Method for preparing dienes

Abstract

The present invention relates to the field of organic synthesis, more particularly to a process for the preparation of compounds of formula (I) catalyzed by nickel complexes. Compounds of formula (II) are also part of the present invention.

Description

[Technical Field]

[0001] This invention relates to the field of organic synthesis, and more specifically to a method for preparing a compound of formula (I) catalyzed by a nickel complex. Compounds of formula (II) are also part of this invention.

[0002] Background of the Invention The 1,3,5-triene or 1,3-diene-5-yine derivatives of formula (I) possess a highly desirable skeleton that can be used on its own or as important intermediates useful for producing more complex compounds in various fields, particularly in fragrances, cosmetics, pharmaceuticals, or agrochemicals. In particular, 1,3-undecadiene-5-yine and 1,3,5-undecadriene are valuable compounds known as fragrance components that impart green notes highly valued by perfumers. However, compounds of formula (I) are mainly obtained by Grignard reactions, which are difficult to manufacture due to the high degree of dilution in hazardous solvents and the generation of large amounts of undesirable waste, especially halogenated waste. For decades, metal-catalyzed couplings have been widely developed to overcome these drawbacks in order to obtain triene building blocks or en-yine building blocks, such as those described in U.S. Patent No. 4,652,692. However, metal-catalyzed couplings involving triple bonds require pre-activation of the triple bond with, for example, tin, silyl, or carboxylic acid functional groups. Coupling at terminal triple bonds has not been reported to date.

[0003] Therefore, there is still a need to develop safer and cleaner methods for obtaining these compounds through the coupling of terminal triple bonds.

[0004] This invention makes it possible to obtain the compound of formula (I) in high yield while avoiding the formation of the (3Z) isomer by combining two steps, both catalyzed by a nickel complex. To the best of our knowledge, neither of these steps has been reported in the prior art.

[0005] SUMMARY OF THE INVENTION The present invention relates to a novel method that enables the preparation of compounds of formula (I) using a methodology not reported or suggested in the prior art.

[0006] Thus, a first object of the present invention is a compound of formula (I) in the form of any one of the stereoisomers or a mixture thereof

Chemical formula

Chemical formula

[0007] A second object of this invention is any one form of the stereoisomer of formula (IV) [ka] [In the formula, R 1 is one or more hydroxyl groups, C 1~15 Alkoxy group, C 2~15 Alkenyloxy group, C 3~15 Heterocycloalkyl groups, C 6~10 Aryloxy group, and / or C 1~4 C may be substituted with a carboxylic acid ester group. 1~10 Represents a hydrocarbon group, R 2 , R 3 , and R 4 These are, independently of each other, hydrogen atoms and C 1~3 It represents an alkyl group or a phenyl group, where Y is a hydrogen atom, and C 1~3 Alkyl alkyl group, or CHR 5 It is an X group, R 5 C is a hydrogen atom. 1~3 It is an alkyl group or a phenyl group, and X is OR 6 Base, OC(=O)R 6 Base, OC(=O)OR 6 Base, or OSO2R 6 Represents the base, R 6 is a hydrogen atom or C 1~4 [It is an alkyl group or a phenyl group.] A method for preparing the compound, In the presence of a nickel catalyst, the following formula is obtained for one of the stereoisomers: [ka] [In the formula, R 1 [This has the same meaning as defined in equation (IV)] The compound is expressed in one of the following stereoisomer forms: [ka] [where X, Y, R 2 , R 3 , and R 4These terms, independently of each other, have the same meaning as those defined in equation (IV). This method involves reacting it with the compound.

[0008] The third object of this invention is the following formula of any one form of the stereoisomer [ka] [In the formula, the dotted line represents a carbon-carbon double bond or a carbon-carbon triple bond, R 1 is one or more hydroxyl groups, C 1~15 Alkoxy group, C 2~15 Alkenyloxy group, C 3~15 Heterocycloalkyl groups, C 6~10 Aryloxy group, and / or C 1~4 Linear or branched carbon atoms may be substituted with carboxylic acid ester groups. 1~10 R represents an alkyl group. 2 , R 3 , R 4 , and R 5 These are, independently of each other, hydrogen atoms and C 1~3 X represents an alkyl group or a phenyl group, and X is OR 6 Base, OC(=O)R 6 Base, OC(=O)OR 6 Base, or OSO2R 6 Represents the base, R 6 is a hydrogen atom or C 1~4 [It is an alkyl group or a phenyl group.] It is a compound of [the compound].

[0009] Description of the Invention Remarkably, it was discovered that the compound of formula (I) can be produced in a favorable manner by a Ni-catalyzed coupling reaction followed by a Ni-catalyzed elimination reaction. These unprecedented steps allow for the production of the compound of formula (I), in which the double bond at position 3 is primarily E, while avoiding the use of strong bases and the generation of halide waste.

[0010] Therefore, the first subject of the present invention is formula (I) in the form of one or a mixture thereof of stereoisomers. [ka] [In the formula, the dotted line represents a carbon-carbon double bond or a carbon-carbon triple bond, R 1 is one or more hydroxyl groups, C 1~15 Alkoxy group, C 2~15 Alkenyloxy group, C 3~15 Heterocycloalkyl groups, C 6~10 Aryloxy group, and / or C 1~4 C may contain a carboxylic acid ester group. 1~10 Represents a hydrocarbon group, R 2 , R 3 , R 4 , and R 5 These are, independently of each other, hydrogen atoms and C 1~3 [Represents an alkyl group or a phenyl group] A method for preparing a compound of formula (II) in which one of the stereoisomers is obtained [ka] [In the formula, dotted line, R 1 , R 2 , R 3 , R 4 , and R 5 The expression has the same meaning as defined in equation (I), and X is OR. 6 Base, OC(=O)R 6 Base, OC(=O)OR 6 Base, or OSO2R 6 Represents the base, R 6 is a hydrogen atom or C 1~4 [It is an alkyl group or a phenyl group.] The method involves reacting the compound using a nickel catalyst.

[0011] For the sake of clarity, it is noted that the term "any one of the stereoisomers or a mixture thereof" or a similar expression has the ordinary meaning understood by those skilled in the art, that is, it is intended that the compounds recited in the present invention may be either pure enantiomers or mixtures of enantiomers. In other words, the compounds recited in the present invention may have at least one stereocenter that can have two different stereochemistries (e.g., R or S), for example R 1 The group may contain at least one stereocenter. The compound may be in the form of a pure enantiomer or a mixture of enantiomers. When the compounds recited in the present invention have two or more stereocenters, the compound may be in the form of a pure diastereoisomer or a mixture of diastereoisomers. The compound may be in racemic form or scalemic form. Therefore, the compound may be in the form of a single stereoisomer, or a substance composition containing or consisting of various stereoisomers.

[0012] The wavy line indicates that the double bond may be in the form of its E isomer or Z isomer or a mixture thereof. For example, the present invention includes a substance composition consisting of one or more compounds of formula (I) having the same chemical structure but different double bond arrangements.

