellow oil (7.51 g, 64%). 1H NMR (400 MHz, DMSO-d6) δ ppm 1.10 (m, 6H), 2.36 (m, 4H), 4.01 (m, 3H), 4.17 (m, 1H), 4.34 (m, 1H), 4.74 (m, 2H).

[0473] Example 19: A mixture of mesoerythritol triacetoacetate isomers (16.5 g, 0.04 mol, 1 equiv., Example 16) was placed in an autoclave along with ethyl acetate (140 g, 36 equiv.). Ru / C (5 wt %, 5.5 g, 2.7 mmol, 0.06 equiv.) was added, and the atmosphere was exchanged by pressurizing the reactor three times with nitrogen and then three times with hydrogen. The hydrogen pressure was adjusted to 10 bar, and the mixture was heated to 40 °C while stirring at 1000 rpm to observe possible hydrogen uptake (1 day). Afterwards, the mixture was cooled to room temperature, and the hydrogen atmosphere was exchanged with nitrogen. The reaction mixture was mixed with activated carbon and filtered through Celite. The solvent was evaporated from the filtrate, and the product was analyzed. The resulting mixture of mesoerythritol tri(3-hydroxybutanoate) isomers was isolated as a yellow oil (16.6 g, 99%). 1H NMR (400 MHz, DMSO-d6) δ ppm 1.09 (m, 9H), 2.37 (m, 6H), 3.99 (m, 3H), 4.15 (m, 1H), 4.31 (m, 1H), 4.74 (m, 3H). A portion of the claims of this application as filed is reproduced below. (Item 1) A compound of formula 1, wherein A is obtained from an organic polyol having at least four hydroxyl groups, X is -C(H)(OH)- or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial organic polyol A). (Item 2) A compound of formula 1, wherein A is obtained from an organic polyol having at least four hydroxyl groups, X is -C(H)(OH)- or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial organic polyol A. 1. A process for preparing (i) reacting an organic polyol of formula 2 with diketene 3 to form a compound of formula 4; and (iia) reacting a compound of formula 4 with hydrogen in the presence of a catalyst to form a compound of formula 5 and optionally, (iib) The compound of formula 5 is reacted with the compound LG-R 1 wherein LG is a leaving group to form a compound of formula 6 The above process, comprising: (Item 3) The organic polyol is a linear or branched C substituted with at least four hydroxyl groups. 2~12 C substituted with alkyl or at least four hydroxyl groups 3~8 Item 1. The compound according to item 1 or the process according to item 2, wherein the aryl group is selected from cycloalkyl. (Item 4) The linear or branched chain C substituted with at least four hydroxyl groups 2~12 The alkyl is selected from the group consisting of pentaerythritol, butane tetrol, pentane tetrol, hexane tetrol, and hexane pentol; and / or the C substituted with at least four hydroxyl groups.3~8 4. The compound or process according to item 3, wherein cycloalkyl is selected from the group consisting of cyclopentane tetrol, cyclopentane pentol, cyclohexane tetrol, cyclohexane pentol, and cyclohexane hexol. (Item 5) The compound of item 1 or the process of item 2, wherein the organic polyol is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids. (Item 6) The monosaccharide is selected from pentose, hexose, and heptose, preferably, the monosaccharide is selected from aldopentose, ketopentose, aldohexose, ketohexose, aldoheptose, and ketoheptose; Preferably, the monosaccharide is ribose, arabinose, xylose, lyxose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, N-acetyl-D-glucosamine, glucosamine, N-acetyl-D-galactosamine, fucose, rhamnose, synovose, fructose, 2-deoxy-D-glucose, fluorodeoxyglucose, 6-deoxyglucose, 2-deoxy-D- ... 6. The compound or process of item 5, wherein the sugar is selected from the group consisting of oxyfructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, mannoheptulose, L-glycero-D-mannoheptose, and combinations thereof. 7. The compound or process of claim 5 or 6, wherein the sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof; and / or the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof. (Item 8) The compound or process of any one of items 1 to 7, wherein the organic polyol is selected from the group consisting of sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, and pentaerythritol. (Item 10) A compound of formula 9 (wherein z is 0 or 1, A is derived from an organic polyol having at least three hydroxyl groups; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial polyol A). (Item 11) The organic polyol is a linear or branched C substituted with at least three hydroxyl groups. 2~12 C substituted with alkyl or at least three hydroxyl groups 3~8 11. The compound according to item 10, wherein the aryl group is selected from cycloalkyl. (Item 12) The linear or branched C substituted with at least three hydroxyl groups2~ 12 wherein the alkyl is selected from the group consisting of glycerol, trimethylolpropane, butanetriol, 2-methyl-propanetriol, pentanetriol, 3-methyl-pentanetriol, hexanetriol, pentaerythritol, butanetetrol, pentanetetrol, hexanetetrol, hexanepentol, and combinations thereof, and / or the C substituted with at least three hydroxyl groups. 