Method for producing fragrance intermediates

Abstract

The present invention relates to the perfumery field. More particularly, the present invention relates to novel valuable chemical intermediates for the preparation of perfuming ingredients. Furthermore, the present invention also includes a process for the preparation of the compound of formula (I).

Description

[Technical field]

[0001] The present invention relates to the perfumery field. More particularly, the present invention relates to novel valuable chemical intermediates for the preparation of perfuming ingredients. Furthermore, the present invention also includes a process for the preparation of the compound of formula (I).

[0002] 2. Background of the Invention In the perfume industry, there is a constant need to provide compounds that impart new sensory notes. In particular, there is interest in the aldehydic note, which is one of the important sensory facets of the lily of the valley scent. Compounds that impart this note are therefore especially sought in order to reconstitute the delicate floral scent of lily of the valley, which does not tolerate even the most gentle extraction methods to obtain the essential oil. 3-(Cyclohex-1-en-1-yl)propanal, 3-phenylpropanal or 3-phenylpentenal derivatives are representative of compounds that impart muguet-aldehyde olfactory notes, such as, for example, 3-(4,4-dimethyl-1-cyclohexen-1-yl)propanal reported in EP 1529770, 3-[4-(2-methyl-2-propanyl)-1-cyclohexen-1-yl]propanal reported in EP 1054053 or 4-methyl-5-(4-methylphenyl)-4-pentenal reported in WO 2010052635. However, obtaining these derivatives is time-consuming, requires Grignard reagents, radical chemistry or pyrolysis, and provides the desired compound in low yield and / or low selectivity.

[0003] Because of the industrial importance of these products, new methods that demonstrate improved yields and productivity are constantly being sought.

[0004] The present invention makes it possible to obtain the compound of formula (I) by cross-metathesis between the commercially available or readily available compounds of formula (II) and (III), while avoiding the use of toxic acrolein and crotonaldehyde, which can be readily converted to the compound of formula (V). The key intermediates in this process, the compounds of formula (I), (IV) and (VII), have not been reported or suggested in the context of the preparation of the compound of formula (V).

[0005] Summary of the Invention The present invention relates to a new process that allows the preparation of new compounds of formula (I), which provide new access to compounds of formula (V) in high yield and high selectivity. The process of the present invention represents a new and efficient route to compounds of formula (V).

[0006] A first subject of the invention is a compound of formula [ka] [In the formula, m is 0 or 1; R a is C 1-4 Alkyl group, trimethylsilyl group, C(=O)-R c Group, C(=O)-OR c group, CH2(OR c ) group, CH(OR c ) CH3 group, where R c is C 1-4 R is an alkyl group; b is C 1-4 Alkyl group, C(=O)-R c group, where R c is C 1-4 is an alkyl group; or R a and R b Together, C 2-6 represents an alkanediyl group, and X is a group represented by the formula a), b) or c). [ka] wherein each R 1 , R 2 , R3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally hydroxyl or C 1-3 substituted with an alkoxy group; or R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 Two of the groups together form C 3-8 Cycloalkyl group or C 5-8 cycloalkenyl groups, each of which optionally contains a hydroxy group, C 1-3 Alkyl group or C 1-3 substituted with an alkoxy group, the other groups having the same meaning as defined above; 8 , R 9 and R 10 are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally hydroxyl or C 1-3 substituted with an alkoxy group; or R 8 , R 9 , R 10 Two of the groups together form C 3-8 Cycloalkyl group or C 5-8 cycloalkenyl groups, each of which optionally contains a hydroxy group, C 1-3 Alkyl group or C 1-3 alkoxy group, the other groups being as defined above; n is 0 or 1, and Y is -CH=CR 11 -group, -CHR 12 -CHR 11 - group or -CH2-C(OH)R 11 - group, where R 11 is a hydrogen atom, a methyl group, or an ethyl group, and R 12is a hydroxy group or an acetate group; with the proviso that when X is a group of formula b), m is 1. or a mixture thereof, comprising a cross-metathesis step between any one of the stereoisomers of the compound of formula (IIa), (IIb) or (IIc) and any one of the stereoisomers of the compound of formula (III) or a mixture thereof in the presence of a metathesis catalyst. [ka] [In the formula, each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , n and Y have the same meaning as defined above. [ka] wherein m is 0 or 1 when the cross-metathesis step is carried out on a compound of formula (IIa) or (IIc), m is 1 when the cross-metathesis step is carried out on a compound of formula (IIb), and R a is C 1-4 Alkyl group, trimethylsilyl group, C(=O)-R c Group, C(=O)-OR c group, CH2(OR c ) group, CH(OR c ) CH3 group, where R c is C 1-4 R is an alkyl group; b is C 1-4 Alkyl group, C(=O)-R c group, where R c is C 1-4 is an alkyl group; or R a and R b Together, C 2-6 R represents an alkanediyl group; dis a hydrogen atom or CH(OR a )(OR b ) m group, where m, R a and R b have the same meaning as defined above]

[0007] Another subject of the invention is a compound of formula [ka] [In the formula, X is a compound represented by the formula b) or d). [ka] In one of the stereoisomers of the group p is 0 when the dotted line is a carbon-carbon double bond, and p is 1 when the dotted line is a carbon-carbon single bond; Each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally hydroxyl or C 1-3 substituted with an alkoxy group; or R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 Two of the groups together form C 3-8 Cycloalkyl group or C 5-8 cycloalkenyl groups, each of which optionally contains a hydroxy group, C 1-3 Alkyl group or C 1-3 substituted with an alkoxy group, the other groups having the same meaning as defined above; Each R 8 , R 9 and R 10 are each independently a hydrogen atom, C 1-6Alkyl group or C 2-6 alkenyl groups, each of which is optionally hydroxyl or C 1-3 substituted with an alkoxy group; or R 8 , R 9 and R 10 Two of the groups together form C 3-8 Cycloalkyl group or C 5-8 cycloalkenyl groups, each of which optionally contains a hydroxy group, C 1-3 Alkyl group or C 1-3 substituted with an alkoxy group, the other groups having the same meaning as defined above; n is 0 or 1; Y is -CH=CR 11 -group, -CHR 12 -CHR 11 - group or -CH2-C(OH)R 11 - group, and R 11 is a hydrogen atom, a methyl group, or an ethyl group, and R 12 is a hydroxy group or an acetate group; Z is a CHO group, a CHOH group, or a CH(OR a )(OR b ) m group, where m is 0 or 1; R a is C 1-4 Alkyl group, trimethylsilyl group, C(=O)-R c Group, C(=O)-OR c group, CH2(OR c ) group, CH(OR c ) CH3 group, where R c is C 1-4 R is an alkyl group; b is C 1-4 Alkyl group, C(=O)-R c group, where R c is C 1-4 is an alkyl group; or R a and R b Together, C 2-6 represents an alkanediyl group; or Z is CH(OR a )(OR b ) group, where R a and R b are each independently a methyl group or C 3-4 Alkyl group, C(=O)-R c group, where R c is C 1-4 is an alkyl group; or R a and R b Together, C 3-6 Represents an alkanediyl group; However, when X is a group of formula (d), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 At least one group of 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally a hydroxy group or a C 1-3 substituted with an alkoxy group; X is a group of formula (d) and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 If six of the groups are hydrogen atoms, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 The non-hydrogen group in is not a methyl group; X is a group of formula (d) and R 2 , R 3 , R 4 , R 5 , R 6 and R 7 When is a hydrogen atom, R 1 is not a prop-1-en-2-yl group] or mixtures thereof, provided that: 3-(4-(tert-butyl)cyclohex-1-en-1-yl)acrylaldehyde, 3-(4-(tert-butyl)-1-hydroxycyclohexyl)acrylaldehyde, 1-(tert-butyl)-4-(3,3-diethoxyprop-1-en-1-yl)benzene, 2-(4-(tert-butyl)styryl)-1,3-dioxolane, 3-(4-(tert-butyl)-1-hydroxycyclohexyl)allyl acetate, 3-(2-allyl-1-hydroxycyclohexyl)allyl acetate, 4-(tert-butyl)-1-(3-hydroxyprop-1-en-1-yl)cyclohexan-1-ol, 2-allyl-1-(3-hydroxyprop-1-en-1-yl)cyclohexane ... ol, 2-(4-isopropylstyryl)-1,3-dioxane, 2-(4-isopropylstyryl)-4-methyl-1,3-dioxolane, 3-(2-(buta-1,3-dien-1-yl)-1-hydroxycyclohexyl)acrylaldehyde, 3-(5,5-dimethylcyclohex-1-en-1-yl)acrylaldehyde, 3-((1S,5R)-6,6-dimethylbicyclo[3.1.1] (1R,2S,5R)-1-(3-(tert-butoxy)prop-1-en-1-yl)-2-isopropyl-5-methylcyclohexan-1-ol, 2-allyl-1-(3-hydroxyprop-1-en-1-yl)cyclohexan-1-ol, and (3,3-dimethoxyprop-1-en-1-yl)benzene are excluded.

[0008] Description of the Invention Surprisingly, it has now been found that the compounds of formula (I), which are key building blocks of perfuming ingredients, can be advantageously prepared by a cross-metathesis reaction between compounds of formula (II) and compounds of formula (III).The conditions of the present invention allow direct access to the valuable perfuming ingredients 3-(cyclohex-1-en-1-yl)propanal derivatives, 3-(phenyl)propanal derivatives or 5-(phenyl)-4-pentenal of formula (V), using novel intermediates never reported in the art, such as compounds of formula (I) and (IV).

[0009] The first subject of the present invention is therefore a compound of formula [ka] [In the formula, m is 0 or 1; R a is C 1-4 Alkyl group, trimethylsilyl group, C(=O)-R c Group, C(=O)-OR c group, CH2(OR c ) group, CH(OR c ) CH3 group, where R c is C 1-4 R is an alkyl group; b is C 1-4 Alkyl group, C(=O)-R c group, where R c is C 1-4 is an alkyl group; or R a and R b Together, C 2-6 represents an alkanediyl group, and X is a group represented by the formula a), b) or c). [ka] wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom, C 1-6 Alkyl group or C2-6 alkenyl groups, each of which is optionally hydroxyl or C 1-3 substituted with an alkoxy group; or R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 Two of the groups together form C 3-8 Cycloalkyl group or C 5-8 cycloalkenyl groups, each of which optionally contains a hydroxy group, C 1-3 Alkyl group or C 1-3 substituted with an alkoxy group, the other groups having the same meaning as defined above; 8 , R 9 and R 10 are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally hydroxyl or C 1-3 substituted with an alkoxy group; or R 8 , R 9 , R 10 Two of the groups together form C 3-8 Cycloalkyl group or C 5-8 cycloalkenyl groups, each of which optionally contains a hydroxy group, C 1-3 Alkyl group or C 1-3 alkoxy group, the other groups being as defined above; n is 0 or 1, and Y is -CH=CR 11 -group, -CHR 12 -CHR 11 - group or -CH2-C(OH)R 11 - group, where R 11 is a hydrogen atom, a methyl group, or an ethyl group, and R 12 is a hydroxy group or an acetate group; with the proviso that when X is a group of formula b), m is 1. or a mixture thereof, comprising a cross-metathesis step between any one of the stereoisomers of the compound of formula (IIa), (IIb) or (IIc) and any one of the stereoisomers of the compound of formula (III) or a mixture thereof in the presence of a metathesis catalyst. [ka] [In the formula, each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , n and Y have the same meaning as defined above. [ka] wherein m is 0 or 1 when the cross-metathesis step is carried out on a compound of formula (IIa) or (IIc), m is 1 when the cross-metathesis step is carried out on a compound of formula (IIb), and R a is C 1-4 Alkyl group, trimethylsilyl group, C(=O)-R c Group, C(=O)-OR c group, CH2(OR c ) group, CH(OR c ) CH3 group, where R c is C 1-4 R is an alkyl group; b is C 1-4 Alkyl group, C(=O)-R c group, where R c is C 1-4 is an alkyl group; or R a and R b Together, C 2-6 represents an alkanediyl group, R d is a hydrogen atom or CH(OR a )(OR b ) mgroup, where m, R a and R b have the same meaning as defined above]

[0010] For clarity, the wavy bonds in compounds such as those of formula (I) and (III) have the ordinary meaning understood by one of ordinary skill in the art, i.e., that the double bonds may have a cis configuration, a trans configuration, or a mixture thereof.

[0011] For the sake of clarity, expressions such as "any one of its stereoisomers or a mixture thereof" have the usual meaning understood by a person skilled in the art, i.e., the compounds of formulae (I), (II) and (III) may be pure enantiomers or mixtures of enantiomers. In other words, the compounds of formulae (I), (II) and (III) may have at least one stereocenter that may have two different stereochemistries (e.g., R or S). The compounds of formulae (I), (II) and (III) may be in the form of pure enantiomers or even mixtures of enantiomers. The compounds of formulae (I), (II) and (III) may be in the form of pure diastereomers or even mixtures of diastereomers, in the case where the compounds of formulae (I), (II) and (III) have two or more stereoisomers. The compounds of formulae (I), (II) and (III) may be in racemic or scalemic form. Thus, the compounds of formula (I), (II) and (III) can be in the form of one stereoisomer or a composition of matter comprising or consisting of various stereoisomers.Furthermore, said compounds of formula (I) or (III) can be in the form of their E-isomers, Z-isomers or mixtures thereof, for example, the present invention includes compositions of matter consisting of one or more compounds of formula (I) or (III) having the same chemical structure but differing in the configuration of the double bonds.

[0012] The term "optionally" is understood to mean that a particular group that is optionally substituted may or may not be substituted with a particular functional group.