[0013] According to any one of the above embodiments of the present invention, the compound of formula (I) may be in the form of its E isomer, Z isomer, or a mixture thereof. For example, the present invention includes a material composition comprising one or more compounds of formula (I) having the same chemical structure but differing in the arrangement of their double bonds. According to a particular embodiment of the present invention, compound (I) may be in the form of a mixture comprising isomers 3E and 3Z, wherein isomer 3E accounts for at least 50%, more preferably at least 75%, and more preferably at least 90% of the total mixture (i.e., the E / Z mixture is included in 90 / 10 to 100 / 0). According to another particular embodiment of the present invention, compound (I) may be in the form of a mixture comprising isomers (3E,5Z) and (3Z,5Z), wherein isomer (3E,5Z) accounts for at least 50%, more preferably at least 75%, and more preferably at least 90% of the total mixture (i.e., the E / Z mixture is included in 90 / 10 to 100 / 0).

[0014] For the sake of clarity, the statement "the dotted line represents a carbon-carbon double bond or carbon-carbon triple bond" or similar is intended to have the usual meaning as understood by those skilled in the art, that is, the entirety of the bonds between carbon atoms connected by the dotted line (solid and dotted lines) is intended to represent a carbon-carbon double bond or carbon-carbon triple bond.

[0015] "...hydrocarbon group..." means that the group consists of a hydrogen atom and a carbon atom and may be in the form of an aliphatic hydrocarbon, i.e., a linear or branched saturated hydrocarbon (e.g., alkyl group), a linear or branched unsaturated hydrocarbon (e.g., alkenyl or alkynyl group), a saturated cyclic hydrocarbon (e.g., cycloalkyl), or an unsaturated cyclic hydrocarbon (e.g., cycloalkenyl or cycloalkynyl), or in the form of an aromatic hydrocarbon, i.e., an aryl group, or in the form of a mixture of the above types of groups, and it is understood that, for example, a particular group may include linear alkyl, branched alkenyl (e.g., having one or more carbon-carbon double bonds), (poly)cycloalkyl, and aryl moieties unless a specific limitation to only one type is mentioned. Similarly, in all embodiments of the present invention, when a group is mentioned as being in the form of two or more types of topology (e.g., linear, cyclic, or branched) and / or saturated or unsaturated (e.g., alkyl, aromatic, or alkenyl), it also means a group that may have any one of the topologies described above, or that may include a moiety that is saturated or unsaturated. Similarly, in all embodiments of the present invention, where a group is referred to as being in one type of form (e.g., alkyl), either saturated or unsaturated, it means that the group may be in any type of topology (e.g., linear, cyclic, or branched) or may have multiple sites with various topologies.

[0016] The term "optionally" is understood to mean that a group may or may not contain a particular functional group. The term "one or more" is understood to mean containing 1 to 7, preferably 1 to 5, and more preferably 1 to 3 functional groups.

[0017] According to any embodiment of the present invention, R 1 It optionally consists of one or more hydroxyl groups, C 1~5 Alkoxy group, C 2~5 Alkenyloxy group, C 3~6 Heterocycloalkyl groups, C 6~10An aryloxy group and / or a C 1~4 hydrocarbon group containing a carboxylic acid ester group may be used. In particular, R 1~10 may be an optionally substituted C 1 alkyl group having one hydroxy group or a C 1~4 hydrocarbon group containing a carboxylic acid ester group. In particular, R 1~10 may be a linear C 2~10 alkyl group or a linear C 1 alkenyl group having one hydroxy group or a C 1~4 hydrocarbon group containing a carboxylic acid ester group. In particular, R 1~10 may be a linear C 2~10 alkyl group, a linear C 3~10 alkenyl group, a branched C 3~10 alkyl group or a branched C 5~10 alkenyl group, a cyclic C 5~10 alkyl group or a cyclic C 6~10 alkenyl group, or a C 1 aryl group. In particular, R 1~4 may be a linear C 1~10 alkyl group, a linear C 2~10 alkenyl group, a branched C 3~10 alkyl group or a branched C 3~10 alkenyl group, or a C 6~10 aryl group. In particular, R 1 may be a linear C 1~10 alkyl group, a branched C 3~10 alkyl group, or a C 6~10 aryl group. In particular, R 1 may be a linear C 1~10 alkyl group, a branched C 3~10 alkyl group, or a phenyl group. In particular, R 1 may be a linear C 4~8 alkyl group. More specifically, R 1 may be a pentyl group.

[0018] According to any embodiment of the present invention, R 2 , R 3 , R 4 , and R 5 are each independently a hydrogen atom or a C1~3 It may be an alkyl group. In particular, R 2 , R 3 , R 4 , and R 5 These may be a hydrogen atom, a methyl group, or an ethyl group, independently of each other. In particular, R 2 , R 3 , R 4 , and R 5 These may be a hydrogen atom or a methyl group, independently of each other. In particular, R 2 , R 3 , R 4 , and R 5 Two of the groups may be hydrogen atoms or methyl groups, independently of each other, and the remaining one is a hydrogen atom. In particular, R 2 , R 3 , R 4 , and R 5 One of the groups may be a hydrogen atom or a methyl group, independently of the others, and the rest are hydrogen atoms. More specifically, R 2 , R 3 , R 4 , and R 5 It can be a hydrogen atom.

[0019] According to any embodiment of the present invention, R 6 is C 1~3 It may be an alkyl group. In particular, R 6 R may be a methyl group or an ethyl group. More specifically, 6 It may be a methyl group.

[0020] According to any embodiment of the present invention, X is OC(=O)R 6 It can represent the base, R 6 is a hydrogen atom or C 1~4 It is an alkyl group or a phenyl group. In particular, X is R 6 C 1~3 OC(=O)R is an alkyl group 6 It represents a group. More specifically, X represents an acetate group.

[0021] The terms “alkyl,” “alkoxy,” and “alkenyl” are understood to include branched and linear alkyl and alkenyl groups. The terms “alkenyl” and “alkenyloxy” are understood to include one, two, or three olefin double bonds, preferably one or two olefin double bonds. The term “heterocycloalkyl” is understood to include monocyclic, or condensed, spiro, and / or crosslinked bicyclic or tricyclic heterocycloalkyl groups, preferably monocyclic heterocycloalkyl groups. The term “heterocycloalkyl” is understood to include cycloalkyl groups containing one or more heteroatoms, particularly one or two oxygen atoms.

[0022] The terms "aryl" or "aryloxy" are understood to include any group containing at least one aromatic group, such as phenyl, indenyl, indanyl, benzodioxolyl, dihydrobenzodioxynyl, tetrahydronaphthalenyl, or a naphthalenyl group.

[0023] According to a particular embodiment of the present invention, the dotted line represents a triple bond. In other words, the compound of formula (I) is in the form of one or a mixture thereof of the following formula [ka] [In the formula, R 1 , R 2 , R 3 , R 4 , and R 5 [This has the same meaning as defined above.] It is a compound of the following formula. Furthermore, the compound of formula (II) is a stereoisomer of any one of the following forms. [ka] [In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , and X have the same meaning as defined above. It belongs to them.