3~8 Item 12. The compound according to item 11, wherein the cycloalkyl is selected from the group consisting of cyclopentanetriol, cyclohexanetriol, cyclopentanetetrol, cyclohexanetetrol, and combinations thereof. (Item 13) The compound according to Item 10, wherein the organic polyol is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids. (Item 14) The monosaccharide is selected from tetrose, pentose, hexose, and heptose, preferably, the monosaccharide is selected from aldotetrose, ketotetrose, aldopentose, ketopentose, aldohexose, ketohexose, aldoheptose, and ketoheptose; Preferably, the monosaccharide is erythrose, threose, erythrulose, ribose, arabinose, xylose, lyxose, deoxyribose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, N-acetyl-D-glucosamine, glucosamine, N-acetyl-D-galactosamine, fucose, rhamnose, synovose, fructose, or 2-deoxy-D-glucose. 14. The compound according to item 13, wherein the compound is selected from the group consisting of fluorodeoxyglucose, 6-deoxyfructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, mannoheptulose, L-glycero-D-mannoheptose, and combinations thereof. (Item 15) The sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof; and / or the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof. (Item 16) The compound according to any one of Items 10 to 15, wherein the organic polyol is selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, pentaerythritol, and trimethylolpropane. (Item 17) The compound according to any one of Items 10 to 16, wherein the organic polyol is erythritol. (Item 19) The compound or process of any one of items 1 to 18, wherein y is from 3 to the number of hydroxyl groups in the initial polyol A, or y is from 4 to the number of hydroxyl groups in the initial polyol A, or y is equal to the number of hydroxyl groups in the initial polyol A. (Item 20)R 1 is a fatty acid residue selected from an omega fatty acid, a medium chain fatty acid, or a combination thereof, preferably wherein the omega fatty acid is an omega 3 fatty acid, an omega 6 fatty acid, an omega 3,6 fatty acid, or a combination thereof, and / or the medium chain fatty acid is selected from the group consisting of caproic acid, caprylic acid, capric acid, lauric acid, and a combination thereof. (Item 21) A compound of formula 9, wherein z is 0 or more, A is derived from an organic polyol having at least three hydroxyl groups, provided that the organic polyol is not erythritol; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8 Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial polyol A). (Item 22) The compound according to Item 21, wherein z is 0 to 100, for example, 0 to 95, 0 to 90, 0 to 85, 0 to 80, 0 to 75, 0 to 70, 0 to 65, 0 to 60, 0 to 55, 0 to 50, 0 to 45, 0 to 40, 0 to 35, 0 to 30, 0 to 25, or 0 to 20, preferably z is 0 to 20, for example, 0 to 19, for example, 0 to 18, for example, 0 to 17, for example, 0 to 16, for example, 0 to 15, for example, 0 to 14, for example, 0 to 13, for example, 0 to 12, for example, 0 to 11, for example, 0 to 10, for example, 0 to 9, for example, 0 to 8, for example, 0 to 7, for example, 0 to 6, for example, 0 to 5, for example, 0 to 4, for example, 0 to 3, or 0 to 2, more preferably z is 0 or 1. (Item 23) The organic polyol is a linear or branched C substituted with at least three hydroxyl groups. 2~12 C substituted with alkyl or at least three hydroxyl groups 3~8 23. The compound according to item 21 or 22, selected from cycloalkyl. (Item 24) The linear or branched chain C substituted with at least three hydroxyl groups 2~12wherein the alkyl is selected from the group consisting of glycerol, trimethylolpropane, butanetriol, 2-methyl-propanetriol, pentanetriol, 3-methyl-pentanetriol, hexanetriol, pentaerythritol, butanetetrol, pentanetetrol, hexanetetrol, hexanepentol, and combinations thereof, and / or the C substituted with at least three hydroxyl groups. 3~8 24. The compound according to item 23, wherein the cycloalkyl is selected from the group consisting of cyclopentanetriol, cyclohexanetriol, cyclopentanetetrol, cyclohexanetetrol, and combinations thereof. (Item 25) The compound according to Item 21 or 22, wherein the organic polyol is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids. (Item 26) The monosaccharide is preferably selected from tetrose, pentose, hexose, and heptose, and the monosaccharide is preferably selected from aldotetrose, ketotetrose, aldopentose, ketopentose, aldohexose, ketohexose, aldoheptose, and ketoheptose; Preferably, the monosaccharide is erythrose, threose, erythrulose, ribose, arabinose, xylose, lyxose, deoxyribose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, N-acetyl-D-glucosamine, glucosamine, N-acetyl-D-galactosamine, fucose, rhamnose, synovose, fructose, or 2-deoxy-D-glucose. 26. The compound according to item 25, wherein the compound is selected from the group consisting of fluorodeoxyglucose, 6-deoxyfructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, mannoheptulose, L-glycero-D-mannoheptose, and combinations thereof. (Item 27) The sugar alcohol is selected from the group consisting of threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof; and / or the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof. (Item 28) The compound according to any one of Items 21 to 27, wherein the organic polyol is selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, maltitol, glucose, glucitol, ribulose, pentaerythritol, and trimethylolpropane. (Item 30) The compound according to any one of Items 21 to 29, wherein y is from 3 to the number of hydroxyl groups in the initial polyol A, or y is from 4 to the number of hydroxyl groups in the initial polyol A, or