[0013] The terms "alkyl" and "alkenyl" are understood to include branched and straight chain alkyl and alkenyl groups. The terms "alkenyl" and "cycloalkenyl" are understood to include one, two or three olefinic double bonds, preferably one or two olefinic double bonds. In particular, in the case of alkenyl, the olefinic double bond is not a terminal double bond. The terms "cycloalkyl" and "cycloalkenyl" are understood to include monocyclic or fused, spiro and / or bridged bicyclic or tricyclic cycloalkyl and cycloalkenyl groups, preferably monocyclic cycloalkyl and cycloalkenyl groups.

[0014] To be clear, "R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 Two of the groups together form C 3-8 Cycloalkyl group or C 5-8 The phrase "form a cycloalkenyl group" means that the carbon atom to which the two groups are attached is C 5-8 Cycloalkyl group or C 5-8 It is meant to be included in the cycloalkenyl group.

[0015] According to any embodiment of the present invention, when m is 1, R a and R b is C 1-4 Alkyl group, R c is C 1-4 C(=O)-R is an alkyl group c group; or R a and R b Together, C 2-6 In particular, when m is 1, R a , R b are identical.

[0016] According to any embodiment of the present invention, the method of the present invention comprises the step of: [ka] [In the formula, m is 0 or 1; R a is C 1-4 Alkyl group, trimethylsilyl group, C(=O)-R c Group, C(=O)-OR c group, CH2(OR c ) group, CH(OR c ) CH3 group, where R c is C 1-4 R is an alkyl group; b is C 1-4 Alkyl group, C(=O)-R c group, where R c is C 1-4 is an alkyl group; or R a and R b Together, C 2-6 represents an alkanediyl group, and X represents the formula a) or c): [ka] wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally hydroxyl or C 1-3 substituted with an alkoxy group; or R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 Two of the groups together form C 3-8 Cycloalkyl group or C 5-8 cycloalkenyl groups, each of which optionally contains a hydroxy group, C 1-3Alkyl group or C 1-3 substituted with an alkoxy group, the other groups having the same meaning as defined above. or a mixture thereof, comprising a cross-metathesis step between any one of the stereoisomers of the compound of formula (IIa) or (IIc) and any one of the stereoisomers of the compound of formula (III) or a mixture thereof in the presence of a metathesis catalyst. [ka] [In the formula, each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 have the same meaning as defined above] [ka] [In the formula, m is 0 or 1; R a is C 1-4 Alkyl group, trimethylsilyl group, C(=O)-R c Group, C(=O)-OR c group, CH2(OR c ) group, CH(OR c ) CH3 group, where R c is C 1-4 R is an alkyl group; b is C 1-4 Alkyl group, C(=O)-R c group, where R c is C 1-4 is an alkyl group or R a and R b Together, C 2-6 represents an alkanediyl group, R d is a hydrogen atom or CH(OR a )(OR b ) m Based on

[0017] According to any embodiment of the present invention, the method of the present invention comprises the step of: [ka] [In the formula, R a and R b are independent of each other, C 1-4 Alkyl group, C(=O)-R c group, where R c is C 1-4 is an alkyl group; or R a and R b Together, C 2-6 represents an alkanediyl group, and X represents a group represented by formula b): [ka] wherein each R 8 , R 9 and R 10 are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally hydroxyl or C 1-3 substituted with an alkoxy group; or R 8 , R 9 , R 10 Two of the groups together form C 3-8 Cycloalkyl group or C 5-8 cycloalkenyl groups, each of which optionally contains a hydroxy group, C 1-3 Alkyl group or C 1-3 alkoxy group, the other groups being as defined above; n is 0 or 1, and Y is -CH=CR 11 -group, -CHR 12 -CHR 11 - group or -CH2-C(OH)R 11 - group, where R 11 is a hydrogen atom, a methyl group, or an ethyl group, and R 12 is a hydroxy group or an acetate group. or a mixture thereof, comprising a cross-metathesis step between any one of the stereoisomers of the compound of formula (IIb) and any one of the stereoisomers of the compound of formula (III) or a mixture thereof in the presence of a metathesis catalyst. [ka] [In the formula, R 8 , R 9 , R 10 , n and Y have the same meaning as defined above. [ka] [In the formula, R a and R b are independent of each other, C 1-4 Alkyl group, C(=O)-R c group, where R c is C 1-4 is an alkyl group; or R a and R b Together, C 2-6 represents an alkanediyl group, R d is a hydrogen atom or CH(OR a )(OR b ) group]

[0018] According to any embodiment of the present invention, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 At least one group of 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally a hydroxy group or a C 1-3 The other groups may be independently selected from hydrogen atoms, C 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally a hydroxy group or a C1-3 In particular, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 At least three of the groups may be hydrogen atoms, and the other groups may be, independently of one another, hydrogen atoms, C 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally a hydroxy group or a C 1-3 In particular, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 Four of the groups may be hydrogen atoms, and the other groups may be, independently of one another, hydrogen atoms, C 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally a hydroxy group or a C 1-3 In particular, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 One, two, three or four of the groups are C 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally a hydroxy group or a C 1-3 The other groups may be hydrogen atoms. 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 One or two of the groups are C 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally a hydroxy group or a C 1-3It may be substituted with an alkoxy group, and the other groups may be hydrogen atoms.

[0019] According to any embodiment of the present invention, R 3 , R 4 , R 5 、 R 6 and R 7 are each independently a hydrogen atom or C 1-4 The alkyl group may optionally be a hydroxy group or a C 1-3 In particular, R 3 , R 4 , R 5 、 R 6 and R 7 are each independently a hydrogen atom or C 1-3 In particular, R 3 , R 4 , R 5 、 R 6 and R 7 may each independently be a hydrogen atom.

[0020] According to a particular embodiment of the present invention, R 1 , R 2 , R 3 , R 6 and R 7 may each independently be a hydrogen atom; R 4 and R 5 is a hydrogen atom or C 1-3 In particular, R 1 , R 2 , R 3 , R 6 and R 7 may each independently be a hydrogen atom; R 4 may be a hydrogen atom, R 5 is C 1-3 may be an alkyl group, or R 4 is C 1-3 may be an alkyl group, R 5 may be a hydrogen atom.

[0021] According to any embodiment of the present invention, R 8 , R 9 and R 10 At least one group of 1-6 Alkyl group or C 2-6 alkenyl group, which may optionally be a hydroxy group or a C 1-3 The other groups may be independently selected from hydrogen atoms, C 1-6 Alkyl group or C 2-6 alkenyl group, which may optionally be a hydroxy group or a C 1-3 In particular, R 8 , R 9 and R 10 At least one group among the groups may be a hydrogen atom, and the other groups are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 alkenyl group, which may optionally be a hydroxy group or a C 1-3 In particular, R 8 , R 9 and R 10 Two of the groups may be hydrogen atoms, and the other groups are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally a hydroxy group or a C 1-3 In particular, R 8 , R 9 and R 10 One or two of the groups are C 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally a hydroxy group or a C 1-3 The other groups may be hydrogen atoms. 8 , R 9 and R 10 One of the groups is C 1-6 Alkyl group or C 2-6alkenyl groups, each of which is optionally a hydroxy group or a C 1-3 It may be substituted with an alkoxy group, and the other groups may be hydrogen atoms.

[0022] According to any embodiment of the present invention, R 8 and R 9 are each independently a hydrogen atom or C 1-4 The alkyl group may optionally be a hydroxy group or a C 1-3 In particular, R 8 and R 9 are each independently a hydrogen atom or C 1-3 In particular, R 8 and R 9 may each independently be a hydrogen atom.

[0023] According to any embodiment of the present invention, R 10 is a hydrogen atom or C 1-4 The alkyl group may optionally be a hydroxy group or a C 1-3 In particular, R 10 is C 1-4 The alkyl group may optionally be a hydroxy group or a C 1-3 In particular, R 10 is C 1-3 It may be an alkyl group.

[0024] According to any embodiment of the present invention, Y is -CH=CR 11 - group, where R 11 is a hydrogen atom or a methyl group or an ethyl group.

[0025] According to any embodiment of the present invention, R 11 may be a hydrogen atom or a methyl group.

[0026] According to any embodiment of the present invention, X may be a group of formula a) or c). In particular, X may be a group of formula a).

[0027] According to any embodiment of the present invention, the compound of formula (I) has the formula [ka] [In the formula, m, R a , R b , R 1 and R 2 have the same meaning as defined in claim 1. or a mixture thereof, and the compound of formula (II) is of the formula [ka] [In the formula, each R 1 and R 2 have the same meaning as defined in claim 1. The compound may be in the form of any one of the stereoisomers or a mixture thereof.

[0028] According to any embodiment of the present invention, the compound of formula (I) has the formula [ka] [In the formula, m, R a , R b , R 1 and R 2 have the same meaning as defined in claim 1. or a mixture thereof, and the compound of formula (II) is of the formula [ka] [In the formula, each R 1 and R 2 have the same meaning as defined in claim 1. The compound may be in the form of any one of the stereoisomers or a mixture thereof.

[0029] According to any embodiment of the present invention, R 1 is C 1-4 Alkyl group or C 2-4 In particular, R 1 may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group or an n-butyl group. 1 may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a sec-butyl group or an n-butyl group. 1 may be a methyl group.

[0030] According to any embodiment of the present invention, R 2 is a hydrogen atom, C 1-3 Alkyl group or C 2-3 In particular, R 2 may be a hydrogen atom, a methyl group, an ethyl group, a propyl group or an isopropyl group. Even more particularly, R 2 , may be a methyl group.

[0031] According to any embodiment of the present invention, when m is 1, R a and R b are independent of each other, C 1-4 Alkyl group, C(=O)-R c group, where R c is C 1-4 or R may be an alkyl group; a and R b Together, C 2-6 In particular, when m is 1, R a and R b are independent of each other, C 1-3 Alkyl group, C(=O)-R c group, where R c is C 1-3 or R may be an alkyl group; a and R b Together, C 2-4In particular, when m is 1, R a and R b are independent of each other, C 1-2 Alkyl group, C(=O)-R c group, where R c is C 1-2 or R may be an alkyl group; a and R b Together, (CH2) n group, where n is 2 or 3; preferably, n is 2. In particular, when m is 1, R a and R b are each independently an ethyl group, C(=O)-R c group, where R c is a methyl group; or R a and R b Together they represent the (CH2)2 group.

[0032] According to any embodiment of the present invention, when m is 0, R a is C 1-4 Alkyl group, trimethylsilyl group, C(=O)-R c Group, C(=O)-OR c group, CH2(OR c ) group, CH(OR c ) CH3 group, where R c is C 1-4 In particular, when m is 0, R a is C 1-4 Alkyl group, C(=O)-R c group, where R c is C 1-4 In particular, when m is 0, R a is C 1-3 Alkyl group, C(=O)-R c group, where R c is C 1-3 In particular, when m is 0, R a is C 1-2Alkyl group, C(=O)-R c group, where R c is C 1-2 In particular, when m is 0, R a is C(=O)-R c group, where R c is a methyl group.

[0033] According to any embodiment of the present invention, m may be 1.

[0034] According to any embodiment of the present invention, R d may be a hydrogen atom.

[0035] Non-limiting examples of suitable compounds of formula (I) include 1-(3,3-diethoxyprop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol, 3-(1-hydroxy-4,4-dimethylcyclohexyl)allyl acetate, 1-(3-butoxyprop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol, 1-(3-(1-butoxyethoxy)prop-1-en-1-yl)-4,4-dimethylcyclohexan 1-(3-hydroxyprop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol, 3-(1-hydroxy-4,4-dimethylcyclohexyl)acrylaldehyde, 3-(1-hydroxy-4,4-dimethylcyclohexyl)prop-2-en-1,1-diyl diacetate, 1-(2-(1,3-dioxolan-2-yl)vinyl)-4,4-dimethylcyclohexan-1-ol, 3-(4,4-dimethyl 1-(3,3-diethoxyprop-1-en-1-yl)-4,4-dimethylcyclohex-1-ene, 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)vinyl)-1,3-dioxolane, 4-butyl-1-(3,3-diethoxyprop-1-en-1-yl)cyclohexan-1-ol, 3-(4-butyl-1-hydroxycyclohexan-1-ol, hexyl)prop-2-en-1,1-diyl diacetate, 1-(2-(1,3-dioxolan-2-yl)vinyl)-4-butylcyclohexan-1-ol, 4-butyl-1-(3,3-diethoxyprop-1-en-1-yl)cyclohex-1-ene, 3-(4-butylcyclohex-1-en-1-yl)prop-2-en-1,1-diyl diacetate, 2-(2-(4-butylcyclohex-1-en-1-yl)vinyl)-1,3-Dioxolane, 3-(4-butyl-1-hydroxycyclohexyl)acrylaldehyde, 4-butyl-1-(3-hydroxyprop-1-en-1-yl)cyclohexan-1-ol, 3-(4-butyl-1-hydroxycyclohexyl)allyl acetate, 1-(3-butoxyprop-1-en-1-yl)-4-butylcyclohexan-1-ol, 1-(3-(1-butoxyethoxy)prop-1-en-1-yl)-4-butylcyclohexan-1-ol, 1-(3,3-diethoxyprop-1-en-1-yl) -3-Isopropylcyclohexan-1-ol, 3-(1-hydroxy-3-isopropylcyclohexyl)prop-2-ene-1,1-diyl diacetate, 1-(2-(1,3-dioxolan-2-yl)vinyl)-3-isopropylcyclohexan-1-ol, 3-(5-isopropylcyclohex-1-en-1-yl)prop-2-ene-1,1-diyl diacetate, 3-(3-isopropylcyclohex-1-en-1-yl)prop-2-ene-1,1-diyl diacetate, 1-(3,3-diethoxypropan- 1-en-1-yl)-5-isopropylcyclohex-1-ene, 1-(3,3-diethoxyprop-1-en-1-yl)-3-isopropylcyclohex-1-ene, 2-(2-(5-isopropylcyclohex-1-en-1-yl)vinyl)-1,3-dioxolane, 2-(2-(3-isopropylcyclohex-1-en-1-yl)vinyl)-1,3-dioxolane, 3-(1-hydroxy-3-isopropylcyclohexyl)acrylaldehyde, 1-(3-hydroxyprop-1-en-1-yl)-3-isopropyl Pyrcyclohexan-1-ol, 3-(1-hydroxy-3-isopropylcyclohexyl)allyl acetate, 1-(3-butoxyprop-1-en-1-yl)-3-isopropylcyclohexan-1-ol, 1-(3-(1-butoxyethoxy)prop-1-en-1-yl)-3-isopropylcyclohexan-1-ol, 1-(5,5-diethoxy-2-methylpenta-1,3-dien-1-yl)-4-methylbenzene, 5,5-diethoxy-2-methyl-1-(p-tolyl)pent-3-en-2-ol, 5,5-diethoxy-2-methyl-1-(p-tolyl)pent-3-en-1-yl acetate, 5,5-diethoxy-2-methyl-1-(p-tolyl)pent-3-en-1-ol, 4-methyl-5-(p-tolyl)penta-2,4-diene-1,1-diyl diacetate, 4-hydroxy-4-methyl-5-(p-tolyl)pent-2-ene-1,1-diyl diacetate, 5-hydroxy-4-methyl-5-(p-tolyl)pent-2-ene-1,1-diyl diacetate, 4-methyl-5-(p-tolyl) Mention may be made of pent-2-ene-1,1,5-triyl triacetate, 1-(tert-butyl)-4-(3,3-diethoxyprop-1-en-1-yl)benzene, 1-(4-(3,3-diethoxyprop-1-en-1-yl)phenyl)-2-methylpropan-2-ol, 3-(4-(2-hydroxy-2-methylpropyl)phenyl)prop-2-ene-1,1-diyl diacetate, or 3-(4-(tert-butyl)phenyl)prop-2-ene-1,1-diyl diacetate.