[0024] According to a particular embodiment of the present invention, the dotted line represents a double bond. In other words, the compound of formula (I) is in the form of one or a mixture thereof of the following formula [ka] [In the formula, R 1 , R 2 , R 3 , R 4 , and R 5 [This has the same meaning as defined above.] It is the compound of formula (II) and one of its stereoisomers is the compound of the following formula. [ka] [In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , and X have the same meaning as defined above. The compound of formula (II'') is obtained by reduction of the compound of formula (II'). According to any embodiment of the present invention, the reduction is hydrogenation. In particular, hydrogenation is performed on palladium (Pd) in its elemental metallic form. 0 This can be carried out in the presence of heterogeneous catalysts such as palladium. In particular, the palladium can be supported on a support material. To clarify, a support material means a material on which such metals can be deposited and which is inert to a hydrogen source and substrate. Supported palladium (Pd 0 ) is a known and commercially available compound. Those skilled in the art can select the proportion of metal on the support material, the form (powder, granules, pellets, extruded, mousse, etc.), and the method of depositing it on the support as the surface area of ​​the support. In particular, hydrogenation can be carried out using a heterogeneous catalyst favorable to the formation of the Z double bond. In particular, the heterogeneous catalyst is the Lindler catalyst. Hydrogenation can be carried out under conditions known to those skilled in the art, which can set the best conditions for converting the compound of formula (II') to the compound of formula (II'').

[0025] Non-limiting examples of suitable compounds for formula (I) include 1,3-undecadien-5-yne, (3E)-1,3-undecadien-5-yne, 1,3,5-undecatriene, (3E,5Z)-1,3,5-undecatriene, (hexa-3,5-diene-1-yin-1-yl)benzene, ((1Z,3E)-hexa-1,3,5-triene-1-yl)benzene, ethylnonano-6,8-diene-4-inoate, and ethyl(4Z,6E)-nonano-4,6,8-tri Examples include enoates, (2E)-3-methylnonano-2,6,8-trien-4-in-1-ol, (2E,4Z,6E)-3-methylnonano-2,4,6,8-tetraen-1-ol, 2-methylocta-5,7-dien-3-in-2-ol, (3Z,5E)-2-methylocta-3,5,7-trien-2-ol, octa-5,7-dien-3-in-1-ol, and (3Z,5E)-octa-3,5,7-trien-1-ol.

[0026] Non-limiting examples of suitable compounds for formula (II) include undec-2-ene-5-in-1-ylacetate, (E)-undec-2-ene-5-in-1-ylacetate, undec-2,5-diene-1-ylacetate, (2E,5Z)-undec-2,5-diene-1-ylacetate, (E)-6-phenylhex-2-ene-5-in-1-ylacetate, (2E,5Z)-6-phenylhexa-2,5-diene-1-ylacetate, ethyl(E)-9-acetoxynon-7-ene-4-inoate, ethyl(4Z,7E)-9-acetoxynona-4,7-dienoate, Examples include (2E,7E)-9-hydroxy-7-methylnonano-2,7-diene-5-in-1-ylacetate, (2E,5Z,7E)-9-hydroxy-7-methylnonano-2,5,7-triene-1-ylacetate, (E)-7-hydroxy-7-methylocto-2-ene-5-in-1-ylacetate, (2E,5Z)-7-hydroxy-7-methylocta-2,5-diene-1-ylacetate, (E)-8-hydroxyocto-2-ene-5-in-1-ylacetate, and (2E,5Z)-8-hydroxyocta-2,5-diene-1-ylacetate.

[0027] According to any embodiment of the present invention, the nickel catalyst has the following formula. [Ni(P)4] (III) or [Ni(PP)2] (III') or [Ni(P)2ML] (III'') or [Ni(PP)ML] (III''') [In the formula, each P is a C3-C atom with one phosphorus atom as a coordinating group, independently of each other.] 30 Representing monodentate ligands, each PP is independent of the other and has two phosphorus atoms as coordinating groups (C5~C). 50 This represents a bidentate ligand, where M and L are independently anionic or neutral ligands, provided that when M is a neutral ligand, L is a neutral ligand, and when M is an anionic ligand, L is an anionic ligand.

[0028] Non-limiting examples of suitable anionic ligands include halogen atoms such as Cl, Br, or I. Non-limiting examples of suitable neutral ligands include olefin-containing compounds such as acrylonitrile, or ML may be a diene such as cycloocta-1,5-diene.

[0029] According to any embodiment of the present invention, the nickel catalyst has the following formula: [Ni(P)4] (III) or [Ni(PP)2] (III') [In the formula, each P is a C3-C atom with one phosphorus atom as a coordinating group, independently of each other.] 30 Representing monodentate ligands, each PP is independent of the other and has two phosphorus atoms as coordinating groups (C5~C). 50 [Represents a bidentate ligand]

[0030] According to any embodiment of the present invention, the phosphorus atom may be in the form of a phosphine group or a phosphite group.

[0031] According to any embodiment of the present invention, the ligand (PP) can be selected from the group consisting of 1,2-bis(diphenylphosphino)ethane and 1,4-bis(diphenylphosphino)butane.

[0032] According to any one embodiment of the present invention, ligand P is C3~C 30 It may be a monophosphine monodentate ligand or a monophosphine monodentate ligand. In particular, ligand P is given by formula P(OR 7 )3 monophosphite or formula PR 7 It can represent the monophosphine of 3, in the formula, R 7 C1-C12 10 These are groups, and each may be substituted. In particular, R 7 C may be substituted. 1~8 Linear alkyl group, C 3~8It can represent a branched alkyl group or a phenyl group. In particular, R 7 C may be substituted. 1~6 Linear alkyl group, C 3~6 It can represent a branched alkyl group or a phenyl group. More specifically, R 7 C 1~3 It can represent a linear alkyl group or a C3 branched alkyl group. Optional substituents include i) halogens (especially when the substituent is in an aromatic moiety); ii) C 1~6 iii) one, two, three, or four groups selected from an alkoxy group, an alkyl group, or an alkenyl group; or one, two, three, or four groups selected from a benzyl group, a condensed phenyl group, or a non-condensed phenyl group, wherein the group is one, two, or three halogens, C 1~8 It may be substituted with an alkyl, alkoxy, amino, nitro, ester, sulfonate, halohydrocarbon, or perhalohydrocarbon group.

[0033] According to any particular embodiment of the present invention, ligand P is given by formula P(OR 7 )3 may be a monophosphine, where R 7 This has the same meaning as defined above.

[0034] According to any embodiment of the present invention, ligand P can be selected from the group consisting of triisopropyl phosphite, triphenylphosphine, trioctylphosphine, tricyclohexylphosphine, trimethyl phosphite, triethyl phosphite, and triphenylphosphite.

