Selective semi-hydrogenation of Allene

Abstract

The present invention relates to the field of catalytic hydrogenation, and more particularly to the hemihydrogenation of allenes to corresponding alkenes in the presence of a homogeneous catalyst system, wherein the homogeneous catalyst system comprises a cobalt salt, a bidentate diphosphine ligand, and a weakly coordinating or non-coordinating monoanion or reducing agent.

Description

[Technical Field]

[0001] The present invention relates to the field of catalytic hydrogenation, and more particularly to the hemihydrogenation of allenes to corresponding alkenes in the presence of a homogeneous catalyst system, the homogeneous catalyst system comprising a cobalt salt, a bidentate diphosphine ligand, and a weakly coordinating or non-coordinating monoanion or reducing agent.

[0002] background Compounds containing alkenes, particularly ω-1 alkenes, possess highly desirable skeletons that can be used as is or as important intermediates, particularly useful for preparing more complex compounds in different fields such as cosmetics, pharmaceuticals, or agricultural chemistry. The alkene group can be obtained by reduction of the corresponding triple bond or by methods suitable for promoting the formation of a double bond via cis stereochemistry. However, access to the corresponding triple bond can be cumbersome. An alternative approach is the hepihydrogenation of allenes. Despite the fact that allenes are readily available, their hepihydrogenation, especially the hepihydrogenation of terminal allenes to ω-1 alkenes, is rarely disclosed in the literature and suffers from moderate to low stereoselectivity and regioselectivity.

[0003] Therefore, there is a need today to develop novel methods that achieve high regioselectivity while controlling stereoselectivity, and to reach the alkene group by semi-hydrogenation of allenes.

[0004] The present invention enables the semi-hydrogenation of allenes to corresponding alkenes using molecule H2, and the process is carried out in the presence of a homogeneous catalytic system comprising a cobalt salt, a bidentate diphosphine ligand, and a weakly coordinating or non-coordinating monoanion or reducing agent. The conditions of the present invention enable the promotion of cis formation while achieving high regioselectivity. To the best of the inventors' knowledge, the process of the present invention has not been reported in the prior art.

[0005] Description of the Invention Surprisingly, it was discovered here that a homogeneous catalyst system comprising a cobalt salt, a bidentate diphosphine ligand, and a weakly coordinating or non-coordinating monoanion or reducing agent enables the hydrogenation of allenes with high regioselectivity and stereoselectivity.

[0006] Therefore, a first object of the present invention is a process for the partial hydrogenation of an allene to a corresponding alkene using molecule H2, the process being carried out in the presence of a homogeneous catalytic system comprising a cobalt salt, a bidentate diphosphine ligand, and a weakly coordinating or non-coordinating monoanion or reducing agent.

[0007] Terms such as "bidentate diphosphine ligand" are understood as ligands that coordinate cobalt metal with two phosphorus atoms.

[0008] For clarity, terms such as “alkene” are used in the ordinary sense as understood by those skilled in the art, namely, that the compound obtained by hemihydrogenation contains a double bond which may have a cis configuration corresponding to the Z isomer, a trans configuration corresponding to the E isomer, or a mixture thereof. In fact, an alkene may be in the form of its E or Z isomer or a mixture thereof. In other words, an alkene may be in the form of its E or Z isomer or a mixture thereof, and for example, the process of the present invention yields a composition of a substance consisting of one or more alkenes having the same chemical structure but different double bond configurations. In particular, the alkene may be in the form of a mixture of isomers E and Z, where isomer Z may constitute at least 50%, or even at least 75%, of the total mixture (i.e., a mixture Z / E between 75 / 25 and 100 / 0).

[0009] According to any embodiment of the present invention, the homogeneous catalyst system comprises cobalt in oxidation state 0, +I, or +II.

[0010] According to a particular embodiment of the present invention, the homogeneous catalyst system is defined by the formula [Co(PP)(L) q ](Y) x (I) (wherein PP is a bidentate diphosphine ligand; x is 0 or 1; L is a C4-C group containing two or three carbon-carbon double bonds, which may include one or more of oxygen and / or halogen atoms and / or silicon.) 20 In hydrocarbon ligands, q is 1; or L is C2~C 15 It is a Co(0) or Co(I) complex of an alkene ligand where q is 3; Y is a weakly coordinating or non-coordinating monoanion.

[0011] The term "depending on the circumstances" is understood to mean that certain groups that are substituted or may be included may or may not be substituted with certain functional groups, or may or may not include certain atoms. The term "one or more" is understood to mean that the group is substituted with one to seven, preferably one to five, preferably one to three, and more preferably one to two of the particular functional groups.

[0012] "...hydrocarbon ligand..." means that the group consists of hydrogen and carbon atoms 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 an aromatic hydrocarbon, i.e., an aryl group, or a mixture of such groups. 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 to be in the form of two or more topologies (e.g., linear, cyclic, or branched) and / or saturated or unsaturated (e.g., alkyl, aromatic, or alkenyl), it also means a group that may include a moiety having any one of the topologies, or a moiety that is saturated or unsaturated, as described above. Similarly, in all embodiments of the present invention, when it is mentioned that a group is in one type of saturated or unsaturated (e.g., alkyl) form, it means that the group may be of any type of topology (e.g., linear, cyclic, or branched) or may have several parts having various topologies.

[0013] The term "hydrocarbon group, optionally containing..." is understood to mean that the hydrocarbon group optionally contains one, two, or three oxygen atoms in the form of an alcohol, ketone, aldehyde, ether, ester, carboxylic acid, or carbonate group and / or one or two nitrogen atoms in the form of an amine or amide group and / or one sulfur atom in the form of a thiol group. These groups may substitute for hydrogen atoms of the hydrocarbon group and thus laterally bonded to the hydrocarbon, or may substitute for carbon atoms of the hydrocarbon group (where chemically possible) and thus insert into the hydrocarbon chain. For example, the -CH2-CH2-CHOH-CH2- group represents a C4 hydrocarbon group containing an alcohol group (substitution of a hydrogen atom), i.e., a C4 hydrocarbon containing an oxygen atom; the -CH2-CH2-COO-CH2-CH2CH2-CH2- group represents a C7 hydrocarbon group containing one ester group (substitution of a carbon atom / insertion into a hydrocarbon chain), i.e., a C7 hydrocarbon containing two oxygen atoms; and similarly, the -CH2-CH2-O-CH2-CH2-O-CH2-CH2- group represents a C6 hydrocarbon group containing two ether groups, i.e., a C6 hydrocarbon containing two oxygen atoms.

[0014] It is understood that ligand L is a neutral ligand and not an anionic ligand such as an allyl ligand.

[0015] "C3~C 15 The term "alkene ligand" is understood as a ligand containing one double bond, which coordinates to the cobalt metal. The alkene can be linear, cyclic, or branched.

[0016] According to any embodiment of the present invention, x is 1.