[0036] Non-limiting examples of suitable compounds of formula (II) include 4,4-dimethyl-1-vinylcyclohexan-1-ol, 4-butyl-1-vinylcyclohexan-1-ol, 3-isopropyl-1-vinylcyclohexan-1-ol, 4,4-dimethyl-1-vinylcyclohex-1-ene, 4-butyl-1-vinylcyclohex-1-ene, 5-isopropyl-1-vinylcyclohex-1-ene, 3-isopropyl-1-vinylcyclohex-1-ene, 1-methyl-4-(2-methylbuta-1,3-dien-1-yl)benzene, 2-methyl-1-(p-tolyl)but-3-en-2-ol, 2-methyl-1-(p-tolyl)but-3-en-1-yl acetate, 2-methyl-1-(4-vinylphenyl)propan-2-ol or 1-(tert-butyl)-4-vinylbenzene.

[0037] Non-limiting examples of suitable compounds of formula (III) include 3,3-diethoxyprop-1-ene, 1,1,4,4-tetraethoxybut-2-ene, 3,3-dimethoxy-1-propene, 2-vinyl-1,3-dioxolane, 1,2-di(1,3-dioxolan-2-yl)ethene, allyl acetate, allyl methyl carbonate, 1-(allyloxy)butane, 1-(1-(allyloxy)ethoxy)butane, 1,4-dibutoxybut-2-ene, 6,13-dimethyl-5,7,12,14-tetraoxaoctadeca-9-ene, but-2-ene-1,4-diyl diacetate, or prop-2-ene-1,1-diyl diacetate.

[0038] Compounds of formula (II) and (III) are commercially available compounds or can be prepared by several methods, for example 1-methyl-4-(2-methylbuta-1,3-dien-1-yl)benzene can be prepared according to the protocol reported in J. Am. Chem. Soc. 2020, 142, 9932-9937, 4,4-dimethyl-1-vinylcyclohexanol can be prepared from commercially available ketones (vinyl-Grignard addition) according to Angew. Chem. Int. Ed. 2009, 48, 3146 and further converted to 4,4-dimethyl-1-vinylcyclohex-1-ene by acid-catalyzed dehydration according to Angew. Chem. Int. Ed., 2009, 48, 3146.

[0039] According to any embodiment of the present invention, the metathesis catalyst may be a cross-metathesis catalyst. In particular, the metathesis catalyst may be a ruthenium-based catalyst, a molybdenum-based catalyst, a rhenium-based catalyst, or a tungsten-based catalyst. In particular, the metathesis catalyst may be a ruthenium-based catalyst. The ruthenium-based metathesis catalyst may be a ruthenium (II) carbenoid complex. A more detailed description of the nature and type of the ruthenium-based metathesis catalyst used in the method of the present invention is not warranted here and is in any case not exhaustive, and the skilled person may select them based on his or her common sense. Said catalysts are in any case described in references such as Grubbs, RH Handbook of Metathesis; Wiley-VCH: New York, 2003; 1204 pages, 3 volumes, The Strem Chemiker - Vol. XXVIII No. 1, June, 2015, pages 1-24, Booklet Strem Metathesis Catalysts 2 / 2020, RH Grubbs, AG Wenzel, DJ OLeary, E. Khosravi, Handbook of Metathesis, Wiley-VCH, Weinheim, 2015, K. Grela, Olefin Metathesis: Theory and Practice, Wiley, Hoboken, 2014 or other works of a similar nature, as well as in the extensive patent literature in the field of metathesis processes. Non-limiting examples of suitable metathesis catalysts include (1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), (1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)diiodo(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), (1,3-Dimesitylimidazolidin-2-ylidene)dichloro(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), benzylidene-bis(tricyclohexylphosphine)dichlororuthenium, dichloro[1,3-bis(2,6-isopropylphenyl)-2-imidazolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), [1,3-bis(2,6- [1,3-bis(2,6-di-i-propylphenyl)imidazolidin-2-ylidene](2-i-propoxy-5-nitrobenzylidene)ruthenium(II) diiodide, [1,3-bis(2,6-di-i-propylphenyl)imidazolidin-2-ylidene](2-i-propoxy-5-nitrobenzylidene)ruthenium(II) dichloride, (1,3-dimesitylimidazolidin-2-ylidene)diiodo(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), bis(1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidinide (1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene)dichloro(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), (1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene)diiodo(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl) -2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), dichloro[1,3-bis(2-methylphenyl)-2-imidazolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), (2-(2,6-diethylphenyl)-3,3-dimethyl-2-azaspiro[4.5]decan-1-yl)(2-isopropoxy-5-nitrobenzylidene)ruthenium(II) dichloride, [2-(1-methylethoxy-O)phenylmethyl-C](nitrato-O,O′){rel-(2R,5R,7R)-Adamantane-2,1-diyl[3-(2,4,6-trimethylphenyl)-1-imidazolidinyl-2-ylidene]}ruthenium, dichloro(2-isopropoxyphenylmethylene)(tricyclohexylphosphine)ruthenium(II), dichloro(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II), 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5 -(N,N-Dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (resin supported), tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene][3-phenyl-1H-inden-1-ylidene]ruthenium(II) dichloride, dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II ), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitrophenolyl]-[3-phenyl-1H-inden-1-ylidene]ruthenium(II) chloride, dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][[5-[(dimethylamino)sulfonyl]-2-(1-methylethoxy-O)phenyl]methylene-C]ruthenium(II), dichloro[1,3-bis(2 -methylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-methyl-2-butenylidene)(tricyclohexylphosphine)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-methyl-2-butenylidene)(dipyridine)ruthenium(II), [1,3-bis(2,4,6-trimethylphenyl)-4-[(trimethylammonio)methyl]imidazolidin-2-ylidene]-(2-i-propoxy-5-nitrobenzylidene)dichlororuthenium(II) chloride, dichloro[1-(2,6-diisopropylphenyl)-2,2,4-trimethyl-4-phenyl-5-pyrrolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene]dichloro[(2-isopropoxy)(5-trifluoroacetamido)benzylidene]ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](2-methoxyphenylmethylene)ruthenium(II), Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-methyl-2-butenylidene)(dipyridine)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)(diphenylmethoxyphosphine)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)(triphenyl phosphine)ruthenium(II), dichloro[1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)diphenylphenoxyphosphine]ruthenium(II), dichloro[1,3-bis(2-isopropylphenyl)-2-imidazolidinylidene](2-isopropoxyphenylmethylphosphine)ruthenium(II) dichloro[1-(2,4,6-trimethylphenyl)-2,2,4-trimethyl-4-phenyl-5-pyrrolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), dichloro[1-(2,6-diisopropylphenyl)-2,2,4-trimethyl-4-phenyl-5-pyrrolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), dichloro(3-methyl-2-butenylidene)bis(tricyclohexylphosphine)ruthenium(II), dichloro[1,3- Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][2-(N,N-dimethylamino)-phenylmethylene]ruthenium(II), dichloro[1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene][2-(N,N-dimethylamino)-phenylmethylene]ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tri-n-butylphosphine)ruthenium(II), dichlorobis[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)ruthenium(II), dichlorobis[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), (1,3-di-o-tolylimidazolidin-2-ylidene)dichloro(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), dichloro(2-isopropoxy-5-nitrophenylmethylene)(tricyclohexylphosphine)ruthenium(II ), 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)chloro(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(II), 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)chloro(tricyclohexylphosphine)-(2-oxo-5-nitrobenzylidene)ruthenium(II), 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)iodo(tricyclohexylphosphine)-(2-oxobenzylidene) (1,3-dimesitylimidazolidin-2-ylidene)dichloro(2-((2-ethoxy-2-oxoethylidene)amino)benzylidene)ruthenium(II), (1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((2-ethoxy-2-oxoethylidene)amino)benzylidene)ruthenium(II), (4-((4-ethyl-4-methylpiperazin-1-ium-1-yl)methyl)-1,3-dimesitylimidazolidin-2-ylidene (4-((4-ethyl-4-methylpiperazin-1-ium-1-yl)methyl)-1,3-dimesitylimidazolidin-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II) hexafluorophosphate, (1,3-dimesitylimidazolidin-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II) hexafluorophosphate, (1,3-Dimesityl-4-((trimethylammonio)methyl)imidazolidin-2-ylidene)dichloro(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), (1,3-Dimesityl-4-((trimethylammonio)methyl)imidazolidin-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II) tetrafluoroborate, (1,3-Bis(2,6-diisopropylphenyl)-4-((4-ethyl-4-methylpiperazin-1-ium-1-yl)methyl)imidazolidin-2-ylidene)dichloro(2- isopropoxybenzylidene)ruthenium(II) chloride, (1,3-bis(2,6-diisopropylphenyl)-4-((4-ethyl-4-methylpiperazin-1-ium-1-yl)methyl)imidazolidin-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II) hexafluorophosphate, bis(2-(2,6-diethylphenyl)-3,3-dimethyl-2-azaspiro[4.5]decan-1-ylidene)dichloro(3-phenyl-1H-inden-1-ylidene)ruthenium(II) dichloromethane complex, [1, 3-Bis(2,6-di-i-propylphenyl)imidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(II) chloride, bis(tricyclohexylphosphine)[(phenylthio)methylene]ruthenium(II) dichloride, [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(2-methylphenyl)imino]methyl]phenolyl]-[3-phenyl-1H-inden-1-ylidene]ruthenium(II) chloride, 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(2-methylphenyl)imino]methyl]phenolyl]-[3-phenyl-1H-inden-1-ylidene]ruthenium(II) chloride, trimethylphenyl)-2-imidazolidinylidene)(3-phenyl-1H-inden-1-ylidene)(4,5-dichloro-1,3-diethyl-1,3-dihydro-2H-imidazol-2-ylidene)ruthenium(II) dichloride, 3-phenyl-1H-inden-1-ylidene[bis(i-butylphoban)]ruthenium(II) dichloride, {[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methylene}(tricyclohexylphosphine)ruthenium(II) dichloride, tricyclohexylphosphine[1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][(phenylthio)methylene]ruthenium(II) dichloride, tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene][2-thienylmethylene]ruthenium(II) dichloride, tricyclohexylphosphine[2,4-dihydro-2 ,4,5-triphenyl-3H-1,2,4-triazol-3-ylidene][2-thienylmethylene]ruthenium(II) dichloride, tricyclohexylphosphine[4,5-dimethyl-1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene][2-thienylmethylene]ruthenium(II) dichloride, tri(i-propoxy)phosphine(3-phenyl-1H-isopropyl)phosphine(1H-isopropyl) dichloro[1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene][(5-(2-ethoxy-2-oxoethanamide))-(2-isopropoxy)benzylidene]ruthenium(II), dichloro[1, 3-Bis(2,6-diisopropylphenyl)-2-imidazolidinylidene][(2-isopropoxy)(5-pentafluorobenzoylamino)benzylidene]ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]{[5-(2-ethoxy-2-oxoethanamido)]-2-isopropoxybenzylidene}ruthenium(II), Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][(2-isopropoxy)(5-pentafluorobenzoylamino)benzylidene]ruthenium(II), (1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-3-methyl-1-oxobutan-2-yl)oxy)benzylidene)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)(pyridyl)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)(pyridyl)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][(2-isopropoxy)(5-trifluoroacetamido)benzylidene]ruthenium(II), dichloro[1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene][(5-isobutoxycarbonylamino)-(2-isopropoxy)benzylidene]ruthenium(II), or dichloro[1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)(triphenylphosphine)ruthenium(II). Even more particularly, the metathesis catalyst may be (1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), (1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)diiodo(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), (1,3-dimesitylimidazolidin-2-ylidene)dichloro(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), benzylidene-bis(tricyclohexylphosphine)dichlororuthenium, dichloro[1,3-bis(2,6-isopropylphenyl)-2-imidazolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), [1,3-bis(2,6-di-i-propylphenyl)imidazolidin-2-ylidene)(2-i-propoxy-5-nitrobenzylidene)ruthenium (II) diiodide, 1,3-bis(2,6-di-i-propylphenyl)imidazolidin-2-ylidene)(2-i-propoxy-5-nitrobenzylidene)ruthenium(II) dichloride, (1,3-dimesitylimidazolidin-2-ylidene)diiodo(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), bis(1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene)(3-phenyl-1H-inden-1-ylidene)ruthenium(II) II) dichloride, (1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene)dichloro(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), (1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene)diiodo(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), dichloro[1,3-bis(2-methylphenyl)-2-imidazolidinylidene](2-isopropoxyfuran) 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (resin supported), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitrophenolyl]-[3-phenyl-1H-inden-1-ylidene]ruthenium(II) chloride, dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][[5-[(dimethylamino)sulfonyl]-2-(1-methylethoxy-O)phenyl]methylene-C]ruthenium(II), dichloro[1-(2,6-diisopropylphenyl) -2,2,4-trimethyl-4-phenyl-5-pyrrolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene]dichloro[(2-isopropoxy)(5-trifluoroacetamido)benzylidene]ruthenium(II), dichloro[1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), dichloro[1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), Ruthenium(II), dichloro[1-(2,6-diisopropylphenyl)-2,2,4-trimethyl-4-phenyl-5-pyrrolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), dichloro[1-(2,6-diisopropylphenyl)-2,2,4-trimethyl-4-phenyl-5-pyrrolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), dichloro[1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene][(2-isopropoxy)(5-pentene dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][(2-isopropoxy)(5-pentafluorobenzoylamino)benzylidene]ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][(2-isopropoxy)(5-pentafluorobenzoylamino)benzylidene]ruthenium(II), (1,3-bis(2,6-Diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-3-methyl-1-oxobutan-2-yl)oxy)benzylidene)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)(pyridyl)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][(2-isopropoxy) (5-trifluoroacetamido)benzylidene]ruthenium(II), dichloro[1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene][(5-isobutoxycarbonylamino)-(2-isopropoxy)benzylidene]ruthenium(II), and dichloro[1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)(triphenylphosphine)ruthenium(II).