[0035] According to any embodiment of the present invention, the nickel catalyst is of formula (III) or (III'). In particular, the nickel catalyst is of formula (III).

[0036] To form the compound of formula (I), nickel catalysts can be added to the reaction medium of the method of the present invention at a wide range of concentrations. As a non-limiting example, the concentration of the nickel catalyst can range from 0.1 mol% to 7.5 mol% relative to the total amount of substrate. In particular, the nickel catalyst concentration can range from 3 mol% to 6 mol%. Needless to say, the method will also function with more catalyst. However, as those skilled in the art will recognize, the optimal concentration of the nickel catalyst depends on the properties of the latter, the properties of the substrate, the temperature, and the desired reaction time.

[0037] Nickel catalysts are either commercially available compounds or can be prepared by several methods, such as those reported in Inorganic Chemistry 1964, 3, 1062. Nickel catalysts of formula (III), (III'), (III''), or (III''') are formed in situ by the reaction of a nickel(II) complex with a phosphine or phosphite, which is a P or PP ligand as defined above, in the presence of a base such as an amine. The nickel(II) complex is a hydrate. The nickel(II) complex is NiCl2(H2O) x NiBr2(H2O) x Ni(OAc)2(H2O) x NiSO4(H2O) x , and NiI2(H2O) x You can choose from the group consisting of the following, where x is an integer from 1 to 7.

[0038] According to any embodiment of the present invention, the method of the present invention for forming the compound of formula (I) can be carried out in the absence of additives such as bases or acids.

[0039] According to any one embodiment of the present invention, the method of the present invention for forming the compound of formula (I) is carried out at a temperature within the range of 0°C to 150°C. In particular, the temperature is in the range of 30°C to 70°C. Of course, those skilled in the art can also select a preferred temperature as a function of the melting and boiling points of the starting and final products, as well as the desired time of reaction or conversion.

[0040] The method of the present invention for forming the compound of formula (I) can be carried out in or without a solvent. Where a solvent is required or used for practical reasons, any solvent stream of such reaction type can be used for the purposes of the present invention. A non-limiting example is C 6~12 Examples of solvents include aromatic solvents such as xylene, toluene, 1,3-diisopropylbenzene, cumene, or pseudocumene, or mixtures thereof; hydrocarbon solvents such as cyclohexane, heptane, or mixtures thereof; nitrile solvents such as acetonitrile; ester solvents such as ethyl acetate; or ether solvents such as tetrahydrofuran, diethyl ether, methyltetrahydrofuran, or mixtures thereof. The choice of solvent depends on the properties of the substrate and / or catalyst, and those skilled in the art can adequately select the most suitable solvent in each case to optimize the reaction.

[0041] The method of the present invention for forming the compound of formula (I) is carried out in batch or continuous conditions.

[0042] The present invention's method for forming the compound of formula (I) can be carried out at atmospheric pressure.

[0043] Surprisingly, the present invention's method for forming the compound of formula (I) makes it possible to form the compound of formula (I) having a double bond at the 3-position, primarily in an E configuration.

[0044] Compounds of formula (IV), such as those of formula (II'), are obtained by coupling between an alkyne of formula (V) and a compound of formula (VI). Metal-catalyzed cross-coupling reactions have been widely reported in the prior art, particularly palladium-catalyzed cross-coupling reactions. However, all the conditions reported in the prior art were unable to provide compounds of formula (IV) starting from the alkyne of formula (V) and the compound of formula (VI). Therefore, a novel cross-coupling reaction, not mentioned or suggested in the prior art, was developed using a catalyst less expensive than palladium.

[0045] Therefore, another subject of the present invention is any one form of the stereoisomer of formula (IV) [ka] [In the formula, R 1 is one or more hydroxyl groups, C 1~15 Alkoxy group, C 2~15 Alkenyloxy group, C 3~15 Heterocycloalkyl groups, C 6~10 Aryloxy group, and / or C 1~4 C may be substituted with a carboxylic acid ester group. 1~10 Represents a hydrocarbon group, R 2 , R 3 , and R 4 These are, independently of each other, hydrogen atoms and C 1~3 It represents an alkyl group or a phenyl group, where Y is a hydrogen atom, and C 1~3 Alkyl alkyl group, or CHR 5 It is an X group, R 5 C is a hydrogen atom. 1~3 It is an alkyl group or a phenyl group, and X is OR 6 Base, OC(=O)R 6 Base, OC(=O)OR 6 Base, or OSO2R 6 Represents the base, R 6 is a hydrogen atom or C 1~4 [It is an alkyl group or a phenyl group.] A method for preparing the compound, In the presence of a nickel catalyst, the following formula is obtained for one of the stereoisomers: [ka] [In the formula, R 1 [This has the same meaning as defined in equation (IV)] The compound is expressed in one of the following stereoisomer forms: [ka] [where X, Y, R 2 , R 3 , R 4 , and R 5 These terms, independently of each other, have the same meaning as those defined in equation (IV). This method involves reacting it with the compound.

[0046] Surprisingly, the present invention's method for forming the compound of formula (IV) yields either one form of the stereoisomer of formula (IV'). [ka] [In the formula, R 1 , Y, R 2 , R 3 , R 4 , and R 5 This has the same meaning as defined above. The compound of formula (IV) can be formed while suppressing the formation of branched compounds. In particular, up to 50%, further up to 40%, further up to 30%, further up to 25%, further up to 20% of the compound of formula (IV'), and further up to 15% of the compound of formula (IV') can be formed.

[0047] According to any embodiment of the present invention, Y is a hydrogen atom or CHR 5 It may be an X group, R 5 C is a hydrogen atom. 1~3 It is an alkyl group or a phenyl group, and X is OR 6 Base, OC(=O)R 6 Base, OC(=O)OR 6Base, or OSO2R 6 Represents the base, R 6 is a hydrogen atom or C 1~4 It is an alkyl group or a phenyl group. In particular, Y is CHR 5 It may be an X group, R 5 C is a hydrogen atom. 1~3 It is an alkyl group or a phenyl group, and X is OR 6 Base, OC(=O)R 6 Base, OC(=O)OR 6 Base, or OSO2R 6 Represents the base, R 6 is a hydrogen atom or C 1~4 It is an alkyl group or a phenyl group.

[0048] According to any embodiment of the present invention, the compound of formula (IV) is a stereoisomer of any one form of formula (II') [ka] [In the formula, R 1 is one or more hydroxyl groups, C 1~15 Alkoxy group, C 2~15 Alkenyloxy group, C 3~15 Heterocycloalkyl groups, C 6~10 Aryloxy group, and / or C 1~4 C may be substituted with a carboxylic acid ester group. 1~10 Represents a hydrocarbon group, R 2 , R 3 , R 4 , and R 5 These are, independently of each other, hydrogen atoms and C 1~3 X represents an alkyl group or a phenyl group, and X is OR 6 Base, OC(=O)R 6 Base, OC(=O)OR 6 Base, or OSO2R 6 Represents the base, R 6 is a hydrogen atom or C 1~4 [It is an alkyl group or a phenyl group.] It belongs to them.