y is equal to the number of hydroxyl groups in the initial polyol A. (Item 31)R 1 is a fatty acid residue selected from an omega fatty acid, a medium chain fatty acid, or a combination thereof, preferably the omega fatty acid is an omega 3 fatty acid, an omega 6 fatty acid, an omega 3,6 fatty acid, or a combination thereof, and / or the medium chain fatty acid is selected from the group consisting of caproic acid, caprylic acid, capric acid, lauric acid, and a combination thereof. (Item 32) A compound of formula 9, wherein z is 0 or more, A is derived from an organic polyol having at least three hydroxyl groups; X is -C(O)-, -C(H)(OH)-, or -C(H)(OR 1 )- and R 1 is a linear or branched chain C 1~12 Alkyl, C 3~8Cycloalkyl, straight or branched chain C 2~12 Hydroxyalkyl, linear or branched C 1~12 Carboxyalkyl, straight or branched chain saturated or unsaturated C 1~24 selected from alkanoyl, phenyl, and carboxyphenyl; y is from 1 to the number of hydroxyl groups in the initial organic polyol A. 1. A process for preparing (i) reacting a compound of formula 10 with diketene 3 to form a compound of formula 11 and optionally, (iia) reacting a compound of formula 11 with hydrogen in the presence of a catalyst to form a compound of formula 12. and optionally, (iib) The compound of formula 12 is reacted with the compound LG-R 1 wherein LG is a leaving group to form a compound of formula 13. The above process, comprising: (Item 33) The process according to Item 32, wherein z is 0 to 100, for example, 0 to 95, 0 to 90, 0 to 85, 0 to 80, 0 to 75, 0 to 70, 0 to 65, 0 to 60, 0 to 55, 0 to 50, 0 to 45, 0 to 40, 0 to 35, 0 to 30, 0 to 25, or 0 to 20, preferably z is 0 to 20, for example, 0 to 19, for example, 0 to 18, for example, 0 to 17, for example, 0 to 16, for example, 0 to 15, for example, 0 to 14, for example, 0 to 13, for example, 0 to 12, for example, 0 to 11, for example, 0 to 10, for example, 0 to 9, for example, 0 to 8, for example, 0 to 7, for example, 0 to 6, for example, 0 to 5, for example, 0 to 4, for example, 0 to 3, for example, 0 to 2, more preferably z is 0 or 1. (Item 34) The organic polyol is a linear or branched C substituted with at least three hydroxyl groups. 2~12 C substituted with alkyl or at least three hydroxyl groups 3~8 34. The process according to item 32 or 33, wherein the alkyl is selected from cycloalkyl. (Item 35) The linear or branched chain C substituted with at least three hydroxyl groups 2~12wherein the alkyl is selected from the group consisting of glycerol, trimethylolpropane, butanetriol, 2-methyl-propanetriol, pentanetriol, 3-methyl-pentanetriol, hexanetriol, pentaerythritol, butanetetrol, pentanetetrol, hexanetetrol, hexanepentol, and combinations thereof, and / or the C substituted with at least three hydroxyl groups. 3~8 35. The process of claim 34, wherein the cycloalkyl is selected from the group consisting of cyclopentanetriol, cyclohexanetriol, cyclopentanetetrol, cyclohexanetetrol, and combinations thereof. (Item 36) The process described in Items 32 or 33, wherein the organic polyol is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids. (Item 37) The monosaccharide is selected from tetrose, pentose, hexose, and heptose, preferably selected from aldotetrose, ketotetrose, aldopentose, ketopentose, aldohexose, ketohexose, aldoheptose, and ketoheptose; Preferably, the monosaccharide is erythrose, threose, erythrulose, ribose, arabinose, xylose, lyxose, deoxyribose, ketopentose, ribulose, xylulose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, N-acetyl-D-glucosamine, glucosamine, N-acetyl-D-galactosamine, fucose, rhamnose, synovose, fructose, or 2-deoxy-D-glucose. 37. The process of claim 36, wherein the sugar is selected from the group consisting of fluorodeoxyglucose, 6-deoxyfructose, 1,6-dichlorofructose, 3,6-anhydrogalactose, 1-O-methylgalactose, 1-O-methyl-D-glucose, 1-O-methyl-D-fructose, 3-O-methyl-D-fructose, 6-O-methyl-D-galactose, sedoheptulose, mannoheptulose, L-glycero-D-mannoheptose, and combinations thereof. (Item 38) The sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof; 38. The process according to item 36 or 37, wherein the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof. (Item 39) The process described in any one of Items 32 to 38, wherein the organic polyol is selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, pentaerythritol, and trimethylolpropane. (Item 40) The process according to any one of Items 32 to 39, wherein the organic polyol is erythritol. (Item 42) The process according to any one of Items 32 to 41, wherein y is from 3 to the number of hydroxyl groups in the initial polyol A, or y is from 4 to the number of hydroxyl groups in the initial polyol A, or y is equal to the number of hydroxyl groups in the initial polyol A. (Item 43)R 1 is a fatty acid residue selected from an omega fatty acid, a medium chain fatty acid, or a combination thereof, preferably the omega fatty acid is an omega 3 fatty acid, an omega 6 fatty acid, an omega 3,6 fatty acid, or a combination thereof, and / or the medium chain fatty acid is selected from the group consisting of caproic acid, caprylic acid, capric acid, lauric acid, and a combination thereof. (Item 44) The compound or process according to any one of items 1 to 43, wherein all β-hydroxyl butyrate ester units are in the R configuration.