[0040] The metathesis catalyst can be added to the reaction medium of the process of the invention in a wide range of concentrations. As non-limiting examples, values ​​of the catalyst concentration can be mentioned ranging from 2 ppm to 200000 ppm relative to the total amount of compounds of formula (II). Preferably, the catalyst concentration is comprised between 10 ppm and 50000 ppm, or even between 30 ppm and 2000 ppm. It goes without saying that the process also works with more catalyst. However, the optimum concentration of the catalyst depends, as known by the skilled person, on the nature of the catalyst, the nature of the substrate, the temperature and the desired reaction time.

[0041] According to any embodiment of the present invention, a scavenger can be added to the method of the present invention. Specifically, the scavenger can be added after 30 minutes, 1 hour, 2 hours, 3 hours, 10 hours, 20 hours, 24 hours, or 36 hours. Non-limiting examples of suitable scavenger include amines, 1,4-bis(2-isocyanopropyl)piperazine, pyridine, imidazole nitriles (polynitriles), sulfoxides such as DMSO, amides, thiols, Pb(OAc)4, 2-mercaptonicotinic acid (MNA), cysteine, chelating phosphines, triphenylphosphine oxide (TPPO), di(ethylene glycol) vinyl ether, phosphane triyl trimethanol (THMP), Na2S2O5, H2O2, or silica-based heterogeneous particles.

[0042] The scavenger can be added to the reaction medium of the method of the present invention in a wide range of concentrations. As a non-limiting example, the concentration value of the scavenger can be 5 to 10 equivalents relative to the amount of metathesis catalyst. It goes without saying that the optimum concentration of the scavenger depends on the nature of the scavenger, the nature of the substrate, the temperature, the catalyst used in the process, and the desired reaction time, as known by those skilled in the art.

[0043] The compound of formula (III) can be added to the reaction medium of the method of the present invention in a wide range of concentrations. As a non-limiting example, concentrations ranging from 0.5 equivalents to 50 equivalents, or even from 1 equivalent to 5 equivalents relative to the amount of the compound of formula (II), can be mentioned as the concentration value of the compound of formula (III). It goes without saying that the optimum concentration of the compound of formula (III) depends on the nature of the compound of formula (III), the nature of the compound of formula (II), the temperature, the catalyst used in the process, and the desired reaction time, as known by those skilled in the art.

[0044] The process of the present invention may be carried out under batch, semi-batch or continuous conditions.

[0045] The reaction can be carried out without a solvent. If a solvent is required or used for practical reasons, any solvent currently used in metathesis reactions can be used for the purposes of the present invention. Non-limiting examples include C toluene and xylene. 6-10 Aromatic solvents; C such as hexane, heptane, or cyclohexane 5-12 Hydrocarbon solvents; C such as tetrahydrofuran, 2-MeTHF, MTBE 4-8 Ethers; C such as ethyl acetate and i-PrOAc 4-10 Esters; C such as dichloromethane, dichloroethane, or chlorobenzene 1-2 Chlorinated hydrocarbons; C such as isopropanol, methanol, or ethanol 2-6 Primary or secondary alcohols; C such as acetone, HOAc 2-6 These include polar solvents and water (neutral / acidic); or mixtures thereof. In particular, the solvent may be a solvent such as dichloromethane, toluene, or no solvent. The choice of solvent is made according to the nature of the metathesis catalyst and the nature of the compounds of formula (II) and (III). The skilled person is fully capable of choosing the most convenient solvent in each case to optimize the process of the present invention.

[0046] The temperature of the method of the present invention may be 20° C. to 110° C., preferably in the range of 20° C. to 80° C., more preferably in the range of 20° C. to 50° C. Of course, the skilled person can also select the preferred temperature depending on the melting and boiling points of the starting materials and the final product, as well as the desired reaction or conversion time.

[0047] The process of the invention can be carried out at atmospheric pressure or at reduced pressure. The process of the invention can be carried out under an inert atmosphere such as nitrogen and / or argon.

[0048] According to the method of the present invention, 1,1'-(ethene-1,2-diyl)bis(4,4-dimethylcyclohexan-1-ol), 1,2-bis(4,4-dimethylcyclohex-1-en-1-yl)ethene, 4,4'-(2,5-dimethylhexa-1,3,5-triene-1,6-diyl)bis(methylbenzene), 2,5-dimethyl-1,6-di-p-tolylhex-3-ene-1,6-diyl diacetate, 2,5-dimethyl-1,6-di-p-tolylhex-3-ene-2,5-diol, 1,1'-(ethene-1,2-diylbis(4,1-phenylene))bis(2-methylpropane-2 By-products such as dimers of compounds of formula (II) such as 1,1,4,4-tetraethoxybut-2-ene, 1,1,4,4-tetramethoxybut-2-ene, but-2-ene-1,1,4,4-tetrayltetraacetate and dimers of compounds of formula (III) such as 1,2-di(1,3-dioxolan-2-yl)ethene, but-2-ene-1,4-diyldiacetate, 1,4-dibutoxybut-2-ene, 6,13-dimethyl-5,7,12,14-tetraoxaoctadec-9-ene may occur. Most of the by-products formed can be recycled in the process of the present invention. In addition, unreacted starting materials can also be recycled in the process of the present invention.

[0049] According to the method of the present invention, [ka] wherein X has the same meaning as defined above. The aldehyde may occur in the form of any one of the stereoisomers or in a mixture thereof.

[0050] According to any embodiment of the present invention, the compound of formula (I) has the formula (V) [ka] in which X is a group of formula a) or b) having the same meaning as defined above. The compound of formula (IIa) or (IIb) [wherein Y is -CH=CR 11 - and R 11 is a hydrogen atom or a methyl group or an ethyl group] and a compound of formula (III) [wherein m is 1], the compound of formula (V) can be prepared by a method including a deprotection step and a hydrogenation step. For clarity, the expression "including a deprotection step and a hydrogenation step" means that the deprotection reaction and the hydrogenation reaction can be carried out in any order. In other words, the method of the present invention can include a hydrogenation step after the deprotection step, or a deprotection step after the hydrogenation step.

[0051] According to a particular embodiment, the process for preparing a compound of formula (V) as defined above comprises the steps of: i) Formula (IIa) or (IIb) [wherein Y is -CH=CR 11 - and R 11 is a hydrogen atom, a methyl group, or an ethyl group] with a compound of formula (III) [wherein m is 1 and R a , R b and R d has the same meaning as defined above) to obtain a compound of formula (I) in which X is a group of formula a) or b) with the same meaning as defined above; ii) deprotection to obtain a compound of formula (IV), in which X is a group of formula a) or b) having the same meaning as defined above; iii) hydrogenation to obtain a compound of formula (V); may include.

[0052] According to another particular embodiment, the process for the preparation of a compound of formula (V) as defined above comprises the steps of: i) Formula (IIa) or (IIb) [wherein Y is -CH=CR 11 - and R 11is a hydrogen atom, a methyl group, or an ethyl group] with a compound of formula (III) [wherein m is 1 and R a , R b and R d has the same meaning as defined above) to obtain a compound of formula (I) in which X is a group of formula a) or b) with the same meaning as defined above; ii) Hydrogenation to the formula [ka] in which X is a group of formula a) or b) having the same meaning as defined above, and R a and R b has the same meaning as defined above, iii) deprotection to obtain a compound of formula (V); may include.

[0053] The cross-metathesis step comprises reacting a compound represented by formula (IIc) or (IIb) 12 -CHR 11 - group or -CH2-C(OH)R 11 - group, and R 11 is a hydrogen atom, a methyl group, or an ethyl group, and R 12 is a hydroxy or acetate group and a compound of formula (III) where m is 1, the above defined process for the preparation of a compound of formula (V) further comprises an elimination / dehydration step carried out before or after the deprotection step, in particular before the deprotection step. In particular, the deprotection step and the elimination / dehydration step can be carried out in one pot.

[0054] According to any embodiment of the present invention, the deprotection, hydrogenation and optional elimination / dehydration steps to form a compound of formula (V) can be carried out under conventional conditions known to those skilled in the art, who are able to select the most suitable conditions to carry out said conversions.

[0055] When a cross-metathesis step is carried out between a compound of formula (II) and a compound of formula (III) (wherein m is 0), the compound of formula (V) defined above can be prepared by a process comprising a deprotection step and an isomerization step. For clarity, the expression "comprising a deprotection step and an isomerization step" means that the deprotection reaction and the isomerization reaction can be carried out in any order. In other words, the process of the present invention can comprise an isomerization step after a deprotection step, or a deprotection step after an isomerization step.

[0056] According to a particular embodiment, the process for preparing a compound of formula (V) as defined above comprises the steps of: i) reacting a compound of formula (II) with a compound of formula (III) a and R d has the same meaning as defined above; ii) Deprotection to give the formula [ka] in which X is a group of formula a) or b) having the same meaning as defined above. obtaining a compound of formula (I); iii) isomerization to obtain a compound of formula (V); may include.

[0057] In case the cross-metathesis step is carried out between a compound of formula (II) of formula (IIc) and a compound of formula (III) where m is 0, the process for the preparation of a compound of formula (V) as defined above further comprises an elimination step carried out before or after the deprotection step, in particular before the deprotection step. In particular, the deprotection and elimination steps can be carried out in one pot.

[0058] According to any embodiment of the present invention, the isomerization, deprotection and, optionally, elimination steps to form compounds of formula (V) can be carried out under conventional conditions known to those skilled in the art, such as, for example, for isomerization, Journal of the American Chemical Society, 2006, 128(4), 1360-1370 or Chimia, 2009, 63(1-2), 35-37. The skilled artisan can select the most suitable conditions to carry out said conversions.

[0059] The compounds of formulae (I), (IV) and (VII) are generally novel compounds and exhibit many advantages as described above and illustrated in the examples.

[0060] Another subject of the invention is therefore a compound of formula [ka] [In the formula, X is a compound represented by the formula b) or d). [ka] In one of the stereoisomers of the group where p is 0 when the dotted line is a carbon-carbon double bond, and p is 1 when the dotted line is a carbon-carbon single bond; Each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally hydroxyl or C 1-3 substituted with an alkoxy group; or R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 Two of the groups together form C3-8 Cycloalkyl group or C 5-8 cycloalkenyl groups, each of which optionally contains a hydroxy group, C 1-3 Alkyl group or C 1-3 substituted with an alkoxy group, the other groups having the same meaning as defined above; Each R 8 , R 9 and R 10 are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally hydroxyl or C 1-3 substituted with an alkoxy group; or R 8 , R 9 and R 10 Two of the groups together form C 3-8 Cycloalkyl group or C 5-8 cycloalkenyl groups, each of which optionally contains a hydroxy group, C 1-3 Alkyl group or C 1-3 substituted with an alkoxy group, the other groups having the same meaning as defined above; n is 0 or 1; Y is -CH=CR 11 -group, -CHR 12 -CHR 11 - group or -CH2-C(OH)R 11 - group, and R 11 is a hydrogen atom, a methyl group, or an ethyl group, and R 12 is a hydroxy group or an acetate group; Z is a CHO group, a CHOH group, or a CH(OR a )(OR b ) m group, where m is 0 or 1; R a is C 1-4 Alkyl group, trimethylsilyl group, C(=O)-R c Group, C(=O)-OR c group, CH2(OR c ) group, CH(OR c ) CH3 group, where R c is C1-4 R is an alkyl group; b is C 1-4 Alkyl group, C(=O)-R c group, where R c is C 1-4 is an alkyl group; or R a and R b Together, C 2-6 represents an alkanediyl group; Z is CH(OR a )(OR b ) group, where R a and R b are each independently a methyl group or C 3-4 Alkyl group, C(=O)-R c group, where R c is C 1-4 is an alkyl group; or R a and R b Together, C 3-6 Represents an alkanediyl group; However, when X is a group of formula (d), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 At least one group of 1-6 Alkyl group or C 2-6 alkenyl groups, each of which is optionally a hydroxy group or a C 1-3 substituted with an alkoxy group; X is a group of formula (d) and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 If six of the groups are hydrogen atoms, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7The non-hydrogen group in is not a methyl group; X is a group of formula (d) and R 2 , R 3 , R 4 , R 5 , R 6 and R 7 When is a hydrogen atom, R 1 is not a prop-1-en-2-yl group] or mixtures thereof, provided that: 3-(4-(tert-butyl)cyclohex-1-en-1-yl)acrylaldehyde, 3-(4-(tert-butyl)-1-hydroxycyclohexyl)acrylaldehyde, 1-(tert-butyl)-4-(3,3-diethoxyprop-1-en-1-yl)benzene, 2-(4-(tert-butyl)styryl)-1,3-dioxolane, 3-(4-(tert-butyl)-1-hydroxycyclohexyl)allyl acetate, 3-(2-allyl-1-hydroxycyclohexyl)allyl acetate, 4-(tert-butyl)-1-(3-hydroxyprop-1-en-1-yl)cyclohexan-1-ol, 2-allyl-1-(3-hydroxyprop-1-en-1-yl)cyclohexane ... ol, 2-(4-isopropylstyryl)-1,3-dioxane, 2-(4-isopropylstyryl)-4-methyl-1,3-dioxolane, 3-(2-(buta-1,3-dien-1-yl)-1-hydroxycyclohexyl)acrylaldehyde, 3-(5,5-dimethylcyclohex-1-en-1-yl)acrylaldehyde, 3-((1S,5R)-6,6-dimethylbicyclo[3.1.1] (1R,2S,5R)-1-(3-(tert-butoxy)prop-1-en-1-yl)-2-isopropyl-5-methylcyclohexan-1-ol, 2-allyl-1-(3-hydroxyprop-1-en-1-yl)cyclohexan-1-ol, and (3,3-dimethoxyprop-1-en-1-yl)benzene are excluded.