[0049] According to any embodiment of the present invention, the compound of formula (VI) is a stereoisomer of any one form of formula (VII) [ka] [In the formula, R 2 , R 3 , R 4 , R 5 , and each X independently has the same meaning as defined in equation (II'). It belongs to them.

[0050] According to any embodiment of the present invention, the nickel catalyst is of formula (III), (III'), (III''), or (III'''), and has the same meaning as defined above, i.e., as defined in the method of the present invention for producing the compound of formula (I). In particular, the nickel catalyst may be of formula (III) or (III''), in which the P ligand may be a monophosphine monodentate ligand.

[0051] The nickel catalysts used in both processes may be different or similar. In particular, the nickel catalyst used in both processes is Ni(P(Oi-Pr)3)4. Both processes can be carried out in a single pot.

[0052] To form the compound of formula (IV), nickel catalysts can be added to the reaction medium of the method of the present invention at a wide range of concentrations. As a non-limiting example, the concentration of the nickel catalyst can range from 0.1 mol% to 7.5 mol% relative to the total amount of substrate. In particular, the nickel catalyst concentration can range from 3 mol% to 6 mol%. Needless to say, the method will also function with more catalyst. However, as those skilled in the art will recognize, the optimal concentration of the nickel catalyst depends on the properties of the latter, the properties of the substrate, the temperature, and the desired reaction time.

[0053] Non-limiting examples of suitable compounds for formula (V) include 1-propyne, 1-butyne, 1-heptine, 1-pentine, 1-hexine, 1-octin, 1-nonine, 1-decine, phenylacetylene, ethyl 4-pentinoate, (E)-3-methylpento-2-en-4-in-1-ol, 2-methyl-3-butyne-2-ol, 7-methyl-3-methyleneocto-6-en-1-yne, 1-ethynyl-3,3-dimethylcyclohexane-1-ol, 1-ethynyl-5,5-dimethylcyclohex-1-ene, 1-ethynyl-3,3-dimethylcyclohex-1-ene, and 3-butyne-1-ol.

[0054] Non-limiting examples of suitable compounds for formula (VI) include buto-2-ene-1,4-diyldiacetate, buto-2-ene-1,4-diyldipropionate, buto-2-ene-1,4-diyldibenzoate, buto-2-ene-1,4-diyldipivalate, allyl acetate, 3-buten-2-yl acetate, clotyl acetate, prenyl acetate, and cinnamyl acetate.

[0055] Non-limiting examples of suitable compounds for formula (IV) include undec-2-en-5-in-1-yl acetate, (E)-undec-2-en-5-in-1-yl acetate, (E)-6-phenylhex-2-en-5-in-1-yl acetate, ethyl(E)-9-acetoxynon-7-en-4-inoate, (2E,7E)-9-hydroxy-7-methylnona-2,7-diene-5-in-1-yl acetate, (E)-8-hydroxyocto-2-en-5-in-1-yl acetate, dec-1-en-4-in, (E)-7-hydroxy-7-methyl Examples include thioocto-2-en-5-in-1-yl acetate, (E)-undec-2-en-5-in, 10-methyl-6-methyleneundec-1,9-dien-4-in, 3,3-dimethyl-1-(pento-4-en-1-in-1-yl)cyclohexane-1-ol, 5,5-dimethyl-1-(pento-4-en-1-in-1-yl)cyclohex-1-en, 3,3-dimethyl-1-(pento-4-en-1-in-1-yl)cyclohex-1-en, dec-1-en-4-in, and ethylocto-7-en-4-inoate.

[0056] According to any embodiment of the present invention, the method of the present invention for forming the compound of formula (IV) can be carried out in the absence of additives such as a base or acid.

[0057] According to any one embodiment of the present invention, the method of the present invention for forming the compound of formula (IV) is carried out at a temperature within the range of 0°C to 150°C. In particular, the temperature is in the range of 15°C to 30°C. Of course, those skilled in the art may also select a preferred temperature as a function of the melting and boiling points of the starting and final products, as well as the desired time of reaction or conversion.

[0058] The method of the present invention for forming the compound of formula (IV) can be carried out in or without a solvent. Where a solvent is required or used for practical reasons, any solvent stream of such reaction type can be used for the purposes of the present invention. A non-limiting example is C 6~12Examples of solvents include aromatic solvents such as xylene, toluene, 1,3-diisopropylbenzene, cumene, or pseudocumene, or mixtures thereof; hydrocarbon solvents such as cyclohexane, heptane, or mixtures thereof; nitrile solvents such as acetonitrile; and ester solvents such as isopropyl acetate. The choice of solvent depends on the properties of the substrate and / or catalyst, and those skilled in the art can adequately select the most suitable solvent in each case to optimize the reaction.

[0059] The present invention's method for forming the compound of formula (IV) is carried out in batch or continuous conditions.

[0060] The present invention's method for forming the compound of formula (IV) can be carried out at atmospheric pressure.

[0061] The compound of formula (II) is a novel compound and exhibits many advantages, as described above and as shown in the examples.

[0062] Therefore, another subject of the present invention is the following formula for any one form of the stereoisomer [ka] [In the formula, the dotted line represents a carbon-carbon double bond or a carbon-carbon triple bond, R 1 is one or more hydroxyl groups, C 1~15 Alkoxy group, C 2~15 Alkenyloxy group, C 3~15 Heterocycloalkyl groups, C 6~10 Aryloxy group, and / or C 1~4 Linear or branched carbon atoms may be substituted with carboxylic acid ester groups. 1~10 Represents alkyl, R 2 , R 3 , R 4 , and R 5 These are, independently of each other, hydrogen atoms and C 1~3 X represents an alkyl group or a phenyl group, and X is OR 6 Base, OC(=O)R 6 Base, OC(=O)OR6 Base, or OSO2R 6 Represents the base, R 6 is a hydrogen atom or C 1~4 [It is an alkyl group or a phenyl group.] It is a compound of [the compound].

[0063] According to a particular embodiment, the compound of formula (II) is a stereoisomer of any one form of the following formula [ka] [In the formula, R 1 is one or more hydroxyl groups, C 1~15 Alkoxy group, C 2~15 Alkenyloxy group, C 3~15 Heterocycloalkyl groups, C 6~10 Aryloxy group, and / or C 1~4 Linear or branched carbon atoms may be substituted with carboxylic acid ester groups. 1~10 R represents an alkyl group. 2 , R 3 , R 4 , and R 5 These are, independently of each other, hydrogen atoms and C 1~3 X represents an alkyl group or a phenyl group, and X is OR 6 Base, OC(=O)R 6 Base, OC(=O)OR 6 Base, or OSO2R 6 Represents the base, R 6 is a hydrogen atom or C 1~4 [It is an alkyl group or a phenyl group.] It belongs to them.