Claims

1. Compound of Formula 1 【Chemistry 1】 (In the formula, A is derived from an organic polyol having at least four hydroxyl groups (A is referred to as initial organic polyol A); X is —C(H)(OH)— or —C(H)(OR １ ) - and R １ is a linear or branched chain C １～１２ Alkyl, C ３～８ Cycloalkyl, straight or branched chain C ２～１２ Hydroxyalkyl, straight or branched chain C １～１２ Carboxyalkyl, straight or branched chain saturated or unsaturated C １～２４ selected from alkanoyl, phenyl, and carboxyphenyl; y is equal to the number of hydroxyl groups in the initial organic polyol A; The initial organic polyol A is a linear or branched C substituted with at least four hydroxyl groups. ２～１２ alkyl, or C substituted with at least four hydroxyl groups ３～８ cycloalkyl; The above compound, wherein the linear or branched C 2-12 alkyl substituted with at least four hydroxyl groups is selected from the group consisting of pentaerythritol, butane tetrol, pentane tetrol, hexane tetrol, and hexane pentol; and / or the C 3-8 cycloalkyl substituted with at least four hydroxyl groups is selected from the group consisting of cyclopentane tetrol, cyclopentane pentol, cyclohexane tetrol, cyclohexane pentol, and cyclohexane hexol.