[0061] In particular, when X is of formula b), Z is CH(OR a )(ORb ) group, where R a and R b are identical and are either methyl or C 3-4 Alkyl group, C(=O)-R c group, where R c is C 1-4 is an alkyl group; or R a and R b Together, C 3-6 Represents an alkanediyl group.

[0062] In particular, when Z is a CH2OH group, X is of formula d), where the dotted line is a carbon-carbon single bond and p is 1.

[0063] Typical modes for carrying out the method of the invention are reported herein below in the Examples. EXAMPLES

[0064] The invention will now be described in more detail by the following examples, in which the abbreviations have their usual meaning in the art and temperatures are given in degrees Celsius (° C.). NMR spectra were obtained using a 400 MHz ( 1 H) and 100MHz ( 13 C) or Bruker Avance II Ultrashield 400 plus, 500MHz ( 1 H) and 125MHz ( 13 C) operating at Bruker Avance III 500 or 600MHz ( 1 H) and 150MHz ( 13 C). Spectra were internally referenced to tetramethylsilane at 0.0 ppm. 1 H NMR signal shifts are expressed in δ ppm and coupling constants (J) are expressed in Hz with the following multiplicities: s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; and b, broad (indicating non-separable bonds) and were interpreted using Bruker Topspin software.13 C NMR data are expressed as chemical shifts δ ppm and hybridizations obtained from DEPT 90 and DEPT 135 experiments, where C is quaternary (s); CH is methine (d); CH is methylene (t); and CH is methyl (q).

[0065] [Example 1] Cross metathesis of 4,4-dimethyl-1-vinylcyclohexan-1-ol with 3,3-diethoxyprop-1-ene to produce (E)-1-(3,3-diethoxyprop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol To a stirred solution of 2.5 g of 4,4-dimethyl-1-vinylcyclohexan-1-ol (98% pure, 15.883 mmol) and 8.79 g of 3,3-diethoxyprop-1-ene (63.533 mmol, 4 eq) in 10 mL of EtOAc at 50 °C under argon atmosphere was added 10 mg (0.0127 mmol, 0.080 mol%) of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6). Next, 50 mg (0.0637 mmol, 0.40 mol%, GreenCat) was dissolved in 5 mL of EtOAc and added over 3 h using a syringe pump. After adding 148 mg of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4), the mixture was stirred at room temperature for 1 h and the solvent was evaporated under reduced pressure. The crude was purified by column chromatography (330 g cartridge, Cyclo 9 / AcOEt 1 to Cyclo 8 / AcOEt 2) to give 2.98 g (95% purity, 11.04 mmol, 69.5% yield) of (E)-1-(3,3-diethoxyprop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol and 2.9 g (25.4 mmol) of (E)-1,1,4,4-tetraethoxybut-2-ene. Unreacted 3,3-diethoxyprop-1-ene and 4,4-dimethyl-1-vinylcyclohexan-1-ol could also be isolated. (E)-1,1'-(ethene-1,2-diyl)bis(4,4-dimethylcyclohexan-1-ol) was observed only in small amounts (1.4%) in the GC of the crude.

[0066] (E)-1-(3,3-diethoxyprop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol [ka]

[0067] (E)-1,1,4,4-Tetraethoxybut-2-ene [ka]

[0068] (E)-1,1'-(ethene-1,2-diyl)bis(4,4-dimethylcyclohexan-1-ol) [ka]

[0069] (E)-1-(3,3-Diethoxyprop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol can be easily deprotected by the addition of drops of HPO and water at room temperature to give (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)acrylaldehyde (quantitative yield): 98 mg (0.382 mmol) of (E)-1-(3,3-diethoxyprop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol was dissolved in 2 mL of THF. Then, 1 mL of water and one drop (2 mg, 5 mol%) of phosphoric acid (85%) were added. The mixture was stirred at room temperature for 10 min and diluted with 5 mL of diethyl ether. After washing with 2 mL of saturated aqueous NaHCO3, the organic phase was dried over Na2SO4. The solvent was evaporated under reduced pressure to give 68 mg (0.373 mmol, 98% yield) of pure (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)acrylaldehyde.

[0070] (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)acrylaldehyde [ka]

[0071] (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)acrylaldehyde could be converted to (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)acrylaldehyde in the presence of HPO and water droplets at 100° C. (35 min): To a stirred solution of 40 mg (0.2195 mmol) of (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)acrylaldehyde in toluene was added phosphoric acid (85%) (1 drop). The mixture was stirred at 100 °C for 35 min and diluted with 5 mL of diethyl ether. After washing with 2 mL of saturated aqueous NaHCO3 and brine, the organic phase was dried over Na2SO4. The solvent was evaporated under reduced pressure to give 30 mg (0.1826 mmol, 83% yield) of pure (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)acrylaldehyde.

[0072] (E)-3-(4,4-Dimethylcyclohex-1-en-1-yl)acrylaldehyde [ka]

[0073] [Example 2] Cross metathesis of 1-vinylcyclohexan-1-ol with 3,3-diethoxyprop-1-ene to produce (E)-1-(3,3-diethoxyprop-1-en-1-yl)cyclohexan-1-ol Following the procedure of Example 1, (E)-1-(3,3-diethoxyprop-1-en-1-yl)cyclohexan-1-ol was prepared from 1-vinylcyclohexan-1-ol (86% yield).

[0074] (E)-1-(3,3-diethoxyprop-1-en-1-yl)cyclohexan-1-ol [ka]

[0075] (E)-1-(3,3-Diethoxyprop-1-en-1-yl)cyclohexan-1-ol can be converted to (E)-3-(1-hydroxycyclohexyl)acrylaldehyde and further to (E)-3-(cyclohex-1-en-1-yl)acrylaldehyde under Dean-Stark conditions (toluene or cyclohexane) in the presence of acid (pTsOH, oxalic acid, tartaric acid, KHSO4).

[0076] (E)-3-(1-hydroxycyclohexyl)acrylaldehyde [ka]

[0077] (E)-3-(Cyclohex-1-en-1-yl)acrylaldehyde [ka]

[0078] [Example 3] Cross metathesis of 4,4-dimethyl-1-vinylcyclohexan-1-ol with 2-vinyl-1,3-dioxolane to produce (E)-1-(2-(1,3-dioxolan-2-yl)vinyl)-4,4-dimethylcyclohexan-1-ol To a stirred solution of 2.0 g 4,4-dimethyl-1-vinylcyclohexan-1-ol (96.3% purity, 12.486 mmol) and 3.75 g 2-vinyl-1,3-dioxolane (37.459 mmol, 3 eq) at 40 °C under argon atmosphere was added 50.8 mg (0.0648 mmol, 0.5 mol%) of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6). After 20 min at 40° C., 25.4 mg (0.032 mmol, 0.26 mol%) of GreenCat was added and the mixture was stirred for 20 min at 40° C. 107 mg of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4) was added and the mixture was stirred at room temperature for 1 h. The crude material (5.29 g) was purified by column chromatography (330 g cartridge, DCM 95 / AcOEt 5 to DCM 90 / AcOEt 10) to give 2.26 g (9.99 mmol, 80.0% yield) of (E)-1-(2-(1,3-dioxolan-2-yl)vinyl)-4,4-dimethylcyclohexan-1-ol, 0.120 g (0.658 mmol, 5.3% yield) of (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)acrylaldehyde and 424 mg (2.45 mmol) of (E)-1,2-di(1,3-dioxolan-2-yl)ethene. Unreacted 2-vinyl-1,3-dioxolane (2.26 g, 22.5 mmol) and 4,4-dimethyl-1-vinylcyclohexan-1-ol (GC crude: 4.6%) could also be isolated. (E)-1,1'-(ethene-1,2-diyl)bis(4,4-dimethylcyclohexan-1-ol) was only observed in small amounts in the GC of the crude (1.7%, isolated 90 mg).

[0079] (E)-1-(2-(1,3-dioxolan-2-yl)vinyl)-4,4-dimethylcyclohexan-1-ol [ka]

[0080] (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)acrylaldehyde [ka]

[0081] (E)-1,2-di(1,3-dioxolan-2-yl)ethene: [ka]

[0082] (E)-1,1'-(ethene-1,2-diyl)bis(4,4-dimethylcyclohexan-1-ol) [ka]

[0083] (E)-1-(2-(1,3-dioxolan-2-yl)vinyl)-4,4-dimethylcyclohexan-1-ol can be converted to (E)-2-(2-(4,4-dimethylcyclohex-1-en-1-yl)vinyl)-1,3-dioxolane under Dean-Stark conditions (toluene or cyclohexane) in the presence of acid (pTsOH, oxalic acid, tartaric acid, KHSO4).

[0084] (E)-2-(2-(4,4-dimethylcyclohex-1-en-1-yl)vinyl)-1,3-dioxolane [ka]

[0085] (E)-1-(2-(1,3-dioxolan-2-yl)vinyl)-4,4-dimethylcyclohexan-1-ol can be converted to (E)-2-(2-(4,4-dimethylcyclohex-1-en-1-yl)vinyl)-1,3-dioxolane in the presence of POCl3 / pyridine (0 °C to room temperature).

[0086] (E)-2-(2-(4,4-dimethylcyclohex-1-en-1-yl)vinyl)-1,3-dioxolane can be deprotected in the presence of water and HPO (10 mol%) at room temperature or in the presence of AcOH / water at 50 °C (30 min) to give (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)acrylaldehyde in quantitative yield.

[0087] (E)-1-(2-(1,3-dioxolan-2-yl)vinyl)-4,4-dimethylcyclohexan-1-ol can be deprotected in the presence of water and HPO (10 mol%) at room temperature or in the presence of AcOH / water at 50° C. (30 min) to give (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)acrylaldehyde.

[0088] [Example 4] Preparation of (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)allyl acetate by cross metathesis of 4,4-dimethyl-1-vinylcyclohexan-1-ol with allyl acetate To a stirred solution of 4,4-dimethyl-1-vinylcyclohexan-1-ol (0.964 g, 6.25 mmol) and allyl acetate (1.95 g, 19.49 mmol) at 40° C., 1.25 mol % of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6) was added in small portions (0.25 mol % x 6, 10 min each) over 1 h. After the last addition, the mixture was cooled to room temperature and stirred for 1 week. Then, 89.1 mg of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4) was added and the mixture was stirred at room temperature for 30 min. The crude (2.35 g) was purified by column chromatography (80 g cartridge, cyclohexane 9 / MTBE 1 to cyclohexane 65 / MTBE 35) to give 0.590 g (2.61 mmol, 42% yield) of (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)allyl acetate. Unreacted 4,4-dimethyl-1-vinylcyclohexan-1-ol (546 mg, 3.53 mmol, 57% recycled yield) and (E)-but-2-ene-1,4-diyl diacetate (705 mg, and a small amount of (Z)-but-2-ene-1,4-diyl diacetate) could also be isolated. The formation of (E)-1,1'-(ethene-1,2-diyl)bis(4,4-dimethylcyclohexan-1-ol) was observed only in trace amounts.

[0089] (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)allyl acetate [ka]

[0090] Minor isomer: (Z)-3-(1-hydroxy-4,4-dimethylcyclohexyl)allyl acetate (characteristic signal) [ka]

[0091] (E)-But-2-ene-1,4-diyl diacetate [ka]

[0092] (Z)-But-2-ene-1,4-diyl diacetate (minor isomer) [ka]

[0093] (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)allyl acetate (0.5 g, 2.209 mmol) was deprotected in the presence of KOH (372 mg, 6.62 mmol) in 5 mL of methanol at room temperature (overnight) to give (E)-1-(3-hydroxyprop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol. Methanol was evaporated under reduced pressure and water (2 mL) and MTBE (10 mL) were added. The mixture was stirred for 5 min and the phases were allowed to separate. The organic phase was washed twice with water (2 mL) and dried over sodium sulfate. The solvent was evaporated under reduced pressure to give 0.399 g (2.165 mmol, 98% yield) of a white solid.