[0064] A typical method for carrying out the present invention is reported in the following examples. [Examples]

[0065] The present invention will be described in more detail below by the following examples. Abbreviations have their usual meanings in the art, and temperatures are expressed in degrees Celsius (°C). The pre-catalyst and ligand solutions were prepared in an inert atmosphere (argon) using standard Schlenk techniques. The solvents were dried by conventional procedures and distilled in an argon atmosphere. NMR spectra were recorded at 20°C using a Bruker AV300, AV400, or AV 500 MHz spectrometer. Chemical shifts were measured against the solvent signal (chloroform, δ). H =7.26 ppm, δ C It is reported in ppm relative to (=77.0 ppm). 1 H, 1 H-COSY, -NOESY, 13 C, 1 Signal assignment was confirmed by recording H-HSQC and -HMBC experiments. Gas chromatography was performed on an Agilent 7890A series with an HP5 column (30 m × 0.25 mm ID, film thickness 0.25 μm), using tetradecane as the internal standard.

[0066] [Example 1] Preparation of (E)-Undec-2-en-5-in-1-ylacetate 27 g (0.25 equivalents) of triethylamine was added to a stirred suspension containing 13 g (0.05 equivalents) of nickel dichloride hexahydrate and 28.5 g (0.125 equivalents) of triisopropyl phosphite in 150 ml of isopropyl acetate. 188 g (1 equivalent) of 1,4-diacetoxy(Z)-buto-2ene, followed by 105 g (1 equivalent) of 1-heptine, was added, and the mixture was stirred overnight at 20°C. The reaction was then treated with aqueous Na2EDTA, followed by dilute potassium carbonate. The resulting product was concentrated under vacuum, and 230 g was flash-distilled, followed by fractionation in a packed 3 m Sulzer laboratory distillation apparatus. The first fraction (50°C / 5mbar) consisting of unreacted 1-heptin (24g, 22.8%) was recovered, followed by the second fraction (55-85°C / 3mbar) consisting of a mixture of unreacted 1,4-diacetoxybut-2-ene and 2-vinylnon-3-in-1-yl acetate (81g), and the third fraction (102-110°C / 3mbar) consisting of (E)-undec-2-ene-5-in-1-yl acetate (109g, purity 98%, yield 48%).

[0067] (E)-Undek-2-en-5-in-1-ilacetate: [ka]

[0068] [Example 2] Preparation of (3E / Z)-1,3-undecadien-5-yne A suspension of 5.7 g of nickel dichloride hexahydrate in 200 g of acetonitrile was stirred at 25°C in the presence of 15 g of triisopropyl phosphite. After stirring for 1 hour, 36 g of triethylamine was added, followed by 100 g of (E)-undec-2-ene-5-yin-1-yl acetate. The mixture was then heated to 50°C for 5 hours. After the reaction was complete, the mixture was cooled to 35°C, transferred to 200 g of cyclohexane, and washed twice with aqueous Na2EDTA solution. Finally, the mixture was neutralized with dilute potassium bicarbonate and evaporated to dryness. The resulting oil (90 g) was flash-distilled (50°C / 1 mbar) to obtain 58 g of 1,3-undecadien-5-yin (E / Z ratio 73:27) with a purity of 97% and a yield of 79%.

[0069] (3E)-1,3-Undecadien-5-ine: [ka]

[0070] [Example 3] Preparation of (2E,5Z)-undeca-2,5-diene-1-yl (E)-Undec-2-ene-5-in-1-yl acetate, Lindler catalyst (0.11 wt%, 0.011 mol% Pd), and 3,6-dithia-1,8-octanediol (Lindler catalyst poison, CAS number: 5244-34-8) (0.0014 wt%, 0.0016 mol%, i.e., approximately 15 mol% relative to Pd) were placed together in a 100 mL or 1 L autoclave equipped with a mechanical sitting device, pressure and internal temperature sensors, and a heating / cooling system for internal temperature control. The mixture was then purged with nitrogen (three times at 5 bar) while the sealed autoclave was stirred, and then stirred at 25°C for 30 minutes under a nitrogen pressure of 1 bar. After this period, the autoclave was purged with hydrogen while stirring (three times at 1 bar), and then pressurized to a hydrogen pressure of 1 bar using a hydrogen tank equipped with an outlet pressure regulator and an internal pressure sensor to track and determine hydrogen consumption. The reaction mixture was then stirred at 50°C (1000 rpm) under a hydrogen pressure of 3 bar, maintaining the pressure at this value throughout the reaction. After the completion of alkyne hydrogenation (2-3 hours), which was also determined by GC analysis on a short polar column (DB-Wax 10m × 0.1mm × 0.1mm), the autoclave was cooled to room temperature, stirring was stopped, the autoclave was depressurized, and purged with nitrogen (three times at 5 bar). The reaction mixture was passed through multiple filters to remove the Lindler catalyst. The target (2E,5Z)-undeca-2,5-diene-1-yl acetate was obtained without further purification, with a complete conversion rate, a 99 / 1(2E,5Z) / (2E,5E) ratio, GC chemoselectivity exceeding 99.5%, and no residue formation (determined by valve-to-valve distillation of the sample). (2E,5Z)-Undeca-2,5-Diene-1-Ilacetate: [ka]

[0071] [Example 4] Preparation of (3E,5Z)-1,3,5-undecatriene A suspension of 5.7 g of nickel dichloride hexahydrate was stirred in 200 g of acetonitrile at 25°C in the presence of 15 g of triisopropyl phosphite. After stirring for 1 hour, 36 g of triethylamine was added, followed by 100 g of (2E,5Z)-undeca-2,5-diene-1-ylacetate (Ib). The mixture was then heated to 50°C for 5 hours. After the reaction was complete, the mixture was cooled to 35°C, transferred to 200 g of cyclohexane, and washed twice with aqueous Na2EDTA solution. Finally, the mixture was neutralized with dilute potassium bicarbonate and evaporated to dryness. The resulting oil (92 g) was flash-distilled (50°C / 1 mbar) to obtain 63 g of (3E,5Z)-1,3,5-undecatriene (3E / 3Z ratio 98:2) with a purity of 95% and a yield of 85%.

[0072] (3E,5Z)-1,3,5-Undecatriene: [ka]

[0073] [Example 5] Preparation of (E)-6-phenylhex-2-ene-5-in-1-yl acetate 0.66 g (0.25 equivalents) of triethylamine was added to a stirred suspension containing 0.31 g (0.05 equivalents) of nickel dichloride hexahydrate and 0.68 g (0.125 equivalents) of triisopropyl phosphite in 3.6 ml of isopropyl acetate. 4.48 g (1 equivalent) of 1,4-diacetoxy(Z)-buto-2ene, followed by 2.66 g (1 equivalent) of phenylacetylene, was added, and the mixture was stirred overnight at 20°C. The reaction was then treated with an aqueous solution of Na2EDTA, followed by dilute potassium carbonate. To isolate the pure product, the reaction mixture containing 31% GC unreacted phenylacetylene, 46% GC (E)-6-phenylhex-2-en-5-in-1-yl acetate, and 15% GC 2-(phenylethynyl)but-3-en-1-yl acetate (linear / branched ratio 75 / 25) was purified by chromatography on silica gel (30 / 50 petroleum ether / Et2O 10 / 0~9 / 1).