[0017] According to any embodiment of the present invention, q is either 1 or q is 3. When q is 3, L is C2~C 12 Alkene ligands, especially C2-C 10The alkene ligand can be a C2-C8 alkene ligand, more particularly a C2-C6 alkene ligand. Examples of suitable alkene ligands include, but are not limited to, ethylene, cyclooctene, cyclohexene, prop-1-ene, but-1-ene, but-2-ene, cycloheptene, cyclopentene, cyclododecene, tetramethylethylene, substituted stilbene (ArCH=CHAr). Preferably, q is 1 and L is a straight-chain or branched C4-C hydrocarbon containing two or three carbon-carbon double bonds 15 a hydrocarbon compound, or a cyclic C6-C hydrocarbon containing two or three carbon-carbon double bonds 20 a hydrocarbon group, or a C 1~6 an alkyl group, a C 1~6 an arene optionally substituted with one or more of an alkoxyl group, a hydroxy group or a halogen atom. Preferably, L is a cyclic C6-C hydrocarbon containing two or three carbon-carbon double bonds, whether conjugated or not 15 a hydrocarbon group, or a C 1~4 an alkyl group, a C 1~4 an arene optionally substituted with one or more of an alkoxyl group, a hydroxy group or a halogen atom. Preferably, L is a cyclic C6-C hydrocarbon containing two or three carbon-carbon double bonds 10 a hydrocarbon group, or a C 1~3 an alkyl group, a C 1~3 an arene optionally substituted with one or more of an alkoxyl group, a hydroxy group or a halogen atom. Even more preferably, L is a cyclic C6-C 10 an alkadiene group, or a C 1~3 an alkyl group, a C 1~3 an arene optionally substituted with one or more of an alkoxyl group, a hydroxy group or a halogen atom. Examples of suitable L include, but are not limited to, 1,5-cyclooctadiene (COD), 1,3-cyclooctadiene, norbornadiene, 2,4-dimethyl-1,3-pentadiene, cyclohepta-1,4-diene, cycloheptatriene, cyclooctatriene, 1,1-dimethyl-2,3-dimethylenecyclohexane, dimethyldivinylsilane, or (η6 -C6H6), (η 6 -C6H5CH3), (η 6 -C6H5OCH3), (η 6 -C6H4(CH3)2), (η 6 -C6H5CF3), (η 6 -C6H5F), (η 6 -C6H4F2) and (η 6 - Selected from the group consisting of C6H4(CF3)2) 6 Ligands are one example.

[0018] According to any embodiment of the present invention, the weakly coordinating or non-coordinating monoanion Y is sterically hindrance. In particular, the weakly coordinating or non-coordinating monoanion Y is SbF6 - Or formula BR'4 - (wherein R' is a halogen atom, or a phenyl group optionally substituted with 1 to 5 halogen atoms, methyl or CF3 groups) or formula Al(OR")4 - (In the formula, R'' is C, which may be substituted with one or more halogen atoms) 1~6 It may be an alkyl group. In particular, a weakly coordinating or non-coordinating coordinating monoanion Y is - SbF6, - BF4, - Al(OC3HF6)4, - Al(OC4F9)4 and - Selected from the group consisting of B(3,5-bis(trifluoromethyl)phenyl)4.

[0019] According to any embodiment of the present invention, a bidentate diphosphine ligand (PP) is an electron-rich ligand. In particular, a bidentate diphosphine ligand (PP) is a C5-C ligand whose coordinating group consists of two phosphorus atoms. 50 It is a bidentate ligand. In particular, the two phosphorus atoms of a bidentate diphosphine ligand (PP) are separated by at least two carbon atoms and up to four carbon atoms. In particular, the bidentate diphosphine ligand (PP) is given by formula [ka] (In the equation, the dotted line represents a single bond where n is 1, or the dotted line represents a double bond where n is 0; R a , R b , R c and R d In separate cases, simultaneously or independently, each is a halogen atom, C 1~10 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~4 Linear C1-C8 alkyl, linear C2-C8 alkenyl, branched or cyclic C3-C8 alkyl or alkenyl, C6-C8, which may be substituted with one or more carboxylic acid ester groups. 10 Represents an aryl group; or R a and R b together, and / or R c and R d Together, they have 4 to 20 atoms, and the R a and R b Base or R c and R d A saturated or unsaturated ring containing a phosphorus atom to which is bonded is formed, and the ring contains a halogen atom, C 1~10 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~4 Carboxylic acid ester, C 6~10 It may be substituted with one or more aryl groups; R e and R f These are, independently of each other, hydrogen atoms or C 1~8 A hydrocarbon group; may contain one or two oxygen atoms or nitrogen atoms; or both R f Together, they each consist of one or two halogen atoms, C 1~10 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~4 It may be substituted with a carboxylic acid ester group, C 3~10 Cycloalkyl, C 5~10 Cycloalkenyl, C 4~10 Heterocycloalkyl, C 4~10 Heterocycloalkenyl, C 4~10 Heteroaryl or C 6~10Forming an aryl group; or R a and R f Furthermore / or R d and R f Together, they have 4 to 20 atoms, and the R a and R f The base and / or R d and R f It forms a saturated or unsaturated ring containing a phosphorus atom to which is bonded, and the ring contains one or two halogen atoms, C 1~10 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~4 It may be a compound that is substituted with a carboxylic acid ester group.

[0020] The terms “alkyl,” “alkenyl,” and “alkoxy” are understood to include branched and linear alkyl and alkenyl groups unless otherwise specified. The terms “alkenyl,” “cycloalkenyl,” and “heterocycloalkenyl” are understood to include one, two, or three olefinic double bonds, preferably one or two. The terms “cycloalkyl,” “cycloalkenyl,” “heterocycloalkyl,” “heterocycloalkenyl,” and “saturated or unsaturated ring” are understood to include monocyclic or condensed, spiro and / or bridged bicyclic or tricyclic cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl groups and saturated or unsaturated rings, preferably monocyclic cycloalkyl, cycloalkenyl, heterocycloalkyl, and heterocycloalkenyl groups.

[0021] The term "halo- or perhalo-hydrocarbon" is understood as a hydrocarbon group in which one or all of the hydrogen atoms are replaced by halogen atoms. Examples of "halo- or perhalo-hydrocarbons" are CClH2 or CF3.

[0022] The term "aryl" is understood to include any group containing at least one aromatic group such as a phenyl, indenyl, indanyl, tetrahydronaphthalenyl or naphthalenyl group.

[0023] The term "heteroaryl" is understood as an aromatic group containing heteroatoms such as a pyridyl group or a furyl group.

[0024] For the sake of clarity, the expression "R a and R b together, and / or R c and R d together form a saturated or unsaturated ring" or "or both R f together form a C 3~10 cycloalkyl..." means, for example, that the atoms to which both groups are attached are included in a C 3~10 cycloalkyl group.

[0025] For the sake of clarity, the expression "R a and R f and / or R d and R f together form a saturated or unsaturated ring having 4 to 20 atoms..." or "R a and R b [[ID=3​​​​​​​​​​​​​​​​​​​Linear C1-C6 alkyl, linear C2-C6 alkenyl, branched or cyclic C3-C6 alkyl or alkenyl, C6-C6, which may be substituted with one or more carboxylic acid ester groups. 10 It can be an aryl group. In particular, R a , R b , R c and R d In separate cases, each is C 1~8 Alkoxy, hydroxy, or C 1~3 Linear C1-C6 alkyl, linear C2-C6 alkenyl, branched or cyclic C3-C6 alkyl or alkenyl, C6-C6, which may be substituted with one or more carboxylic acid ester groups. 10 It can be an aryl group. In particular, R a , R b , R c and R d In separate cases, each is C 1~6 Alkoxy, hydroxy, or C 1~3 Linear C1-C6 alkyl, linear C2-C6 alkenyl, branched or cyclic C3-C6 alkyl or alkenyl, C6-C6, which may be substituted with one or more carboxylic acid ester groups. 10 It can be an aryl group. In particular, R a , R b , R c and R d In separate cases, each is C 1~4 Alkoxy, hydroxy, or C 1~3 Linear C1-C6 alkyl, linear C2-C6 alkenyl, branched or cyclic C3-C6 alkyl or alkenyl, C6-C6, which may be substituted with one or more carboxylic acid ester groups. 10 It can be an aryl group. In particular, R a , R b , R c and R d In separate cases, each is C 1~4 Alkoxy, hydroxy, or C 1~3It may be a linear C1-C6 alkyl, linear C2-C6 alkenyl, branched or cyclic C3-C6 alkyl or alkenyl, or C6 aryl group, which may be substituted with one or more carboxylic acid ester groups. In particular, R a , R b , R c and R d In separate cases, each is C 1~3 Alkoxy, hydroxy, or C 1~3 R may be a linear C1-C6 alkyl, linear C2-C6 alkenyl, branched or cyclic C3-C6 alkyl or alkenyl, or C6 aryl group, which may be substituted with one or more carboxylic acid ester groups. More specifically, R a , R b , R c and R d In separate cases, each is C 1~3 Alkoxy, hydroxy, or C 1~3 The group may be a linear C1-C4 alkyl, linear C2-C4 alkenyl, branched or cyclic C5-C6 alkyl or alkenyl, or C6 aryl group, which may be substituted with one or more carboxylic acid ester groups.