[0094] (E)-1-(3-hydroxyprop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol [ka]

[0095] [Example 5] Cross metathesis of 4,4-dimethyl-1-vinylcyclohexan-1-ol with 1-(allyloxy)butane to produce (E)-1-(3-butoxyprop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol To a stirred solution of 4,4-dimethyl-1-vinylcyclohexan-1-ol (2.889 mg, 18.73 mmol) and 1-(allyloxy)butane (6.42 g, 56.2 mmol) at 40° C., 0.75 mol % of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6) was added in small portions (0.25 mol % x 3, 25 min each) over 1 h 15 min. The mixture was cooled to room temperature and stirred overnight. Then, 154 mg of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4) was added and the mixture was stirred at room temperature for 30 minutes. The crude material was purified by column chromatography (330 g cartridge, 95% cyclohexane / 5% MTBE to 7% cyclohexane / 3% MTBE) to give 1.77 g (7.36 mmol, 39% yield) of (E)-1-(3-butoxyprop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol. Unreacted 1-(allyloxy)butane (2.82 g, 24.7 mmol), 4,4-dimethyl-1-vinylcyclohexan-1-ol (1.53 g, 9.95 mmol, 53% recycled yield) and (E)-1,4-dibutoxybut-2-ene (2.31 g, 11.54 mmol) could also be isolated. The formation of (E)-1,1'-(ethene-1,2-diyl)bis(4,4-dimethylcyclohexan-1-ol) was only observed in trace amounts.

[0096] (E)-1-(3-butoxyprop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol [ka]

[0097] (E)-1,4-Dibutoxybut-2-ene [ka]

[0098] [Example 6] Cross metathesis of 4,4-dimethyl-1-vinylcyclohexan-1-ol with 1-(1-(allyloxy)ethoxy)butane to produce (E)-1-(3-(1-butoxyethoxy)prop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol To a stirred solution of 4,4-dimethyl-1-vinylcyclohexan-1-ol (0.576 g, 3.73 mmol) and 1-(1-(allyloxy)ethoxy)butane 0.59 g, 3.73 mmol) at 40° C., 1.5 mol % of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6) was added in small portions (0.5 mol % x 3, 30 min each) over 1 h 30 min. The mixture was cooled to room temperature and stirred overnight. Then, 64.2 mg of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4) was added and the mixture was stirred at room temperature for 30 minutes. The crude material was purified by column chromatography (330 g cartridge, cyclohexane 99 / MTBE 1 to cyclohexane 7 / MTBE 3) to give 0.408 g (1.43 mmol, 38% yield) of (E)-1-(3-(1-butoxyethoxy)prop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol. Unreacted 1-(1-(allyloxy)ethoxy)butane, 4,4-dimethyl-1-vinylcyclohexan-1-ol (180 mg, 1.17 mmol, 31% recycled yield) and (E)-6,13-dimethyl-5,7,12,14-tetraoxaoctadec-9-ene (18 mg, 0.06 mmol) could also be isolated. The formation of (E)-1,1'-(ethene-1,2-diyl)bis(4,4-dimethylcyclohexan-1-ol) was only observed in trace amounts.

[0099] (E)-1-(3-(1-butoxyethoxy)prop-1-en-1-yl)-4,4-dimethylcyclohexan-1-ol [ka]

[0100] (E)-6,13-Dimethyl-5,7,12,14-tetraoxaoctadec-9-ene [ka]

[0101] [Example 7] Preparation of (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)prop-2-ene-1,1-diyl diacetate by cross metathesis of 4,4-dimethyl-1-vinylcyclohexan-1-ol with prop-2-ene-1,1-diyl diacetate To a stirred solution of 2.5 g of 4,4-dimethyl-1-vinylcyclohexan-1-ol (98% pure, 15.883 mmol) and 10.05 g of prop-2-ene-1,1-diyl diacetate (63.53 mmol, 4 eq) in 10 mL of EtOAc at 50 °C under argon atmosphere was added 20 mg (0.0254 mmol, 0.160 mol%) of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6). Next, 110 mg (0.0637 mmol, 0.88 mol%) of GreenCat was dissolved in 10 mL of EtOAc and added over 3 h using a syringe pump. After addition of 298 mg of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4), the mixture was stirred at room temperature for 1 h and the solvent was evaporated under reduced pressure. The crude product was purified by column chromatography (330 g cartridge, Cyclo 9 / AcOEt 1 to Cyclo 8 / AcOEt 2) to give 2.85 g (99% purity, 9.92 mmol, 62.4% yield) of (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)prop-2-ene-1,1-diyl diacetate. Unreacted prop-2-ene-1,1-diyl diacetate (8.4 g, 0.0536 mmol) and 4,4-dimethyl-1-vinylcyclohexan-1-ol could also be isolated. (E)-1,1'-(ethene-1,2-diyl)bis(4,4-dimethylcyclohexan-1-ol) was observed in only small amounts (<1%) in the GC of the crude product. No formation of (E)-but-2-ene-1,1,4,4-tetrayl tetraacetate was observed.

[0102] (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)prop-2-ene-1,1-diyl diacetate [ka]

[0103] Conversion of (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)prop-2-ene-1,1-diyl diacetate to (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)acrylaldehyde was carried out in the presence of potassium bisulfate and water (toluene, 110° C., 1 h).

[0104] Conversion of (E)-3-(1-hydroxy-4,4-dimethylcyclohexyl)prop-2-ene-1,1-diyl diacetate to (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)prop-2-ene-1,1-diyl diacetate was carried out in the presence of POCl3 / pyridine (0 °C ~ > room temperature, 16 h).

[0105] (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)prop-2-ene-1,1-diyl diacetate [ka]

[0106] Preparation of (E)-3-(1-hydroxycyclohexyl)prop-2-ene-1,1-diyl diacetate: via the preceding procedure from 1-vinylcyclohexan-1-ol (70% yield).

[0107] [ka]

[0108] Conversion of (E)-3-(1-hydroxycyclohexyl)prop-2-ene-1,1-diyl diacetate to (E)-3-(cyclohex-1-en-1-yl)prop-2-ene-1,1-diyl diacetate was carried out in the presence of POCl3 / pyridine (0 °C ~ > room temperature, 16 h).

[0109] (E)-3-(cyclohex-1-en-1-yl)prop-2-ene-1,1-diyl diacetate [ka]

[0110] (E)-3-(cyclohex-1-en-1-yl)prop-2-ene-1,1-diyl diacetate can be deprotected in the presence of 1 eq triethylamine in MeOH (4 h at room temperature) to give (E)-3-(cyclohex-1-en-1-yl)acrylaldehyde.

[0111] (E)-3-(Cyclohex-1-en-1-yl)acrylaldehyde [ka]

[0112] [Example 8] Cross metathesis of 4,4-dimethyl-1-vinylcyclohex-1-ene with prop-2-ene-1,1-diyl diacetate to give (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)prop-2-ene-1,1-diyl diacetate and (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)acrylaldehyde To a stirred solution of 0.56 g of 4,4-dimethyl-1-vinylcyclohex-1-ene (92.8% pure, 3.81 mmol) and 2.57 g of prop-2-ene-1,1-diyl diacetate (15.26 mmol, 4 eq) in 7.4 mL of EtOAc at room temperature under argon atmosphere, 299 mg (0.381 mmol, 10 mol%) of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6) was added in small portions (1 mol%, 2 mol%, 2 mol% and 5 mol%). After each addition, the mixture was heated at 50°C for 1-3 hours. After 472 mg (2.29 mmol) of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4) was added, the mixture was stirred at room temperature for 1 hour. The solvent was evaporated under reduced pressure. The crude was purified by column filtration through a silica pad and the volatiles (unreacted prop-2-ene-1,1-diyl diacetate) were removed by Kugelrohr distillation. 779 mg (2.778 mmol, 73% yield) of (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)prop-2-ene-1,1-diyl diacetate and 98 mg of (E)-but-2-ene-1,1,4,4-tetrayl tetraacetate (0.34 mmol) were obtained. Unreacted 4,4-dimethyl-1-vinylcyclohex-1-ene could also be isolated. Only a small amount of (E)-1,2-bis(4,4-dimethylcyclohex-1-en-1-yl)ethene was isolated (57 mg, 0.234 mmol).

[0113] (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)prop-2-ene-1,1-diyl diacetate [ka]

[0114] (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)prop-2-ene-1,1-diyl diacetate can be deprotected in the presence of 1 eq triethylamine in MeOH (4 h at room temperature) to give (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)acrylaldehyde.

[0115] (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)acrylaldehyde: [ka]

[0116] (E)-But-2-ene-1,1,4,4-tetrayltetraacetate [ka]

[0117] [Example 9] Cross metathesis of 4,4-dimethyl-1-vinylcyclohex-1-ene with 3,3-diethoxyprop-1-ene to give (E)-1-(3,3-diethoxyprop-1-en-1-yl)-4,4-dimethylcyclohex-1-ene and (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)acrylaldehyde To a stirred solution of 0.500 g of 4,4-dimethyl-1-vinylcyclohex-1-ene (92.8% purity, 3.406 mmol) and 1.33 g of 3,3-diethoxyprop-1-ene (10.22 mmol, 3 eq) in 6 mL of EtOAc under argon at 50° C., 26.7 mg (0.0341 mmol, 1 mol%) of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6) was added. The mixture was heated at 50° C. for 30 min. Then, 26.7 mg (0.0341 mmol, 1 mol%) of GreenCat was added 4 times at 30 min intervals and the mixture was stirred for another 30 min at 50° C. After adding 179 mg (0.86 mmol) of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4), the mixture was stirred for 1 h at room temperature. The solvent was evaporated under reduced pressure. The crude was purified by column filtration (25 g cartridge, Cyclo 95 / AcOEt 5 to Cyclo 9 / AcOEt 1) to give 0.748 g (2.96 mmol, 87% yield) of (E)-1-(3,3-diethoxyprop-1-en-1-yl)-4,4-dimethylcyclohex-1-ene and 374 mg (1.61 mmol) of (E)-1,1,4,4-tetraethoxybut-2-ene. Unreacted 3,3-diethoxyprop-1-ene and 4,4-dimethyl-1-vinylcyclohex-1-ene (GC 9%) could also be isolated. E)-1,2-bis(4,4-dimethylcyclohex-1-en-1-yl)ethene was observed only in small amounts in the GC of the crude (2.2%).

[0118] (E)-1-(3,3-diethoxyprop-1-en-1-yl)-4,4-dimethylcyclohex-1-ene [ka]

[0119] (E)-1-(3,3-diethoxyprop-1-en-1-yl)-4,4-dimethylcyclohex-1-ene can be deprotected in the presence of AcOH and water at room temperature to give (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)acrylaldehyde (quantitative yield).

[0120] (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)acrylaldehyde: [ka]

[0121] [Example 10] Cross metathesis of 4,4-dimethyl-1-vinylcyclohex-1-ene with allyl acetate to give (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)allyl acetate and (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)prop-2-en-1-ol To a stirred solution of 0.500 g of 4,4-dimethyl-1-vinylcyclohex-1-ene (91.9% purity, 3.37 mmol) and 1.10 g of allyl acetate (11.01 mmol) in 6 mL of EtOAc under argon at room temperature, 28.8 mg (0.037 mmol, 1 mol%) of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6) was added. The mixture was stirred at room temperature for 20 min. Then, 28.8 mg (0.037 mmol, 1 mol%) of GreenCat was added twice, 30 min apart, and the mixture was stirred at room temperature for another 30 min. After adding 151 mg (0.73 mmol) of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4), the mixture was stirred at room temperature for 1 h. The solvent was evaporated under reduced pressure. The crude (1.76 g) was purified by column filtration (25 g cartridge, Cyclo 98 / MTBE 2 to Cyclo 75 / MTBE 25) to obtain 0.491 g (2.36 mmol, 70% yield) of (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)allyl acetate and 368 mg (2.13 mmol) of (E)-but-2-ene-1,4-diyl diacetate. Unreacted allyl acetate and 4,4-dimethyl-1-vinylcyclohex-1-ene (GC 27%) could also be isolated. E)-1,2-bis(4,4-dimethylcyclohex-1-en-1-yl)ethene was observed in very small amounts in the GC of the crude product (1.0%).

[0122] (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)allyl acetate [ka]

[0123] (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)allyl acetate can be deprotected to give (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)prop-2-en-1-ol in quantitative yield (KOH, MeOH, room temperature, 15 h).

[0124] (E)-3-(4,4-dimethylcyclohex-1-en-1-yl)prop-2-en-1-ol [ka]

[0125] (E)-1-(3-butoxyprop-1-en-1-yl)-4,4-dimethylcyclohex-1-ene could be prepared from 4,4-dimethyl-1-vinylcyclohex-1-ene and 3 eq of 1-(allyloxy)butane using the cross-metathesis protocol described above (29% conversion after 1 h 30 min using 2 mol% Green Cat).