[0074] (E)-6-phenylhex-2-en-5-in-1-yl acetate (main product): [ka]

[0075] 2-(phenylethynyl)buto-3-en-1-yl acetate (trace product): [ka]

[0076] [Example 6] Preparation of ethyl(E)-9-acetoxynone-7-ene-4-inoate 0.66 g (0.25 equivalents) of triethylamine was added to a stirred suspension containing 0.31 g (0.05 equivalents) of nickel dichloride hexahydrate and 0.68 g (0.125 equivalents) of triisopropyl phosphite in 3.6 ml of isopropyl acetate. 4.48 g (1 equivalent) of 1,4-diacetoxy(Z)-buto-2ene, followed by 3.28 g (1 equivalent) of ethyl 4-pentinate, was added, and the mixture was stirred overnight at 20°C. The reaction was then treated with an aqueous solution of Na2EDTA, followed by dilute potassium carbonate. To isolate the pure product, the reaction mixture containing 30% GC unreacted ethyl 4-pentinate, 45% GC ethyl 9-acetoxynone-7-en-4-inoate, and 17% GC ethyl 6-(acetoxymethyl)octo-7-en-4-inoate (linear / branched ratio 72 / 28) was purified by chromatography on silica gel (30 / 50 petroleum ether / Et2O 10 / 0~8 / 2).

[0077] Ethyl 9-acetoxyn-7-ene-4-inoate (main product): [ka] (Note: Because some of the signals from the quaternary carbons of the alkyne moiety are hidden by CDCl3, the signal is in CD2Cl2 instead of CDCl3.)13 (A 13C NMR spectrum was obtained.)

[0078] Ethyl 6-(acetoxymethyl)octo-7-ene-4-inoate (trace product): [ka]

[0079] [Example 7] Preparation of (2E,7E)-9-hydroxy-7-methylnonano-2,7-diene-5-in-1-yl acetate 0.66 g (0.25 equivalents) of triethylamine was added to a stirred suspension containing 0.32 g (0.05 equivalents) of nickel diacetate tetrahydrate and 0.68 g (0.125 equivalents) of triisopropyl phosphite in 3.6 ml of isopropyl acetate. 4.48 g (1 equivalent) of 1,4-diacetoxy(Z)-buto-2ene, followed by 2.50 g (1 equivalent) of (E)-3-methylpento-2-en-4-in-1-ol, was added, and the mixture was stirred at 20°C for 4 hours. The reaction was then treated with an aqueous solution of Na2EDTA, followed by dilute potassium carbonate. To isolate the pure product, the reaction mixture containing 17% GC unreacted (E)-3-methylpento-2-en-4-in-1-ol, 54% GC (2E,7E)-9-hydroxy-7-methylnonano-2,7-diene-5-in-1-yl acetate, and 21% GC (E)-7-hydroxy-5-methyl-2-vinylhept-5-en-3-in-1-yl acetate (linear / branched ratio 72 / 28) was purified by chromatography on silica gel (30 / 50 petroleum ether / Et2O 10 / 0~6 / 4).

[0080] (2E,7E)-9-hydroxy-7-methylnonano-2,7-diene-5-in-1-ylacetate (main product): [ka]

[0081] (E)-7-hydroxy-5-methyl-2-vinylhept-5-ene-3-in-1-ylacetate (trace product): [ka]

[0082] [Example 8] Preparation of (E)-8-hydroxyocto-2-ene-5-in-1-yl acetate 0.66 g (0.25 equivalents) of triethylamine was added to a stirred suspension containing 0.32 g (0.05 equivalents) of nickel diacetate tetrahydrate and 0.68 g (0.125 equivalents) of triisopropyl phosphite in 3.6 ml of isopropyl acetate. 4.48 g (1 equivalent) of 1,4-diacetoxy(Z)-buto-2ene, followed by 1.82 g (1 equivalent) of 3-buty-1-ol, was added, and the mixture was stirred at 20°C for 24 hours. The reaction was then treated with an aqueous solution of Na2EDTA, followed by dilute potassium carbonate. From both GC-MS and NMR analysis, the crude mixture was determined to contain 51% GC of unreacted 3-buty-1-ol, 32% GC of (E)-8-hydroxyocto-2-en-5-in-1-yl acetate, and 11% GC of 6-hydroxy-2-vinylhex-3-in-1-yl acetate (linear / branched ratio 75 / 25).

[0083] [Example 9] Preparation of (E)-Undec-2-en-5-in-1-ylbenzoate 0.66 g (0.25 equivalents) of triethylamine was added to a stirred suspension containing 0.31 g (0.05 equivalents) of nickel dichloride hexahydrate and 0.68 g (0.125 equivalents) of triisopropyl phosphite in 3.6 ml of isopropyl acetate. 7.70 g (1 equivalent) of (Z)-buto-2-ene-1,4-diyldibenzoate, followed by 2.5 g (1 equivalent) of heptine, was added, and the mixture was stirred at 20°C for 20 hours. The reaction was then treated with an aqueous solution of Na2EDTA, followed by dilute potassium carbonate. From both GC-MS and NMR analysis, the crude mixture was determined to contain 51% GC unreacted heptin, 26% GC (E)-undec-2-en-5-in-1-ylbenzoate, and 10% GC 2-vinylnon-3-in-1-ylbenzoate (linear / branched ratio 72 / 28).

[0084] [Example 10] Preparation of Dec-1-en-4-in 0.66 g (0.25 equivalents) of triethylamine was added to a stirred suspension containing 0.32 g (0.05 equivalents) of nickel diacetate tetrahydrate and 0.68 g (0.125 equivalents) of triisopropyl phosphite in 3.6 ml of isopropyl acetate. 2.60 g (1 equivalent) of allyl acetate, followed by 2.5 g (1 equivalent) of heptine, was added, and the mixture was stirred at 20°C for 18 hours. The reaction was then treated with an aqueous solution of Na2EDTA, followed by dilute potassium carbonate. Both GC-MS and NMR analysis determined that the crude mixture contained 10% GC of unreacted heptine and 78% GC of dec-1-en-4-yne.

[0085] [Example 11] Preparation of (E)-Undec-2-ene-5-ine 0.66 g (0.25 equivalents) of triethylamine was added to a stirred suspension containing 0.32 g (0.05 equivalents) of nickel diacetate tetrahydrate and 0.68 g (0.125 equivalents) of triisopropyl phosphite in 3.6 ml of isopropyl acetate. 2.97 g (1 equivalent) of 3-buten-2-yl acetate, followed by 2.5 g (1 equivalent) of heptin, was added, and the mixture was stirred at 20°C for 18 hours. The reaction was then treated with an aqueous solution of Na2EDTA, followed by dilute potassium carbonate. From both GC-MS and NMR analysis, the crude mixture was determined to contain 10% GC of unreacted heptin, 40 GC of (E)-undec-2-en-5-yne, and 40 GC of 3-methyldec-1-en-4-yne (linear / branched ratio 50 / 50).