[0027] According to any embodiment of the present invention, R a and R b together, as well as / or R c and R d Together, they form halogen atoms, C 1~8 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~4 Carboxylic acid ester, C 6~10 C may be substituted with one or more aryl groups. 4~15 It can be an alkanediyl group. In particular, R a and R b together, as well as / or R c and R d Together, C 1~8 Alkoxy, hydroxy, C 1~4 Carboxylic acid ester or C 6~10 C may be substituted with one or more aryl groups. 4~15It can be an alkanediyl group. In particular, R a and R b together, as well as / or R c and R d Together, C 1~6 Alkoxy, hydroxy, C 1~3 C may be substituted with one or more carboxylic acid esters or C6 aryl groups. 4~15 It can be an alkanediyl group. In particular, R a and R b together, as well as / or R c and R d Together, C 1~4 Alkoxy, hydroxy, C 1~3 C may be substituted with one or more carboxylic acid esters or C6 aryl groups. 4~12 It may be an alkanediyl group. More specifically, R a and R b together, as well as / or R c and R d Together, C 4~12 It may be an alkanediyl group.

[0028] According to any embodiment of the present invention, R a and R f And / or R d and R f Together, they have 4 to 15 atoms, and the R a and R f The base and / or R d and R f A saturated or unsaturated ring containing a phosphorus atom to which is bonded is formed, and the ring contains one or two halogen atoms, C 1~10 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~4 It may be substituted with a carboxylic acid ester group. In particular, R a and R f And / or R d and R f Together, they have 4 to 10 atoms, and the R a and Rf The base and / or R d and R f A saturated or unsaturated ring containing a phosphorus atom to which is bonded is formed, and the ring contains one or two halogen atoms, C 1~10 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~4 It may be substituted with a carboxylic acid ester group. In particular, R a and R f And / or R d and R f Together, they have 4 to 10 atoms, and the R a and R f The base and / or R d and R f A saturated or unsaturated ring containing a phosphorus atom to which is bonded is formed, and the ring contains one or two halogen atoms, C 1~8 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~3 It may be substituted with a carboxylic acid ester group. In particular, R a and R f And / or R d and R f Together, they have 4 to 10 atoms, and the R a and R f The base and / or R d and R f A saturated or unsaturated ring containing a phosphorus atom to which is bonded is formed, and the ring contains one or two halogen atoms, C 1~6 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~3 It may be substituted with a carboxylic acid ester group. More specifically, R a and R f And / or R d and R f Together, they have 4 to 10 atoms, and the R a and R f The base and / or R d and R f A saturated or unsaturated ring containing a phosphorus atom to which is bonded is formed, and the ring contains one or two halogen atoms, C1~3 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~3 It may be substituted with a carboxylic acid ester group.

[0029] According to any embodiment of the present invention, the bidentate diphosphine ligand (PP) is: [ka] (In the formula, dotted line, n, R) e and R f m has the same meaning as defined above; m is 0, 1, or 2; r is 1, 2, 3, 4, 5, or 6, and each R g These independently represent at least one substituent of the ring, and independently represent C 1~8 Alkyl or C 6~10 It is an aryl group.

[0030] According to any embodiment of the present invention, r may be 1, 2, or 3. In particular, r may be 2, and R g The group can be the two ortho substituents of the ring relative to the phosphorus atom.

[0031] According to any embodiment of the present invention, the bidentate diphosphine ligand (PP) is: [ka] (In the formula, dotted line, n, R) e and R f m has the same meaning as defined above; m is 0, 1, or 2, and each R g They are independent of each other, C 1~8 Alkyl or C 6~10 It is an aryl group.

[0032] According to any embodiment of the present invention, R e and R f These are, independently of each other, hydrogen atoms or C 1~6 A hydrocarbon group, optionally containing one or two oxygen or nitrogen atoms. In particular, R e and Rf These are, independently of each other, hydrogen atoms or C 1~6 It can be an alkyl group. In particular, R e and R f These are, independently of each other, hydrogen atoms or C 1~4 It can be an alkyl group. In particular, R e and R f These are, independently of each other, hydrogen atoms or C 1~3 It can be an alkyl group. In particular, R e and R f These can be a hydrogen atom or a methyl or ethyl group, independently of each other. In particular, R e and R f These can be a hydrogen atom or a methyl group, independently of each other. More specifically, R e and R f These are hydrogen atoms, independent of each other.

[0033] According to any embodiment of the present invention, both R f Together, they each consist of one or two halogen atoms, C 1~10 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~4 It may be substituted with a carboxylic acid ester group, C 3~8 Cycloalkyl, C 5~8 Cycloalkenyl, C 4~8 Heterocycloalkyl, C 4~8 Heterocycloalkenyl, C 4~8 It forms a heteroaryl or C6aryl group. In particular, according to any embodiment of the present invention, both R f Together, they each consist of one or two halogen atoms, C 1~8 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~3 It may be substituted with a carboxylic acid ester group, C 3~8 Cycloalkyl, C 5~8 Cycloalkenyl, C 4~8 Heterocycloalkyl, C 4~8 Heterocycloalkenyl, C 4~8It forms a heteroaryl or C6aryl group. In particular, according to any embodiment of the present invention, both R f Together, they each consist of one or two halogen atoms, C 1~6 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~3 It may be substituted with a carboxylic acid ester group, C 3~8 Cycloalkyl, C 5~8 Cycloalkenyl, C 4~8 Heterocycloalkyl, C 4~8 Heterocycloalkenyl, C 4~8 It forms a heteroaryl or C6aryl group. In particular, both R f Together, they each consist of one or two halogen atoms, C 1~4 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~3 It may be substituted with a carboxylic acid ester group, C 3~8 Cycloalkyl, C 5~8 Cycloalkenyl, C 4~8 Heterocycloalkyl, C 4~8 Heterocycloalkenyl, C 4~8 It forms a heteroaryl or C6aryl group. In particular, both R f Together, they each consist of one or two halogen atoms, C 1~3 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~3 It may be substituted with a carboxylic acid ester group, C 3~8 Cycloalkyl, C 5~8 Cycloalkenyl, C 4~8 Heterocycloalkyl, C 4~8 Heterocycloalkenyl, C 4~8 It forms a heteroaryl or C6aryl group. In particular, both R f Together, they each consist of one or two halogen atoms, C 1~3 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~3 It may be substituted with a carboxylic acid ester group, C 4~8 Cycloalkyl, C 5~8 Cycloalkenyl, C5~7 Heterocycloalkyl, C 5~7 Heterocycloalkenyl, C 5~7 It forms a heteroaryl or C6aryl group. In particular, both R f Together, they each consist of one or two halogen atoms, C 1~3 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~3 It may be substituted with a carboxylic acid ester group, C 5~7 Cycloalkyl, C 5~7 It forms a cycloalkenyl or C6 aryl group. In particular, both R f Together, they each consist of one or two halogen atoms, C 1~3 Alkoxy, hydroxyl, halo- or perhalo-hydrocarbons, C 1~3 They form a C6 cycloalkyl, C6 cycloalkenyl, or C6 aryl group, which may be substituted with a carboxylic acid ester group. More specifically, both R f Together, they form a C6 aryl group.

[0034] According to any embodiment of the present invention, m is 1.

[0035] According to any embodiment of the present invention, R g They are independent of each other, C 3~8 It is a branched alkyl or phenyl group. In particular, R g They are independent of each other, C 3~6 It is a branched alkyl or phenyl group. More specifically, R g These are, independently of each other, isopropyl or phenyl groups.

[0036] Suitable bidentate diphosphine ligands include, but are not limited to, 1,2-bis(2,5-diisopropylphosphoran-1-yl)benzene, 1,2-bis(2,5-diisopropylphosphoran-1-yl)ethane, 1,2-bis(2,5-diphenylphosphoran-1-yl)ethane, 1,2-bis(2,5-diphenylphosphoran-1-yl)benzene, 1,2-bis(dimethylphosphaneyl)ethane, 1,2-bis(diethylphosphaneyl)ethane, 1,2-bis(diisopropylphosphaneyl)ethane, 1,2-bis(dicyclopentylphosphaneyl)ethane, and 1,2-bis(dicyclohexylphosphaneyl)ethane.