[0126] (E)-1-(3-butoxyprop-1-en-1-yl)-4,4-dimethylcyclohex-1-ene [ka]

[0127] [Example 11] Cross metathesis of (E)-1-methyl-4-(2-methylbuta-1,3-dien-1-yl)benzene with 3,3-diethoxyprop-1-ene to produce 1-((1E,3E)-5,5-diethoxy-2-methylpenta-1,3-dien-1-yl)-4-methylbenzene and (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal Commercially available (E)-2-methyl-3-(p-tolyl)acrylaldehyde (CAS 93614-82-5) was synthesized according to a literature procedure (K.P.S. Cheung, D. Kurandina, T. Yata, and V. Gevorgyan J. Am. Chem. Soc. 2020, 142, To a stirred solution of 0.55 g of (E)-1-methyl-4-(2-methylbut-1,3-dien-1-yl)benzene (99% pure, 3.476 mmol) prepared by Wittig reaction according to (E)-1-methyl-4-(2-methylbut-1,3-dien-1-yl)benzene (99% pure, 3.476 mmol) and 1.444 g of 3,3-diethoxyprop-1-ene (10.427 mmol, 3 eq) in 10 mL of EtOAc at 50 °C under argon atmosphere was added 10 mg (0.0127 mmol, 0.36 mol%) of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6). The mixture was stirred at 50° C. for 30 min. Then, 10 mg (0.0127 mmol, 0.36 mol%) of GreenCat was added three times at 30 min intervals and the mixture was stirred for another 30 min. 100 mg of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4) was added and after stirring for 30 min, the solvent was evaporated under reduced pressure. The crude was purified by column chromatography (80 g cartridge, Cyclo 97.5 / AcOEt 2.5 to Cyclo 9 / AcOEt 1) to give 405 mg (2.022 mmol, 58.2% yield) of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal and 63 mg (0.231 mmol, 6.6% yield) of 1-((1E,3E)-5,5-diethoxy-2-methylpenta-1,3-dien-1-yl)-4-methylbenzene. Unreacted 3,3-diethoxyprop-1-ene and (E)-1-methyl-4-(2-methylbut-1,3-dien-1-yl)benzene (177 mg, 1.118 mmol, 32% yield recycled) could also be isolated.No formation of 4,4'-((1E,3E,5E)-2,5-dimethylhexa-1,3,5-triene-1,6-diyl)bis(methylbenzene) was observed.

[0128] 1-((1E,3E)-5,5-diethoxy-2-methylpenta-1,3-dien-1-yl)-4-methylbenzene [ka]

[0129] (2E,4E)-4-Methyl-5-(p-tolyl)penta-2,4-dienal [ka]

[0130] 1-((1E,3E)-5,5-Diethoxy-2-methylpenta-1,3-dien-1-yl)-4-methylbenzene could be converted to (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal in the presence of AcOH / water at room temperature (quantitative yield).

[0131] [Example 12] Cross metathesis of (E)-1-methyl-4-(2-methylbuta-1,3-dien-1-yl)benzene with 3,3-diethoxyprop-1-ene to produce (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dien-1,1-diyl diacetate and (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal To a stirred solution of 0.50 g of (E)-1-methyl-4-(2-methylbut-1,3-dien-1-yl)benzene (99% purity, 3.160 mmol) and 1.499 g of prop-2-ene-1,1-diyl diacetate (9.48 mmol, 3 eq) in 20 mL of dichloromethane under argon at room temperature, 25 mg (0.0316 mmol, 1 mol%) of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6) was added. The mixture was stirred at room temperature for 30 min. Then, 125 mg (0.158 mmol, 5 mol%) of GreenCat was added and the mixture was stirred at room temperature overnight. After adding 12.5 mg (0.0158 mmol, 0.5 mol%) of GreenCat, the mixture was refluxed for 5 hours. After adding 243 mg of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4) and stirring for 30 minutes, the solvent was evaporated under reduced pressure. The crude was purified by column chromatography (80 g cartridge, Cyclo 95 / AcOEt 5 to Cyclo 9 / AcOEt 1) to give 0.766 g of a mixture of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-diene-1,1-diyl diacetate and (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal (containing some prop-2-ene-1,1-diyl diacetate). (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-diene-1,1-diyl diacetate could be deprotected in the presence of 1 eq triethylamine in MeOH (4 h at room temperature) to give (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal.

[0132] (2E,4E)-4-Methyl-5-(p-tolyl)penta-2,4-diene-1,1-diyl diacetate [ka]

[0133] (2E,4E)-4-Methyl-5-(p-tolyl)penta-2,4-dienal [ka]

[0134] [Example 13] Production of 2-methyl-1-(p-tolyl)but-3-en-1-ol from 4-methylbenzaldehyde To a cooled solution (0°C) of 494.4 mL of 1-methyl-2-propenylmagnesium chloride (0.5 M in THF, 247.2 mmol, 1.1 eq) was slowly added a solution of 4-methylbenzaldehyde (27.0 g, 224.7 mmol) in 135 mL of THF. During the addition of the aldehyde the internal temperature did not exceed 5°C. The mixture was further stirred overnight (16 h) at 0°C and analyzed by GC. The reaction mixture was slowly added to a cooled solution of 16.2 g of AcOH (269.7 mmol) in 200 ml of water. The phases were separated and the aqueous phase was extracted twice with 150 mL of TBME. The combined organic phases were washed with saturated aqueous NaHCO3 and saturated aqueous NaCl. After drying over Na2SO4 the solvent was evaporated under reduced pressure (500-4 mbar, 50°C). The crude product (44.3 g) was purified by distillation through a Vigreux column under reduced pressure (oil bath 120 °C, 900-3 mbar, bp 90 °C / 3 mbar). 39.0 g (221.3 mmol, 98.4% yield) of 2-methyl-1-(p-tolyl)but-3-en-1-ol (syn / anti mixture) was obtained as a colorless liquid.

[0135] NMR analysis in CDCl3 was consistent with literature data for the syn isomer: Shibata, I.; Yoshimura, N.; Yabu, M. Baba, A. Eur. J. Org. Chem. 2001, 3207-3211. S. Hayashi, K. Hirano, H. Yorimitsu, K. Oshima Org. Lett. 2005, 7, 16, 3577-3579. 2-Methyl-1-(p-tolyl)but-3-en-1-ol (syn isomer): [ka]

[0136] 2-Methyl-1-(p-tolyl)but-3-en-1-ol (anti isomer): [ka]

[0137] [Example 14] Production of 2-methyl-1-(p-tolyl)but-3-en-1-yl acetate from 2-methyl-1-(p-tolyl)but-3-en-1-ol To 9.94 g (56.397 mmol) of 2-methyl-1-(p-tolyl)but-3-en-1-ol, under stirring and under N2 atmosphere, was added DMAP (172 mg, 1.41 mmol, 2.5 mol%) and triethylamine (5.71 g, 56.4 mmol, 1 eq). Then, acetic anhydride (11.515 g, 112.79 mmol, 2 eq) was added slowly (exothermic). The mixture was stirred at room temperature for 1.5 h (complete conversion). The mixture was cooled in an ice bath (0° C.) and 5 mL of water was added slowly (hydrolysis of residual Ac2O). 13.8 g of 25% aqueous NaOH (1.5 eq) was added slowly. After stirring for 30 min, 25 mL of MTBE was added. The phases were allowed to separate. The aqueous phase was extracted once with 25 mL of MTBE. The combined organic phases were washed twice with water (15 mL), then once with saturated aqueous NaHCO3 (15 mL) and once with water (15 mL). After a final wash with brine (10 mL), the organic phase was dried over sodium sulfate, filtered and evaporated under reduced pressure (50 °C, 50 mbar). The crude product (12.3 g) was purified by flash chromatography (220 g cartridge, eluent pentane 100% to pentane 95 / MTBE 5). 2-Methyl-1-(p-tolyl)but-3-en-2-yl acetate (1 / 1 mixture of diastereomers) was isolated as a colorless liquid (11.93 g, 54.64 mmol, 97% yield).

[0138] [ka]

[0139] [Example 15] Cross metathesis of 2-methyl-1-(p-tolyl)but-3-en-1-ol with 3,3-diethoxyprop-1-ene to produce (E)-5,5-diethoxy-2-methyl-1-(p-tolyl)pent-3-en-1-ol To a stirred solution of 2-methyl-1-(p-tolyl)but-3-en-1-ol (1.0 g, 5.674 mmol) and 3,3-diethoxyprop-1-ene (2.2 g, 17.02 mmol) in EtOAc (10 ml) at room temperature was added 8 mol % of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6) in small portions (1.6 mol % x 5). After 67 hours of reaction at room temperature, 650 mg of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4) was added and the mixture was stirred at room temperature for 30 minutes. The solvent was evaporated under reduced pressure (20 mbar, 50° C.). The crude was purified by column chromatography (40 g cartridge, cyclohexane 98 / MTBE 2 to cyclohexane 9 / AcOEt 1) to give 0.330 g (1.18 mmol, 21% yield) of (E)-5,5-diethoxy-2-methyl-1-(p-tolyl)pent-3-en-1-ol. Unreacted 3,3-diethoxyprop-1-ene, 2-methyl-1-(p-tolyl)but-3-en-1-ol (369 mg, 2.10 mmol, 37% recycled yield) and (E)-1,1,4,4-tetraethoxybut-2-ene could also be isolated. (E)-2,5-Dimethyl-1,6-di-p-tolylhex-3-ene-1,6-diol was formed only in small amounts.

[0140] (E)-5,5-Diethoxy-2-methyl-1-(p-tolyl)pent-3-en-1-ol Major isomer (ratio 4.4 / 1) [ka]

[0141] Minor isomers [ka]

[0142] When crotonaldehyde was used in a cross-metathesis reaction with 2-methyl-1-(p-tolyl)but-3-en-1-ol in EtOAc (50° C.), only a small amount (2%) of the desired product ((E)-2-methyl-5-oxo-1-(p-tolyl)pent-3-en-1-yl acetate) was observed using 4 mol % of GreenCat. In addition, formation of 2% of (E)-2-methyl-1-(p-tolyl)pent-3-en-1-ol was observed. When 3,3-diethoxyprop-1-ene and 2-methyl-1-(p-tolyl)but-3-en-1-ol in EtOAc (50° C.) were used, 25% of the desired product (E)-5,5-diethoxy-2-methyl-1-(p-tolyl)pent-3-en-1-ol was obtained using 4 mol % of GreenCat.

[0143] (E)-5,5-Diethoxy-2-methyl-1-(p-tolyl)pent-3-en-1-ol can be converted to (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal under Dean-Stark conditions (toluene or cyclohexane) in the presence of acid (pTsOH, oxalic acid, tartaric acid, KHSO4).

[0144] (E)-5,5-Diethoxy-2-methyl-1-(p-tolyl)pent-3-en-1-ol can be deprotected in the presence of AcOH / water / THF (room temperature, 40 min) to give (E)-5-hydroxy-4-methyl-5-(p-tolyl)pent-2-enal in high yield: (E)-5,5-Diethoxy-2-methyl-1-(p-tolyl)pent-3-en-1-ol (46 mg, 0.165 mmol) was stirred in 0.5 mL of THF and 50 mg of AcOH and 50 mg of water were added. After 40 min at room temperature, the solvent was evaporated under reduced pressure. 5 mL of heptane was added (twice) and evaporated under reduced pressure. 32 mg (0.157 mmol, 95% yield) of pure (E)-5-hydroxy-4-methyl-5-(p-tolyl)pent-2-enal was obtained.

[0145] (E)-5-Hydroxy-4-methyl-5-(p-tolyl)pent-2-enal Major isomer (ratio 4.4 / 1) [ka]

[0146] Minor isomers [ka]

[0147] (E)-5-Hydroxy-4-methyl-5-(p-tolyl)pent-2-enal can be converted to (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal under Dean-Stark conditions (toluene or cyclohexane) in the presence of acid (pTsOH, oxalic acid, tartaric acid, KHSO4).

[0148] (E)-5-hydroxy-4-methyl-5-(p-tolyl)pent-2-enal can be converted to ((2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal in the presence of POCl3 / pyridine (0 °C to RT).

[0149] A small amount of ((2E,4Z)-4-methyl-5-(p-tolyl)penta-2,4-dienal was also formed.

[0150] [ka]

[0151] [Example 16] Preparation of (E)-5,5-diethoxy-2-methyl-1-(p-tolyl)pent-3-en-1-yl acetate by cross metathesis of 2-methyl-1-(p-tolyl)but-3-en-1-yl acetate with 3,3-diethoxyprop-1-ene To a stirred solution of 2-methyl-1-(p-tolyl)but-3-en-1-yl acetate (1.0 g, 4.581 mmol) and 3,3-diethoxyprop-1-ene (1.79 g, 13.74 mmol) in EtOAc (8 ml) at 50° C., 1.5 mol % of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6) was added in small portions (0.3 mol % per hour x 5 times) over 5 hours. After the last addition, the mixture was cooled to room temperature and stirred overnight. Then, 100 mg of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4) was added and the mixture was stirred at room temperature for 30 min. The mixture was filtered through a silica pad and the solvent was evaporated under reduced pressure (50 mbar, 50° C.). The crude was purified by column chromatography (40 g cartridge, cyclohexane 98 / MTBE 2 to cyclohexane 9 / AcOEt 1) to give 0.73 g (2.28 mmol, 50% yield) of (E)-5,5-diethoxy-2-methyl-1-(p-tolyl)pent-3-en-1-yl acetate. Unreacted 3,3-diethoxyprop-1-ene, 2-methyl-1-(p-tolyl)but-3-en-1-yl acetate (0.280 g, 1.28 mmol, 28% recycled yield) and (E)-1,1,4,4-tetraethoxybut-2-ene could also be isolated. The formation of (E)-2,5-dimethyl-1,6-di-p-tolylhex-3-ene-1,6-diyl diacetate was only observed in trace amounts.

[0152] (E)-5,5-diethoxy-2-methyl-1-(p-tolyl)pent-3-en-1-yl acetate Major isomer (ratio 1.46 / 1) [ka]

[0153] Minor isomers [ka]

[0154] When crotonaldehyde was used in a cross-metase reaction with 2-methyl-1-(p-tolyl)but-3-en-1-yl acetate in EtOAc (50°C), only a small amount (23.8%) of the desired product ((E)-2-methyl-5-oxo-1-(p-tolyl)pent-3-en-1-yl acetate) was observed by using 2 mol% of GreenCat. In addition, the formation of 21% of (E)-2-methyl-1-(p-tolyl)pent-3-en-1-yl acetate was observed.

[0155] (E)-5,5-Diethoxy-2-methyl-1-(p-tolyl)pent-3-en-1-yl acetate can be converted to (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal in the presence of acid or Lewis acid (5 mol% pTsOH in toluene or cyclohexane at 50 °C or 10 mol% BF3·Et2O at room temperature). 1-((1E,3E)-5,5-diethoxy-2-methylpenta-1,3-dien-1-yl)-4-methylbenzene is observed as the intermediate of the reaction.