2. Compound of Formula 1 【Chemistry 2】 (In the formula, A is derived from an organic polyol having at least four hydroxyl groups (A is referred to as initial organic polyol A); X is —C(H)(OH)— or —C(H)(OR １ ) - and R １ is a linear or branched chain C １～１２ Alkyl, C ３～８ Cycloalkyl, straight or branched chain C ２～１２ Hydroxyalkyl, straight or branched chain C １～１２ Carboxyalkyl, straight or branched chain saturated or unsaturated C １～２４ selected from alkanoyl, phenyl, and carboxyphenyl; y is equal to the number of hydroxyl groups in the initial organic polyol A; The initial organic polyol A is a linear or branched C substituted with at least four hydroxyl groups. ２～１２ alkyl, or C substituted with at least four hydroxyl groups ３～８ cycloalkyl; the linear or branched C 2-12 alkyl substituted with at least four hydroxyl groups is selected from the group consisting of pentaerythritol, butane tetrol, pentane tetrol, hexane tetrol, and hexane pentol; and / or the C 3-8 cycloalkyl substituted with at least four hydroxyl groups is selected from the group consisting of cyclopentane tetrol, cyclopentane pentol, cyclohexane tetrol, cyclohexane pentol, and cyclohexane hexol.

1. A process for preparing (i) reacting an organic polyol of formula 2 with diketene 3 to produce a compound of formula 4 【Transformation 3】 forming a (iia) reacting a compound of formula 4 with hydrogen in the presence of a catalyst to produce a compound of formula 5 【Chemistry 4】 To form and optionally, (iib) The compound of formula 5 is reacted with the compound LG-R １ wherein LG is a leaving group to produce a compound of formula 6 【Transformation 5】 To form The above process, comprising:

3. 2. The compound of claim 1, wherein the initial organic polyol A is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids.

4. 3. The process of claim 2, wherein the initial organic polyol A is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids.

5. 4. The compound of claim 3, wherein the monosaccharide is selected from pentoses, hexoses, and heptoses.

6. 5. The process of claim 4, wherein the monosaccharide is selected from pentoses, hexoses, and heptoses.

7. 4. The compound of claim 3, wherein the sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof; and / or the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof.

8. 5. The process of claim 4, wherein the sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof; and / or the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof.

9. 2. The compound of claim 1, wherein the first organic polyol A is selected from the group consisting of sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, and pentaerythritol.

10. 3. The process of claim 2, wherein the initial organic polyol A is selected from the group consisting of sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, and pentaerythritol.

11. The compound is 【Transformation 6】 【Transformation 7】 2. The compound of claim 1 selected from the group consisting of:

12. The compound is 【Transformation 8】 【Chemistry 9】 3. The process of claim 2, wherein the compound is selected from the group consisting of:

13. Compound of Formula 9 【Chemistry 10】 (In the formula, z is 0 or 1; A is derived from an organic polyol having at least three hydroxyl groups (A is the first (hereinafter referred to as organic polyol A) X is —C(O)—, —C(H)(OH)—, or —C(H)(OR １ ) - and R １ is a linear or branched chain C １～１２ Alkyl, C ３～８ Cycloalkyl, straight or branched chain C ２～１２ Hydroxyalkyl, straight or branched chain C １～１２ Carboxyalkyl, straight or branched chain saturated or unsaturated C １～２４ selected from alkanoyl, phenyl, and carboxyphenyl; y is equal to the number of hydroxyl groups in the initial organic polyol A. And, The initial organic polyol A is selected from the group consisting of trimethylolpropane, butanetriol, 2-methyl-propanetriol, pentanetriol, 3-methyl-pentanetriol, hexanetriol, pentaerythritol, butanetetrol, pentanetetrol, hexanetetrol, hexanepentol, and combinations thereof. ２～１２ C which is alkyl or substituted with at least three hydroxyl groups ３～８ The compound above, wherein the aryl group is selected from cycloalkyl.

14. The C substituted with at least three hydroxyl groups ３～８ 14. The compound of claim 13, wherein the cycloalkyl is selected from the group consisting of cyclopentanetriol, cyclohexanetriol, cyclopentanetetrol, cyclohexanetetrol, and combinations thereof.

15. R １ is a fatty acid residue selected from an omega fatty acid, a medium chain fatty acid, or a combination thereof.

16. R １ 3. The process of claim 2, wherein is a fatty acid residue selected from an omega fatty acid, a medium chain fatty acid, or a combination thereof.