[0037] Examples of suitable Co(I) complexes for formula (I) include, but are not limited to, [Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)benzene)(η 6 -C6H6)]Al(OC4F9)4,[Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)ethane)(η 6 -C6H6)]Al(OC4F9)4,[Co(1,2-bis(2,5-diphenylphosphoran-1-yl)ethane)(η 6 -C6H6)]Al(OC4F9)4,Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)benzene(η 6 -C6H5CH3)]Al(OC4F9)4,[Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)ethane(η 6 -C6H5CH3)]Al(OC4F9)4,[Co(1,2-bis(2,5-diphenylphosphoran-1-yl)ethane)(η 6 -C6H5CH3)]Al(OC4F9)4,Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)benzene(η 6 -C6H5F)]Al(OC4F9)4,[Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)ethane(η 6 -C6H5F)]Al(OC4F9)4,[Co(1,2-bis(2,5-diphenylphosphoran-1-yl)ethane)(η 6-C6H5F)]Al(OC4F9)4,[Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)benzene)(η 6 -C6H6)]B(3,5-bis(trifluoromethyl)phenyl)4, [Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)ethane)(η 6 -C6H6)]B(3,5-bis(trifluoromethyl)phenyl)4,[Co(1,2-bis(2,5-diphenylphosphoran-1-yl)ethane)(η 6 -C6H6)]B(3,5-bis(trifluoromethyl)phenyl)4, Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)benzene(η 6 -C6H5CH3)]B(3,5-bis(trifluoromethyl)phenyl)4,[Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)ethane(η 6 -C6H5CH3)]B(3,5-bis(trifluoromethyl)phenyl)4,[Co(1,2-bis(2,5-diphenylphosphoran-1-yl)ethane)(η 6 -C6H5CH3)]B(3,5-bis(trifluoromethyl)phenyl)4, Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)benzene(η 6 -C6H5F)]B(3,5-bis(trifluoromethyl)phenyl)4,[Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)ethane(η 6 -C6H5F)]B(3,5-bis(trifluoromethyl)phenyl)4 or [Co(1,2-bis(2,5-diphenylphosphoran-1-yl)ethane)(η 6 -C6H5F)]B(3,5-bis(trifluoromethyl)phenyl)4 is one example.

[0038] According to any embodiment of the present invention, the Co(I) complex of formula (I) can be prepared and isolated before use in this process according to general methods described in literature such as ACS Catalysis 2022, 12, 4680-4687.

[0039] Furthermore, the complexes can be prepared in situ by several methods in a hydrogenation medium without isolation or purification immediately before use.

[0040] One possible procedure for advantageously preparing the complex of the present invention in situ is the formula [Co(L) z This method involves reacting a suitable cobalt complex of ]Y (wherein L and Y have the same meanings as defined above, and z is 1 or 2) with the bidentate diphosphine ligand (PP) defined above to obtain a solution of the catalyst according to formula (I).

[0041] According to any embodiment of the present invention, the Co(I) complex of formula (I) can be added to the reaction medium at a wide range of concentrations. Non-limiting examples include complex concentration values ​​ranging from 1 ppm to 50,000 ppm relative to the amount of substrate. Preferably, the complex concentration is in the range of 10 to 10,000 ppm. Preferably, the complex concentration is in the range of 10 to 5,000 ppm. More preferably, the complex concentration is in the range of 50 to 5,000 ppm. As is known to those skilled in the art, it goes without saying that the optimal concentration of the complex depends on the properties of the complex, the properties of the substrate, the pressure of H2 used during the process, and the desired reaction time.

[0042] According to a particular embodiment of the present invention, the homogeneous catalyst system is a) at least a salt of formula MY (wherein M is an alkali metal or alkaline earth metal, and Y is a weakly coordinating or non-coordinating monoanion), and b) Formula [Co(PP)(L')]2(II) (In the formula, PP is a bidentate diphosphine ligand, L' is a halogen atom, C) 1~18 Alkoxide, C 1~8 Co(I) complexes of carboxylate or β-diketonate groups Includes.

[0043] The term "β-diketonate" is derived from C(=O)-CH=C(O -It is understood as a ligand containing a ) group. In particular, β-diketonates are given by formula R 2 -C(=O)-CH=C(O - )-R 3 (In the formula, R 2 and R 3 They are independent of each other, C 1~6 Alkyl groups, especially C 1~4 These are alkyl groups, and more specifically, methyl, propyl, isopropyl, or terbutyl groups. Non-limiting examples of β-diketonates include 4-oxopenta-2-en-2-oleate, 2,2-dimethyl-5-oxohexa-3-en-3-oleate, 2,6-dimethyl-5-oxohepta-3-en-3-oleate, or 2,2,6,6-tetramethyl-5-oxohepta-3-en-3-oleate.

[0044] According to any embodiment of the present invention, the alkali metal M may be selected from the group consisting of lithium, sodium, and potassium, and the alkaline earth metal may be magnesium. The non-coordinating monoanion Y has the same meaning as defined above. In particular, MY may be selected from the group consisting of NaBF4, LiBF4, KBF4, NaSbF6, LiSbF6, KSbF6, NaB(3,5-bis(trifluoromethyl)phenyl)4, LiB(3,5-bis(trifluoromethyl)phenyl)4, KB(3,5-bis(trifluoromethyl)phenyl)4, NaB((pentafluoro)phenyl)4, LiAl(OC4F9)4, NaAl(OC4F9)4, and mixtures thereof. Preferably, MY may be selected from the group consisting of NaB(3,5-bis(trifluoromethyl)phenyl)4, LiB(3,5-bis(trifluoromethyl)phenyl)4, and KB(3,5-bis(trifluoromethyl)phenyl)4.

[0045] The salt of formula MY can be added to the reaction medium of the process of the present invention at a wide range of concentrations. Non-limiting examples include concentrations of the salt of formula MY ranging from 1 to 100 equivalents relative to the total amount of the Co(I) complex of formula (II). In particular, the concentration of the salt of formula MY may be in amounts of 1 to 50 equivalents relative to the total amount of the Co(I) complex of formula (II). More specifically, the concentration of the salt of formula MY may be in amounts of 1 to 50 equivalents relative to the total amount of the Co(I) complex of formula (II). It goes without saying that the process will also work with larger amounts of the salt of formula MY. However, the optimal concentration of the salt of formula MY depends on the properties of the salt of formula MY, the properties of the allene, the temperature, and the desired reaction time, as is known to those skilled in the art.

[0046] According to any embodiment of the present invention, L' is a halogen atom, C 1~15 Alkoxide, C 1~6 It may be a carboxylate or a β-diketonate group. In particular, L' is a halogen atom, C 1~12 Alkoxide, C 1~6 It may be a carboxylate or a β-diketonate group. In particular, L' is a halogen atom, C 1~10 Alkoxide, C 1~6 It may be a carboxylate or a β-diketonate group. In particular, L' is a halogen atom, C 1~8 Alkoxide, C 1~6 It may be a carboxylate or a β-diketonate group. In particular, L' is a halogen atom, C 1~6 Alkoxide, C 1~6 It may be a carboxylate or a β-diketonate group. In particular, L' is a halogen atom, C 1~4 Alkoxide, C 1~4 It may be a carboxylate or a β-diketonate group. In particular, L' is a halogen atom, C 1~3 Alkoxide, C 1~4 It may be a carboxylate or a β-diketonate group. In particular, L' may be a chloride atom or a bromide atom, an acetate, a pivalate, or a 4-oxopenta-2-ene-2-oleate group. More specifically, L' may be a chloride atom.

[0047] According to any embodiment of the present invention, the bidentate diphosphine ligand (PP) has the same meaning as defined above.

[0048] Examples of suitable Co(I) complexes of formula (II), but not limited to these, include [Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)benzene)(Cl)]2, [Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)ethane)(Cl)]2, or [Co(1,2-bis(2,5-diphenylphosphoran-1-yl)ethane)(Cl)]2.