[0086] [Example 12] Preparation of ethyl(E)-9-acetoxynone-7-ene-4-inoate 0.66 g (0.25 equivalents) of triethylamine was added to a stirred suspension containing 0.32 g (0.05 equivalents) of nickel diacetate tetrahydrate and 0.68 g (0.125 equivalents) of triisopropyl phosphite in 3.6 ml of isopropyl acetate. 2.60 g (1 equivalent) of allyl acetate, followed by 3.28 g (1 equivalent) of ethyl 4-pentinate, was added, and the mixture was stirred at 20°C for 8 hours. The reaction was then treated with aqueous Na2EDTA, followed by dilute potassium carbonate. From both GC-MS and NMR analysis, the crude mixture was determined to contain 13% GC of unreacted ethyl 4-pentinate and 80 GC of ethyl octo-7-ene-4-inoate.

Claims

1. Formula (I) of one of the stereoisomers or a mixture thereof 【Chemistry 1】 [In the formula, the dotted line represents a carbon-carbon double bond or a carbon-carbon triple bond, R １ R represents a linear C1-10 alkyl group, a linear C2-10 alkenyl group, a branched C3-10 alkyl group or branched C3-10 alkenyl group, or a C6-10 aryl group, which may contain one hydroxyl group or a C1-4 carboxylic acid ester group. ２ , R ３ , R ４ , and R ５ These are, independently of each other, hydrogen atoms and C １～３ [Represents an alkyl group or a phenyl group] A method for preparing a compound of which is a stereoisomer of any one form of formula (II) 【Chemistry 2】 [wherein, the dotted line, R １ , R ２ , R ３ , R ４ , and R ５ have the same meanings as those defined in formula (I), X represents an OC(=O)R6 group, and R ６ is a hydrogen atom or a C １～４ alkyl group or a phenyl group]] A method comprising reacting a compound with a nickel catalyst.

2. R １ However, one hydroxyl group or C １～４ A linear C that may contain a carboxylic acid ester group. １～１０ Alkyl or branched C ３～１０ The method according to claim 1, which represents an alkyl group.

3. R １ However, linear C ４～８ The method according to claim 1 or 2, wherein the alkyl group, preferably a pentyl group, is represented.

4. R ６ C １～３ The method according to any one of claims 1 to 3, wherein the alkyl group is used.

5. The method according to any one of claims 1 to 4, wherein X represents an acetate group.

6. R ２ , R ３ , R ４ , and R ５ The method according to any one of claims 1 to 5, wherein is a hydrogen atom.

7. The nickel catalyst is defined as follows: [Ni(P)] ４ ] (III) or [Ni(PP)] ２ ] (III') or [Ni(P)] ２ ML] (III'') or [Ni(PP)ML] (III''') [In the formula, each P is a C atom with one phosphorus atom as a coordinating group, independently of each other.] ３ ~C ３０ This represents a monodentate ligand, where each PP is independently of the other, and the coordinating group is a C atom with two phosphorus atoms. ５ ~C ５０ This represents a bidentate ligand, where M and L are independently anionic or neutral ligands, provided that when M is a neutral ligand, L is a neutral ligand, and when M is an anionic ligand, L is an anionic ligand. The method according to any one of claims 1 to 6.

8. P is given by equation P(OR ７ ) ３ [In the formula, R ７ C １～６ Linear alkyl group, C ３～６ The method according to claim 7, wherein the monophosphite is a branched alkyl group or a phenyl group.

9. The method according to claim 7 or 8, wherein the nickel catalyst of formula (III), (III'), (III''), or (III''') is formed in situ by the reaction of a nickel(II) complex with a phosphite or phosphine in the presence of a base such as an amine.

10. The compound of formula (I) is in the form of one of its stereoisomers or a mixture thereof, as shown below. 【Transformation 3】 [In the formula, R １ , R ２ , R ３ , R ４ , and R ５ [This has the same meaning as defined in claim 1] It is a compound of, The compound of formula (II) is a stereoisomer of any one form of the following formula 【Chemistry 4】 [In the formula, R １ , R ２ , R ３ , R ４ , R ５ , and X has the same meaning as defined in claim 1. The method according to any one of claims 1 to 9, wherein the compound is [the compound].

11. The compound of formula (I) is in the form of one of its stereoisomers or a mixture thereof, as shown below. 【Transformation 5】 [In the formula, R １ , R ２ , R ３ , R ４ , and R ５ [This has the same meaning as defined in claim 1] It is a compound of, The compound of formula (II) is a stereoisomer of any one form of the following formula 【Transformation 6】 [In the formula, R １ , R ２ , R ３ , R ４ , R ５ , and X has the same meaning as defined in claim 1. The method according to any one of claims 1 to 9, wherein the compound is [the compound].

12. The method according to claim 11, wherein the compound of formula (II'') is obtained by reduction of the compound of formula (II').

13. Formula (IV) for one of the stereoisomers 【Transformation 7】 [In the formula, R １ R represents a linear C1-10 alkyl group, a linear C2-10 alkenyl group, a branched C3-10 alkyl group or branched C3-10 alkenyl group, or a C6-10 aryl group, which may contain one hydroxyl group or a C1-4 carboxylic acid ester group. ２ , R ３ , and R ４ These are, independently of each other, hydrogen atoms and C １～３ It represents an alkyl group or a phenyl group, where Y is a hydrogen atom, and C １～３ alkyl group, or CHR ５ It is an X group, R ５ C is a hydrogen atom. １～３ It is an alkyl group or a phenyl group, where X represents an OC(=O)R 6 group, and R ６ is a hydrogen atom or C １～４ [It is an alkyl group or a phenyl group.] A method for preparing the compound, In the presence of a nickel catalyst, the following formula is obtained for one of the stereoisomers. 【Transformation 8】 [In the formula, R １ [This has the same meaning as defined in formula (IV)] The compound is expressed in one of the following stereoisomer forms: 【Chemistry 9】 [In the formula, X, Y, R ２ , R ３ , and R ４ These terms, independently of each other, have the same meaning as those defined in formula (IV). A method involving reacting with a compound.

14. The method according to claim 13, wherein the nickel catalyst is one defined in claims 7 to 9.

15. The following formula for one of the stereoisomers 【Chemistry 10】 [In the formula, the dotted line represents a carbon-carbon double bond or a carbon-carbon triple bond, R １ This may contain one hydroxyl group or a C1-4 carboxylic acid ester group, and may be linear or branched C1. １～１０ Represents an alkyl group, R ２ , R ３ , R ４ , and R ５ These are, independently of each other, hydrogen atoms and C １～３ X represents an alkyl group or a phenyl group, and R represents an OC(=O)R 6 group. ６ is a hydrogen atom or C １～４ [It is an alkyl group or a phenyl group.] A compound of [this].

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