17. Compound of Formula 9 【Chemistry 11】 (In the formula, z is 0 or 1; A is derived from an organic polyol having at least three hydroxyl groups, provided that the organic polyol is not erythritol (A is referred to as initial organic polyol A); X is —C(O)—, —C(H)(OH)—, or —C(H)(OR １ ) - and R １ is a linear or branched chain C １～１２ Alkyl, C ３～８ Cycloalkyl, straight or branched chain C ２～１２ Hydroxyalkyl, straight or branched chain C １～１２ Carboxyalkyl, straight or branched chain saturated or unsaturated C １～２４ Alkanoyl, phenyl, and carbo selected from phenyl, y is equal to the number of hydroxyl groups in the initial organic polyol A. And, The initial organic polyol A is selected from the group consisting of trimethylolpropane, butanetriol, 2-methyl-propanetriol, pentanetriol, 3-methyl-pentanetriol, hexanetriol, pentaerythritol, butanetetrol, pentanetetrol, hexanetetrol, hexanepentol, and combinations thereof. ２～１２ C which is alkyl or substituted with at least three hydroxyl groups ３～８ The compound above, wherein the aryl group is selected from cycloalkyl.

18. The C substituted with at least three hydroxyl groups ３～８ 18. The compound of claim 17, wherein the cycloalkyl is selected from the group consisting of cyclopentanetriol, cyclohexanetriol, cyclopentanetetrol, cyclohexanetetrol, and combinations thereof.

19. R １ 18. The compound of claim 17, wherein is a fatty acid residue selected from an omega fatty acid, a medium chain fatty acid, or a combination thereof.

20. Compound of Formula 9 【Chemistry 12】 (In the formula, z is 0 or 1; A is derived from an organic polyol having at least three hydroxyl groups (A is referred to as initial organic polyol A); X is —C(O)—, —C(H)(OH)—, or —C(H)(OR １ ) - and R １ is a linear or branched chain C １～１２ Alkyl, C ３～８ Cycloalkyl, straight or branched chain C ２～１２ Hydroxyalkyl, straight or branched chain C １～１２ Carboxyalkyl, straight or branched chain saturated or unsaturated C １～２４ selected from alkanoyl, phenyl, and carboxyphenyl; y is equal to the number of hydroxyl groups in the initial organic polyol A; The initial organic polyol A is a linear or branched C substituted with at least three hydroxyl groups. ２～１２ C which is alkyl or substituted with at least three hydroxyl groups ３～８ cycloalkyl) 1. A process for preparing (i) reacting a compound of formula 10 with diketene 3 to give a compound of formula 11 【Chemistry 13】 To form and optionally, (iia) reacting a compound of formula 11 with hydrogen in the presence of a catalyst to produce a compound of formula 12 【Chemistry 14】 To form and optionally, (iib) reacting the compound of formula 12 with the compound LG-R １ wherein LG is a leaving group to give a compound of formula 13 【Chemistry 15】 To form The above process, comprising:

21. The linear or branched C substituted with at least three hydroxyl groups ２～１２ The alkyl is selected from the group consisting of glycerol, trimethylolpropane, butanetriol, 2-methyl-propanetriol, pentanetriol, 3-methyl-pentanetriol, hexanetriol, pentaerythritol, butanetetrol, pentanetetrol, hexanetetrol, hexanepentol, and combinations thereof, and / or the C substituted with at least three hydroxyl groups. ３～８ 21. The process of claim 20, wherein the cycloalkyl is selected from the group consisting of cyclopentanetriol, cyclohexanetriol, cyclopentanetetrol, cyclohexanetetrol, and combinations thereof.

22. 21. The process of claim 20, wherein the initial organic polyol A is selected from the group consisting of monosaccharides, sugar alcohols, and sugar acids.

23. 23. The process of claim 22, wherein the monosaccharide is selected from a tetrose, a pentose, a hexose, and a heptose.

24. the sugar alcohol is selected from the group consisting of erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, and combinations thereof; and / or the sugar acid is selected from the group consisting of xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, ketodeoxyoctonic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, sugar acid, and combinations thereof.

25. 21. The process of claim 20, wherein the initial organic polyol A is selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, erythritol, maltitol, glucose, glucitol, ribulose, pentaerythritol, and trimethylolpropane.

26. 21. The process of claim 20, wherein the initial organic polyol A is erythritol.

27. The compound is 【Chemistry 16】 21. The process of claim 20, selected from the group consisting of:

28. R １ 21. The process of claim 20, wherein is a fatty acid residue selected from an omega fatty acid, a medium chain fatty acid, or a combination thereof.

29. 18. The compound of claim 1, 13, or 17, wherein all β-hydroxyl butyrate units are in the R configuration.

30. 21. The process of claim 2 or 20, wherein all of the β-hydroxyl butyrate ester units are in the R configuration.

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