[0049] According to any embodiment of the present invention, the Co(I) complex of formula (II) can be prepared and isolated before use in this process according to general methods described in literature such as Science 2018, 360, 888-893.

[0050] Furthermore, the complexes can be prepared in situ by several methods in a hydrogenation medium without isolation or purification immediately before use, as reported in Science 2018, 360, 888-893.

[0051] According to any embodiment of the present invention, the Co(I) complex of formula (II) can be added to the reaction medium at a wide range of concentrations. Non-limiting examples include complex concentration values ​​ranging from 1 ppm to 50,000 ppm relative to the amount of substrate. Preferably, the complex concentration is in the range of 10 to 10,000 ppm. Preferably, the complex concentration is in the range of 10 to 5,000 ppm. More preferably, the complex concentration is in the range of 50 to 5,000 ppm. As is known to those skilled in the art, it goes without saying that the optimal concentration of the complex depends on the properties of the complex, the properties of the substrate, the pressure of H2 used during the process, and the desired reaction time.

[0052] According to any embodiment of the present invention, the homogeneous catalyst system is a) A reducing agent selected from the group consisting of Zn metal, LiBHEt3, NaBH4, and NaBHEt3, and b) Formula [Co(PP)(Z)2](III a ) or [Co(PP)(Z')](III b It contains the Co(II) complex of ). (wherein PP is a bidentate diphosphine ligand; Z is a halogen atom, optionally substituted with a trimethylsilyl group) 1~4 Alkyl group, β-diketonate group, sulfonate group, phosphate group, C 1~18 Alkoxide group, C 1~8 Carboxylate group, or one or three C 1~8 Alkyl alkyl group, C 3~8 Cycloalkyl group, halogen atom, C 1~3 Alkoxy groups, halo- or perhalo-hydrocarbon groups, or C 1~3 A phenolate group, sometimes substituted with a carboxylic acid ester group, where Z' is a carbonate or sulfate group.

[0053] According to any embodiment of the present invention, the bidentate diphosphine ligand (PP) has the same meaning as defined above.

[0054] According to any embodiment of the present invention, the Co(II) complex is defined by formula (III) above. a It is a complex of ).

[0055] According to any embodiment of the present invention, Z is optionally substituted with a halogen atom, a trimethylsilyl group, and C 1~3 Alkyl alkyl group, C 1~15 Alkoxide, C 1~6 It may be a carboxylate or a β-diketonate group. In particular, Z may be a C atom optionally substituted with a halogen atom or a trimethylsilyl group. 1~2 Alkyl alkyl group, C 1~12 Alkoxide, C 1~6 It may be a carboxylate or a β-diketonate group. In particular, Z is a halogen atom, a methyl group optionally substituted with a trimethylsilyl group, C 1~12Alkoxide, C 1~6 It may be a carboxylate or a β-diketonate group. In particular, Z may be a halogen atom, a CH2SiMe3 group, or C 1~8 Alkoxide, C 1~6 It may be a carboxylate or a β-diketonate group. In particular, Z is a halogen atom, C 1~6 Alkoxide, C 1~6 It may be a carboxylate or a β-diketonate group. In particular, Z is a halogen atom, C 1~4 Alkoxide, C 1~4 It may be a carboxylate or a β-diketonate group. In particular, Z is a halogen atom, C 1~3 Alkoxide, C 1~4 It may be a carboxylate or a β-diketonate group. In particular, Z may be a chloride atom or a bromide atom, an acetate, a pivalate, or a 4-oxopenta-2-ene-2-oleate group. More specifically, Z may be a chloride atom.

[0056] The reducing agent can be added to the reaction medium of the process of the present invention at a wide range of concentrations. As a non-limiting example, the reducing agent concentration can range from 0.01 mol% to 10 mol% relative to the total amount of allene. In particular, the reducing agent concentration can range from 0.5 mol% to 5 mol%. It goes without saying that the process will also function with greater concentrations of reducing agents. However, the optimal concentration of the reducing agent Y depends on the properties of the reducing agent, the properties of allene, the temperature, and the desired reaction time, as is known to those skilled in the art.

[0057] Formula (III a Suitable Co(II) complexes for ) include, but are not limited to, [Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)benzene)(Cl)2], [Co(1,2-bis(2,5-diisopropylphosphoran-1-yl)ethane)(Cl)2], or [Co(1,2-bis(2,5-diphenylphosphoran-1-yl)ethane)(Cl)2].

[0058] According to any embodiment of the present invention, formula (IIIa ) or (III b The Co(II) complex of ) can be prepared and isolated before use in this process according to general methods described in literature such as ARHermes, GSGirolami Inorg, Chem. 1988, 27, 1775-1781 or MRRFriedfeld, GWMargulieux, BASchaefer, PJChirik J.Am Chem.Soc. 2014, 136, 13178-13181.

[0059] Furthermore, the complexes can be prepared in situ in a hydrogenation medium by several methods, without isolation or purification, immediately before use, using cobalt salts such as CoCl2 and diphosphine.

[0060] According to any embodiment of the present invention, formula (III a ) or (III b The Co(II) complex can be added to the reaction medium at a wide range of concentrations. Non-limiting examples include complex concentrations ranging from 1 ppm to 50,000 ppm relative to the amount of substrate. Preferably, the complex concentration is in the range of 10 to 10,000 ppm. More preferably, the complex concentration is in the range of 10 to 5,000 ppm. As is well known to those skilled in the art, the optimal concentration of the complex depends on the properties of the complex, the properties of the substrate, the pressure of H2 used during the process, and the desired reaction time.

[0061] The complex of formula (I) generally represents a preferred embodiment of the present invention for practical reasons.

[0062] According to any embodiment of the present invention, the process of the present invention is the 1,2-hydrogenation of a terminal allene to a corresponding ω-1 alkene.

[0063] According to any embodiment of the present invention, the terminal allene is of the following formula. [ka] (In the formula, R 1 C optionally contains 1 to 3 oxygen atoms and / or 1 to 2 nitrogen atoms and / or 1 sulfur atom. 1~30 It is a hydrocarbon.

[0064] According to any embodiment of the present invention, the ω-1 alkene is given by the following formula. [ka] (In the formula, R 1 (This has the same meaning as defined above.)

[0065] To clarify, the wavy bond in compounds such as formula (V) means in the usual sense as understood by those skilled in the art, that is, the double bond may have a cis configuration corresponding to the Z isomer, a trans configuration corresponding to the E isomer, or a mixture thereof.

[0066] According to any one of the above embodiments of the present invention, Allen is C4-C of formula (IV) 30 Compounds, in particular, C5-C of formula (IV) 20 The compound, more specifically, C5-C of formula (IV) 15 It is a compound.

[0067] According to any embodiment of the present invention, R 1 Depending on the case, linear, branched, or cyclic C1-C are substituted. 30 It may be an alkyl or alkenyl group. In particular, R 1 Depending on the case, linear, branched, or cyclic C4-C4 cells may be substituted. 30 It may be an alkyl or alkenyl group. In particular, R 1 Depending on the case, linear, branched, or cyclic C4-C4 cells may be substituted. 20 It may be an alkyl or alkenyl group. In particular, R 1 Depending on the case, linear, branched, or cyclic C5-C5 cells may be substituted. 20 It may be an alkyl or alkenyl group. More specifically, R 1 Depending on the case, linear, branched, or cyclic C5-C5 cells may be substituted.15 It may be an alkyl or alkenyl group.

[0068] Furthermore, according to even further embodiments, R 1 When representing an alkenyl group, the carbon-carbon double bond is not terminal and is not conjugated to the allene.

[0069] R 1 The possible substituents are one, two, or three OR h Or R h Base, one S(=O)R h or one SO2R h Or one or two NRs h 2 (wherein, R h These are hydrogen atoms, C1~C 10 The group is a cyclic, linear, or branched alkyl or alkenyl group, preferably a C1-C4 linear or branched alkyl or alkenyl group. Other possible substituents include the COOR group. h You could also list these.

[0070] Non-limiting examples of compounds in (IV) include 4,8-dimethylnonano-1,2,7-trien-4-ol, 1-(p-tolyl)buta-2,3-dien-1-ol, 1-cyclohexylbuta-2,3-dien-1-ol, undeca-1,2-dien-4-ol, (E)-5-methylocta-1,2,5-trien-4-ol, 1-phenylhexa-4,5-dien-3-ol, (6R)-6,10-dimethylundeca-1,2,9-trien-4-ol, 2-phenylpenta-3,4-dien-2-ol, 3-phenylhexa-4,5-dien-3-ol, 2-methyl-3-phenylhexa-4,5-dien-3-ol, 4 -methyldeca-1,2-dien-4-ol, 3-methyl-1-phenylhexa-4,5-dien-3-ol, 4,4-dimethyl-1-(propa-1,2-dien-1-yl)cyclohexane-1-ol, 1-(propa-1,2-dien-1-yl)cyclopentan-1-ol, 1-(propa-1,2-dien-1-yl)cyclohexane-1-ol, 1-(propa-1,2-dien-1-yl)cyclooctan-1-ol, 2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol or (4aS,8aS)-2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol.

[0071] According to any embodiment of the present invention, the terminal allene of formula (IV) can be prepared according to general methods described in the literature.

[0072] Non-limiting examples of compounds of formula (V) include (Z)-4,8-dimethylnonano-2,7-dien-4-ol, (Z)-2-phenylpenta-3-en-2-ol, (Z)-3-phenylhexa-4-en-3-ol, (Z)-2-methyl-3-phenylhexa-4-en-3-ol, 4-methyldeca-1,2-dien-4-ol, (Z)-3-methyl-1-phenylhexa-4-en-3-ol, (Z)-4,4-dimethyl-1-(propa-1-en-1-yl)cyclohexane-1-ol, (Z)-1-(propa-1-en-1-yl)cyclopentan-1-ol, (Z)-1-(propa-1-en-1-yl)cycloheptan-1-ol, (Z)-2-(propa-1-en- These are (1-yl)decahydronaphthalen-2-ol, (4aS,8aS)-2-((Z)-propa-1-en-1-yl)decahydronaphthalen-2-ol, (Z)-1-(propa-1-en-1-yl)cyclohexane-1-ol, (Z)-1-(propa-1-en-1-yl)cyclooctan-1-ol, (Z)-1-(p-tolyl)buta-2-en-1-ol, (Z)-1-cyclohexylbuta-2-en-1-ol, (2Z,5E)-5-methylocta-2,5-dien-4-ol, (Z)-1-phenylhexa-4-en-3-ol, (6R,Z)-6,10-dimethylundeca-2,9-dien-4-ol or (Z)-undeca-2-en-4-ol.

[0073] According to any embodiment of the present invention, the process of the present invention is carried out in the absence of a base or additive.

[0074] Hydrogenation reactions can be carried out in or without a solvent. Where a solvent is required or used for practical reasons, the current solvents in hydrogenation reactions can be used for the purposes of the present invention. Non-limiting examples include aromatic solvents such as toluene, fluorobenzene, trifluorotoluene, ortho-difluorobenzene, ortho-dichlorobenzene, chlorobenzene, or xylene; hydrocarbon solvents such as hexane or cyclohexane; polar solvents such as ethers such as tetrahydrofuran, methyltetrahydrofuran, or MTBE; primary or secondary alcohols such as isopropanol or ethanol; or mixtures thereof. The choice of solvent is a function of the properties of the complex, and those skilled in the art can readily select the most convenient solvent in each case to optimize the hydrogenation reaction.

[0075] In the hydrogenation process of the present invention, the reaction is 2 5 Pa~100×10 5 The H2 pressure can be within the range of Pa (1 to 100 bar), or even higher if desired. Here again, those skilled in the art can adjust the pressure sufficiently as a function of the catalytic load and the dilution of the substrate in the solvent. For example, 2 × 10 5 Pa~10×10 5 Typical pressures in Pa (2-10 bar) can be listed.

[0076] The temperature range in which hydrogenation can be carried out is 0°C to 80°C, more preferably 20°C to 50°C. Naturally, 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 for the reaction or conversion.

[0077] The process of the present invention can be carried out under batch or continuous conditions.

[0078] Another aspect of the present invention is 4,8-dimethylnonano-1,2,7-trien-4-ol, 1-(p-tolyl)buta-2,3-dien-1-ol, 1-cyclohexylbuta-2,3-dien-1-ol, undeca-1,2-dien-4-ol, (E)-5-methylocta-1,2,5-trien-4-ol, 1-phenylhexa-4,5-dien-3-ol, (6R)-6,10-dimethylundeca-1,2,9-trien-4-ol, 2-phenylpenta-3,4-dien-2-ol, 3-phenylhexa-4,5-dien-3-ol, 2-methyl-3-phenylhexa-4,5-dien-3-ol, The use of compounds selected from the group consisting of 4-methyldeca-1,2-dien-4-ol, 3-methyl-1-phenylhexa-4,5-dien-3-ol, 4,4-dimethyl-1-(propa-1,2-dien-1-yl)cyclohexane-1-ol and 1-(propa-1,2-dien-1-yl)cyclopentan-1-ol, 1-(propa-1,2-dien-1-yl)cyclohexane-1-ol, 1-(propa-1,2-dien-1-yl)cyclooctane-1-ol and 2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol in the semi-hydrogenation process defined above.

[0079] Some compounds of formula (IV) are novel compounds and exhibit several advantages, as described above and shown in the examples. Therefore, another object of the present invention is a compound for use in the semi-hydrogenation process of the present invention, the compound being selected from the group consisting of 4,8-dimethylnonano-1,2,7trien-4-ol, (E)-5-methylocta-1,2,5trien-4-ol, (6R)-6,10-dimethylundeca-1,2,9trien-4-ol, 2-methyl-3-phenylhexa-4,5-dien-3-ol, 1-(propa-1,2-dien-1-yl)cyclohexane-1-ol, 1-(propa-1,2-dien-1-yl)cyclooctan-1-ol, 2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol and (4aS,8aS)-2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol.

[0080] A typical method for carrying out the process of the present invention is described below in the examples. [Examples]

[0081] The present invention will now be described in more detail by the following examples, where abbreviations have their usual meaning in the art and temperatures are given in degrees Celsius (°C). The pre-catalyst and ligand solutions were prepared under an inert atmosphere (argon) using the standard Schlenk technique. The solvents were dried by conventional procedures and distilled under an argon atmosphere. NMR spectra were recorded at 20°C using a Bruker AV300, AV400, or AV500 MHz spectrometer. Chemical shifts are reported in ppm relative to the solvent signal (chloroform, δH=7.26 ppm, δC=77.0 ppm). The signal assignments are as follows: 1 H, 1 H-COSY, -NOESY, 13 C, 1This was confirmed by recording H-HSQC and HMBC experiments. Gas chromatography was performed using an Agilent 6850 series with DB-1 or DB-Wax columns (10m × 0.1mm inner diameter, 0.1μm film). The cobalt complex was prepared according to the following literature: a) SC Meier, A. Holz, J. Kulenkampff, A. Schmidt, D. Kratzert, D. Himmel, D. Schmitz, E.-W. Scheidd, W. Scherer, C. Bulow, M. Timm, R. Lindblad, STAkin, V. Zamudio-Bayer, B. von Issendorff, MADuncan, J. TLau, and I. Krossing Angew. Chem. Int. Ed. 2018, 57, 9310-9314. b) C.S. MacNeil, H. Zhong, T.P. Abst, M. Shevlin, P.J. Chirik ACS Catalysis 2022, 12, 4680-4687. c) M.R. Friedfeld, H. Zhong, R.R. Track, M. Shevlin, P.J. Chirik Science 2018,360,888-893. (R,R)-iPr-Duphos represents (R,R)-1,2-bis(2,5-diisopropylphosphoran-1-yl)benzene.

[0082] Example 1 Hydrogenation of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol using the Co(I) complex of formula (I) In a 3 ml glass reactor, under argon, (R,R-iPr-Duphos)Co(C6H6)][Al(OC(CF3)3)4] (7.8 mg, 0.005 mmol, 0.5 mol%) was added, followed by a solution of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol (166.5 mg, 1.002 mmol) dissolved in trifluoromethylbenzene (1 ml). A further 1 ml of trifluoromethylbenzene was added and rinsed. The glass flask was then placed in a stainless steel autoclave and pressurized with hydrogen (3 × 10 bar), and the solution was mechanically stirred under hydrogen (5 bar) at 25°C for 6 hours. The autoclave was then evacuated, and the reaction mixture was analyzed by GC (DB-Wax). Analysis revealed a conversion rate exceeding 99% and a formation rate of 93% for (rac)-(Z)-4,8-dimethyl-2,7-nonadien-4-ol.

[0083] Example 2 Hydrogenation of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol using Co(I) complex of formula (I) in various solvents In a 3 ml glass reactor, under argon, (R,R-iPr-Duphos)Co(C6H6)][Al(OC(CF3)3)4] (7.8 mg, 0.005 mmol, 0.5 mol%) was added, followed by the addition of a solution of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol (166.5 mg, 1.002 mmol) dissolved in the desired solvent (2 ml) shown in Table 1. The glass flask was then placed in a stainless steel autoclave and pressurized with hydrogen (3 × 10 bar), and the solution was mechanically stirred under hydrogen (5 bar) at 25°C for 6 hours. The autoclave was then evacuated and purged with nitrogen, and the reaction mixture was analyzed by GC (DB-Wax). The results are shown in Table 1.

[0084] Table 1. Hydrogenation of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol using Co(I) complex of formula (I) in various solvents. 1) [Table 1] 1) Average of two runs. 2) Conversion rate: 100% - % of the starting material measured by GC. 3) Amount of (rac)-(Z)-4,8-dimethyl-2,7-nonadien-4-ol measured by GC.

[0085] Example 3 Hydrogenation of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol using the Co(I) complex of formula (II) General procedure: In a 3 ml glass reactor, under argon, continuously inject [(L)CoCl]2 (0.0025 mmol, 0.25 mol%) and sodium salt Na. + X - (0.05 mmol, 5 mol%) was added, followed by a solution of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol (2 ml, 1 mmol in 0.5 M THF). The glass flask was then placed in a stainless steel autoclave and purged with hydrogen (3 × 10 bar). The solution was then mechanically stirred under hydrogen (5 bar) at 25°C for 6 hours. The autoclave was then evacuated and purged with nitrogen, and the reaction mixture was analyzed by GC (DB-Wax). The results obtained using diphosphine L as described in Table 2 are shown in Table 3.

[0086] Table 2. Table 3: Diphosphine L used [Table 2]

[0087] Table 3: Hydrogenation of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol using the Co(I) complex of formula (II) [Table 3] 1) Conversion rate: 100% - Amount of starting material measured by GC. 2) Amount of (rac)-(Z)-4,8-dimethyl-2,7-nonadien-4-ol measured by GC. 3) Sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate. 4) Sodium hexafluoroantimonate. 5) Sodium tetrafluoroborate.

[0088] Example 4 Hydrogenation of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol using the Co(II) complex of formula (III) with LiEt3BH as a reducing agent. Under argon, 0.03 ml of LiEt3BH (1.7 M solution in THF, 0.05 mmol, 0.5 mol%) was added to a solution of (R,R)-1,2-bis(2,5-dimethylphosphoran-1-yl)benzenecobalt dichloride (9.9 mg, 0.023 mmol, 0.2 mol%) in THF (2 ml). The purple solution was stirred for 5 minutes and then added to a solution of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol (1.67 g, 10 mmol) in THF (20 ml) placed in a stainless steel autoclave. Further THF (2 × 2 ml) was added for rinsing. The autoclave was closed, purged with hydrogen (3 × 5 bar), and the solution was mechanically stirred under hydrogen (5 bar) at 25°C for 16 hours. Next, the autoclave was evacuated and purged with nitrogen, and the reaction mixture was analyzed by GC (DB-Wax). The analysis showed a conversion rate of 99% and a formation rate of 66% for (rac)-(Z)-4,8-dimethyl-2,7-nonadien-4-ol.

[0089] Example 5 Hydrogenation of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol using a Co(II) complex of formula (III) with zinc as a reducing agent. Under argon conditions, (R,R)-1,2-bis(2,5-dimethylphosphoran-1-yl)benzenecobalt dichloride (43.8 mg, 0.1 mmol, 1 mol%), zinc powder (132.5 mg, 2.03 mmol, 20 mol%), and methanol (24 ml) were successively added to a stainless steel autoclave. The autoclave was closed, purged with hydrogen (3 × 5 bar), and the solution was mechanically stirred at 50°C under hydrogen (25 bar) for 21.5 hours. The autoclave was then cooled to room temperature, evacuated, purged with nitrogen, and the reaction mixture was analyzed by GC (DB-Wax). Analysis showed a conversion rate of over 99% and a formation rate of 65% of (rac)-(Z)-4,8-dimethyl-2,7-nonadien-4-ol.

[0090] Example 6 Hydrogenation of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol using the Co(II) complex of formula (III) as a reducing agent. Under argon, NaBH4 (35.8 mg, 0.95 mmol, 9.5 mol%) was added to a blue suspension of 1,4-bis(diphenylphosphanyl)butanecobalt dichloride (54.6 mg, 0.098 mmol, 1 mol%) in THF (5 ml). The suspension was stirred for 1 hour until it turned dark brown. The solution was then added to a solution of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol (1.665 g, 10 mmol) in THF (20 ml) placed in a stainless steel autoclave. The autoclave was closed, purged with hydrogen (3 × 5 bar), and the solution was mechanically stirred under hydrogen (5 bar) at 50°C for 5 hours. The autoclave was then cooled to room temperature, evacuated, purged with nitrogen, and the reaction mixture was analyzed by GC (DB-Wax). Analysis revealed a conversion rate exceeding 99% and a formation rate of 59% for (rac)-(Z)-4,8-dimethyl-2,7-nonadien-4-ol.

[0091] Example 7 Hydrogenation of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol using the Co(II) complex of formula (III) as a reducing agent. Under argon, NaBH4 (35.6 mg, 0.94 mmol, 9.5 mol%) was added to a suspension of 1,4-bis(diphenylphosphanyl)butanecobalt bispivarate (65.5 mg, 0.095 mmol, 1 mol%) in THF (5 ml). The suspension was stirred for 1 hour until it turned dark brown. The solution was then added to a solution of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol (1.668 g, 10 mmol) in THF (20 ml) placed in a stainless steel autoclave. The autoclave was closed, purged with hydrogen (3 × 5 bar), and the solution was mechanically stirred under hydrogen (5 bar) at 50°C for 4.5 hours. The autoclave was then cooled to room temperature, evacuated, purged with nitrogen, and the reaction mixture was analyzed by GC (DB-Wax). Analysis revealed a conversion rate exceeding 99% and a formation rate of 61% for (rac)-(Z)-4,8-dimethyl-2,7-nonadien-4-ol.

Claims

1. Molecule H ２ A method for semi-hydrogenating an allene to a corresponding alkene using, This is carried out in the presence of a homogeneous catalyst system. The homogeneous catalyst system comprises a cobalt salt, a bidentate diphosphine ligand, and a weakly coordinating or non-coordinating monoanion or reducing agent.

2. The method according to claim 1, wherein the homogeneous catalyst system is a cobalt complex of the following formula. [t(PP)(L) ｑ ](Y) ｘ (I) (wherein PP is a bidentate diphosphine ligand; x is 0 or 1; L is a C containing two or three carbon-carbon double bonds, which may contain one or more oxygen and / or halogen atoms) ４ ~C ２０ A hydrocarbon ligand, and q is 1; or L is C ３ ~C １５ (An alkene ligand where q is 3; Y is a weakly coordinating or non-coordinating monoanion.)

3. The aforementioned homogeneous catalyst system is a) at least a salt of formula MY (wherein M is an alkali metal or alkaline earth metal, and Y is a weakly coordinating or non-coordinating monoanion), and b) Co(I) complex of the following formula ["(PP)(L')] ２ (II) (wherein, PP is a bidentate diphosphine ligand, and L' is a halogen atom, C １～１８ alkoxide, C １～８ carboxylate or β-diketonate group) The method according to claim 1, including the method described in claim 1.

4. The aforementioned homogeneous catalyst system is a) Zn metal, LiBHEt ３ NaBH ４ and NaBHEt ３ A reducing agent selected from the group consisting of, b) Co(II) complex of the following formula [Co(PP)(Z) ２ ](III ａ )または[Co(PP)(Z')](III ｂ ) (wherein PP is a bidentate diphosphine ligand; Z may be substituted with a halogen atom or a trimethylsilyl group C) １～４ Alkyl group, β-diketonate group, sulfonate group, phosphate group, C １～１８ Alkoxide group, C １～８ Carboxylate group, or one or three C １～８ alkyl group, C ３～８ Cycloalkyl group, halogen atom, C １～３ Alkoxy groups, halo or perhalo hydrocarbon groups, or C １～３ (A phenolate group which may be substituted with a carboxylic acid ester group, and Z' is a carbonate or sulfate group.) The method according to claim 1, including the method described in claim 1.

5. The method according to any one of claims 1 to 4, wherein the bidentate diphosphine ligand is an electron-rich ligand.

6. The method according to any one of claims 1 to 5, wherein the bidentate diphosphine ligand has the following formula. 【Chemistry 1】 (In the formula, the dotted line represents a single bond where n is 1, or the dotted line represents a double bond where n is 0; R ａ , R ｂ , R ｃ and R ｄ In separate cases, simultaneously or independently, each is a halogen atom, C １～１０ Alkoxy, hydroxyl, halo or perhalo hydrocarbons, C １～４ A linear C group which may be substituted with one or more carboxylic acid ester groups. １ ~C ８ Alkyl, linear C ２ ~C ８ Alkenyl, branched or ring C ３ ~C ８ Alkyl or alkenyl, C ６ ~C １０ Represents an aryl group; or R ａ and R ｂ together, and / or R ｃ and R ｄ Together, they have 4 to 20 atoms, and the R ａ and R ｂ Base or R ｃ and R ｄ The group forms a saturated or unsaturated ring containing a phosphorus atom to which the group is bonded, and the ring contains a halogen atom, C １～１０ Alkoxy, hydroxyl, halo or perhalo hydrocarbons, C １～４ Carboxylic acid ester, C ６～１０ It may be substituted with one or more aryl groups; R ｅ and R ｆ These are, independently of each other, hydrogen atoms or C １～８ A hydrocarbon group; may contain one or two oxygen atoms or nitrogen atoms; or both R ｆ Together, they each consist of one or two halogen atoms, C １～１０ Alkoxy, hydroxyl, halo or perhalo hydrocarbons, C １～４ It may also be substituted with a carboxylic acid ester group, C ３～１０ Cycloalkyl, C ５～１０ Cycloalkenyl, C ４～１０ Heterocycloalkyl, C ４～１０ Heterocycloalkenyl, C ４～１０ Heteroaryl or C ６～１０ Forming an aryl group; or R ａ and R ｆ And / or R ｄ and R ｆ Together, they have 4 to 20 atoms, and the R ａ and R ｆ The base and / or R ｄ and R ｆ It forms a saturated or unsaturated ring containing a phosphorus atom to which is bonded, and the ring contains one or two halogen atoms, C １～１０ Alkoxy, hydroxyl, halo or perhalo hydrocarbons, C １～４ (It may be substituted with a carboxylic acid ester group.)

7. The method according to any one of claims 1 to 6, wherein the bidentate diphosphine ligand has the following formula. 【Chemistry 2】 (In the formula, the dotted line, n, and R are shown above.) ｅ and R ｆ m has the same meaning as defined in claim 6; m is 0, 1 or 2, and each R ｇ They are independent of each other, C １～８ Alkyl or C ６～１０ It is an aryl group; preferably, R ｇ They are independent of each other, C ３～８ (It is a branched alkyl or phenyl group.)

8. The method according to any one of claims 1 to 7, wherein the bidentate diphosphine ligand is selected from the group consisting of 1,2-bis(2,5-diisopropylphosphoran-1-yl)benzene, 1,2-bis(2,5-diisopropylphosphoran-1-yl)ethane, 1,2-bis(2,5-diphenylphosphoran-1-yl)ethane, 1,2-bis(2,5-diphenylphosphoran-1-yl)benzene, 1,2-bis(dimethylphosphanail)ethane, 1,2-bis(diethylphosphanail)ethane, 1,2-bis(diisopropylphosphanail)ethane, 1,2-bis(dicyclopentylphosphanail)ethane, and 1,2-bis(dicyclohexylphosphanail)ethane.

9. The weakly coordinating or non-coordinating monoanion is sterically hindered; preferably, the weakly coordinating or non-coordinating monoanion is Sb － F ６ or of formula B － R' ４ (wherein R' is a halogen atom, or a phenyl group optionally substituted with 1 to 5 halogen atoms or methyl or CF ３ groups), or Al － (OR'') ４ (wherein R'' is C １～６ alkyl optionally substituted with one or more halogen atoms); even more preferably, the weakly coordinating or non-coordinating monoanion is － SbF ６ , － BF ４ , － Al(O C ３ HF ６ ) ４ , － Al(O C ４ F ９ ) ４ , － B(3,5-bis(trifluoromethyl)phenyl) ４ The method according to any one of claims 1 to 8, selected from the group consisting of.

10. L is (η ６ -C ６ H ６ ), (η ６ -C ６ H ５ CH ３ ), (η ６ -C ６ H ５ OCH ３ ), (η ６ -C ６ H ４ (CH ３ ) ２ ), (η ６ -C ６ H ５ CF ３ ), (η ６ -C ６ H ５ F), (η ６ -C ６ H ４ F ２ ), and (η ６ -C ６ H ４ (CF ３ ) ２ η selected from the group consisting of ) ６ The method according to any one of claims 1 to 9, wherein the ligand is...

11. The method according to any one of claims 1 to 10, wherein L' is a chloride atom.

12. The method according to any one of claims 1 to 11, wherein the 1,2-hemihydrogenation of the terminal allene to the corresponding ω-1 alkene.

13. The method according to any one of claims 1 to 12, wherein the terminal allene is of the following formula. 【Transformation 3】 (In the formula, R １ C may contain 1 to 3 oxygen atoms and / or 1 to 2 nitrogen atoms and / or 1 sulfur atom. １～３０ It is a hydrocarbon.

14. The method according to any one of claims 1 to 13, carried out in the absence of a base or additive.

15. 4,8-dimethylnonano-1,2,7-trien-4-ol, 1-(p-tolyl)buta-2,3-dien-1-ol, 1-cyclohexylbuta-2,3-dien-1-ol, undeca-1,2-dien-4-ol, (E)-5-methylocta-1,2,5-trien-4-ol, 1-phenylhexa-4,5-dien-3-ol, (6R)-6,10-dimethylundeca-1,2,9-trien-4-ol, 2-phenylpenta-3,4-dien-2-ol, 3-phenylhexa-4,5-dien-3-ol, 2-methyl-3-phenylhexa-4,5-dien-3-ol, 4-methyldeca-1 Use of a compound selected from the group consisting of ,2-dien-4-ol, 3-methyl-1-phenylhexa-4,5-dien-3-ol, 4,4-dimethyl-1-(propa-1,2-dien-1-yl)cyclohexane-1-ol and 1-(propa-1,2-dien-1-yl)cyclopentan-1-ol, 1-(propa-1,2-dien-1-yl)cyclohexane-1-ol, 1-(propa-1,2-dien-1-yl)cyclooctane-1-ol and 2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol in the hemihydrogenation method according to any one of claims 1 to 14.

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