[0156] A small amount of ((2E,4Z)-4-methyl-5-(p-tolyl)penta-2,4-dienal was also formed.

[0157] [ka]

[0158] (E)-5,5-Diethoxy-2-methyl-1-(p-tolyl)pent-3-en-1-yl acetate can be deprotected in the presence of AcOH / water / THF (room temperature, 30 min) to give (E)-2-methyl-5-oxo-1-(p-tolyl)pent-3-en-1-yl acetate in quantitative yield.

[0159] (E)-2-Methyl-5-oxo-1-(p-tolyl)pent-3-en-1-yl acetate Major isomer (ratio 1.37 / 1) [ka]

[0160] Minor isomers [ka]

[0161] (E)-2-Methyl-5-oxo-1-(p-tolyl)pent-3-en-1-yl acetate can be converted to (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal under Dean-Stark conditions (toluene or cyclohexane) in the presence of acid (pTsOH, oxalic acid, tartaric acid, KHSO4).

[0162] (E)-2-Methyl-5-oxo-1-(p-tolyl)pent-3-en-1-yl acetate can be deprotected in the presence of KOH / MeOH to give (E)-5-hydroxy-4-methyl-5-(p-tolyl)pent-2-enal (quantitative yield).

[0163] (E)-5-Hydroxy-4-methyl-5-(p-tolyl)pent-2-enal can be converted to (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal under Dean-Stark conditions (toluene or cyclohexane) in the presence of acid (pTsOH, oxalic acid, tartaric acid, KHSO4).

[0164] (E)-5-hydroxy-4-methyl-5-(p-tolyl)pent-2-enal can be converted to ((2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal in the presence of POCl3 / pyridine (0 °C to RT).

[0165] A small amount of ((2E,4Z)-4-methyl-5-(p-tolyl)penta-2,4-dienal was also formed.

[0166] [ka]

[0167] [Example 17] Preparation of 2-methyl-1-(p-tolyl)but-3-en-2-ol from 4-methylphenylacetone To a cooled solution (0°C) of 139.9 mL of vinylmagnesium chloride (1.6 M in THF, 254.4 mmol, 1.1 eq) was slowly added a solution of 1-(p-tolyl)propan-2-one (37.7 g, 254.4 mmol) in 153 mL of THF. During the addition of the ketone, the internal temperature did not exceed 5°C. The mixture was further stirred at 0°C overnight (16 h). The reaction mixture was slowly added to a cooled solution of 18.3 g of AcOH (305.2 mmol) in 200 ml of water. The phases were separated and the aqueous phase was extracted with 150 mL of TBME. The combined organic phases were washed with saturated aqueous NaHCO3 and saturated aqueous NaCl. After drying over Na2SO4, the solvent was evaporated under reduced pressure (500-20 mbar, 50°C). The crude product (48.2 g) was purified by distillation through a Vigreux column under reduced pressure (oil bath 40°C-125°C, 50-4 mbar, bp 97°C / 4 mbar). 35.5 g (201.4 mmol, 79% yield) of 2-methyl-1-(p-tolyl)but-3-en-2-ol was obtained as a colorless liquid.

[0168] 2-Methyl-1-(p-tolyl)but-3-en-2-ol: CDCl3 1 H-NMR analysis results were consistent with literature data: Araki, S.; Ohmura, M.; Butsugan, Y. Bulletin of the Chemical Society of Japan(1986), 59(6),2019-20 [ka]

[0169] [Example 18] Cross metathesis of 2-methyl-1-(p-tolyl)but-3-en-2-ol with 3,3-diethoxyprop-1-ene to produce (E)-5,5-diethoxy-2-methyl-1-(p-tolyl)pent-3-en-2-ol To a stirred solution of 2-methyl-1-(p-tolyl)but-3-en-2-ol (1.6 g, 9.078 mmol) and 3,3-diethoxyprop-1-ene (3.77 g, 27.2 mmol) in EtOAc (16 ml) at 50° C., GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6) was added in small portions (0.2 mol% per hour, 5 h). Then, 0.5 mol% of GreenCat was added and the mixture was stirred at room temperature overnight. The mixture was heated again to 50° C. and after 2 h of heating, 0.5 mol % of GreenCat was added twice (total reaction time 30 h, total GreenCat added: 178 mg, 2.5 mol %). Heating was stopped and then 187 mg of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4) was added and the mixture was stirred at room temperature for 30 min. The mixture was filtered through a silica pad and the solvent was evaporated under reduced pressure (50 mbar, 50° C.). The crude was purified by column chromatography (40 g cartridge, cyclohexane 95 / MTBE 5 to cyclohexane 9 / AcOEt 1) to give 1.57 g (5.64 mmol, 62% yield) of (E)-5,5-diethoxy-2-methyl-1-(p-tolyl)pent-3-en-2-ol. Unreacted 3,3-diethoxyprop-1-ene, 2-methyl-1-(p-tolyl)but-3-en-2-ol (0.42 g, 2.389 mmol, 26% recycled yield) and (E)-1,1,4,4-tetraethoxybut-2-ene could also be isolated. No formation of (E)-2,5-dimethyl-1,6-di-p-tolylhex-3-ene-2,5-diol was observed.

[0170] (E)-5,5-diethoxy-2-methyl-1-(p-tolyl)pent-3-en-2-ol [ka]

[0171] When crotonaldehyde was used in a cross-metathesis reaction with 2-methyl-1-(p-tolyl)but-3-en-2-ol in EtOAc (50° C.), only a small amount (34%) of the desired product ((E)-4-hydroxy-4-methyl-5-(p-tolyl)pent-2-enal) was observed by using 3 mol % of GreenCat. Additionally, the formation of 21% of (E)-2-methyl-1-(p-tolyl)pent-3-en-2-ol was observed.

[0172] (E)-5,5-Diethoxy-2-methyl-1-(p-tolyl)pent-3-en-2-ol can be converted to (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal under Dean-Stark conditions (toluene or cyclohexane) in the presence of acid (pTsOH, oxalic acid, tartaric acid, KHSO4).

[0173] (E)-5,5-Diethoxy-2-methyl-1-(p-tolyl)pent-3-en-2-ol can be deprotected in the presence of AcOH / water / heptane (room temperature, 30 min) to give (E)-4-hydroxy-4-methyl-5-(p-tolyl)pent-2-enal in high yield: (E)-5,5-Diethoxy-2-methyl-1-(p-tolyl)pent-3-en-2-ol (200 mg, 0.718 mmol) was stirred in 1 mL of heptane and 215 mg of AcOH and 207 mg of water were added. After 40 min at room temperature, the solvent was evaporated under reduced pressure. 5 mL of heptane was added and evaporated under reduced pressure (evaporation of 5 mL of heptane was repeated twice). 146 mg (0.715 mmol, 99% yield) of pure (E)-5-hydroxy-4-methyl-5-(p-tolyl)pent-2-enal was obtained.

[0174] (E)-4-Hydroxy-4-methyl-5-(p-tolyl)pent-2-enal [ka]

[0175] (E)-4-Hydroxy-4-methyl-5-(p-tolyl)pent-2-enal can be converted to (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal under Dean-Stark conditions (toluene or cyclohexane) in the presence of acid (pTsOH, oxalic acid, tartaric acid, KHSO4).

[0176] (E)-4-hydroxy-4-methyl-5-(p-tolyl)pent-2-enal can be converted to ((2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal in the presence of POCl3 / pyridine (0 °C to RT).

[0177] A small amount of ((2E,4Z)-4-methyl-5-(p-tolyl)penta-2,4-dienal was also formed.

[0178] [Example 19] Preparation of (E)-4-methyl-5-(p-tolyl)pent-2-ene-1,1,5-triyl triacetate by cross metathesis of 2-methyl-1-(p-tolyl)but-3-en-1-yl acetate with prop-2-ene-1,1-diyl diacetate To a stirred solution of 2-methyl-1-(p-tolyl)but-3-en-1-yl acetate (1.0 g, 4.581 mmol) and prop-2-ene-1,1-diyl diacetate (2.2 g, 13.74 mmol) in EtOAc (8 ml) at 50° C., 2 mol % of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6) was added in small portions (1 mol % per hour) over 2 hours. After the last addition, the mixture was cooled to room temperature and stirred overnight. 2 mol % of GreenCat was added and the mixture was stirred at room temperature for 90 hours. Then, 472 mg of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4) was added and the mixture was stirred at room temperature for 30 min. The solvent was evaporated under reduced pressure (50 mbar, 50° C.). The crude product (4.21 g) was purified by column chromatography (40 g cartridge, cyclohexane 95 / MTBE 5 to cyclohexane 6 / MTBE 4) to give 0.230 g (0.66 mmol, 14.4% yield) of (E)-4-methyl-5-(p-tolyl)pent-2-ene-1,1,5-triyl triacetate and (E)-but-2-ene-1,1,4,4-tetrayl tetraacetate (130 mg). Unreacted prop-2-ene-1,1-diyl diacetate (1.68 g), 2-methyl-1-(p-tolyl)but-3-en-1-yl acetate (0.722 g, 3.31 mmol, 72% recycled yield) and (E)-1,1,4,4-tetraethoxybut-2-ene could also be isolated. The formation of (E)-2,5-dimethyl-1,6-di-p-tolylhex-3-ene-1,6-diyl diacetate was only observed in trace amounts.

[0179] (E)-4-Methyl-5-(p-tolyl)pent-2-ene-1,1,5-triyl triacetate [ka]

[0180] Minor isomers (characteristic signals): [ka]

[0181] (E)-4-methyl-5-(p-tolyl)pent-2-ene-1,1,5-triyl triacetate can be deprotected in the presence of KOH, MeOH and water at room temperature to give (E)-5-hydroxy-4-methyl-5-(p-tolyl)pent-2-ene-1,1-diyl diacetate. (E)-5-hydroxy-4-methyl-5-(p-tolyl)pent-2-ene-1,1-diyl diacetate can be deprotected in the presence of 1 eq triethylamine in MeOH (4 hours at room temperature) to give (E)-5-hydroxy-4-methyl-5-(p-tolyl)pent-2-enal.

[0182] [Example 20] Cross metathesis of 1-(tert-butyl)-4-vinylbenzene with 3,3-diethoxyprop-1-ene to produce (E)-1-(tert-butyl)-4-(3,3-diethoxyprop-1-en-1-yl)benzene To a stirred solution of 0.50 g 1-(tert-butyl)-4-vinylbenzene (94% pure, 2.933 mmol) and 1.22 g 3,3-diethoxyprop-1-ene (8.798 mmol, 3 eq) in 10 mL EtOAc under argon at 50° C., 10 mg (0.0127 mmol, 0.43 mol%) of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6) was added. The mixture was stirred at 50° C. for 30 min. Then, 10 mg (0.0127 mmol, 0.43 mol%) of GreenCat was added twice, 30 min apart, and the mixture was stirred for another 30 min. 70 mg of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4) was added and after stirring for 30 min, the solvent was evaporated under reduced pressure. The crude material was purified by column chromatography (80 g cartridge, Cyclo 95 / AcOEt 5 to Cyclo 9 / AcOEt 1) to give 371 mg (1.341 mmol, 45.7% yield) of (E)-1-(tert-butyl)-4-(3,3-diethoxyprop-1-en-1-yl)benzene, 110 mg (0.584 mmol, 19.9% ​​yield, deprotection confirmed during column chromatography) of (E)-3-(4-(tert-butyl)phenyl)acrylaldehyde and 0.45 g (1.84 mmol) of (E)-1,1,4,4-tetraethoxybut-2-ene. Unreacted 3,3-diethoxyprop-1-ene and 1-(tert-butyl)-4-vinylbenzene (26.3 mg, 0.164 mmol, 5.6% recycled yield) could also be isolated. The formation of 97 mg (0.332 mmol, 22% recycled yield) of (E)-1,2-bis(4-(tert-butyl)phenyl)ethene was also observed.

[0183] (E)-1-(tert-butyl)-4-(3,3-diethoxyprop-1-en-1-yl)benzene [ka]

[0184] (E)-3-(4-(tert-butyl)phenyl)acrylaldehyde [ka]

[0185] (E)-1,2-Bis(4-(tert-butyl)phenyl)ethene [ka]

[0186] (E)-1-(tert-butyl)-4-(3,3-diethoxyprop-1-en-1-yl)benzene can be converted to (E)-3-(4-(tert-butyl)phenyl)acrylaldehyde in the presence of water and AcOH (80° C.).

[0187] [Example 21] Preparation of (E)-3-(4-(tert-butyl)phenyl)prop-2-ene-1,1-diyl diacetate by cross metathesis of 1-(tert-butyl)-4-vinylbenzene with prop-2-ene-1,1-diyl diacetate To a stirred solution of 0.60 g of 1-(tert-butyl)-4-vinylbenzene (94% purity, 3.519 mmol mmol) and 2.369 g of prop-2-ene-1,1-diyl diacetate (14.976 mmol, 4 eq) in 15 mL of dichloromethane at 40 °C (reflux) under argon atmosphere, 37 mg (0.047 mmol, 1.3 mol%) of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6) was added. The mixture was stirred (reflux) for 24 h. Then, 37 mg (0.047 mmol, 1.3 mol%) of GreenCat was added and the mixture was stirred (reflux) for another 24 h. 103 mg (0.468 mmol) of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4) was added and stirred at room temperature for 30 min, after which the solvent was evaporated under reduced pressure. The crude was purified by column chromatography (80 g cartridge, Cyclo 95 / AcOEt 5 to Cyclo 9 / AcOEt 1) to give 423 mg (1.46 mmol, 41.4% yield) of (E)-3-(4-(tert-butyl)phenyl)prop-2-ene-1,1-diyl diacetate. Unreacted prop-2-ene-1,1-diyl diacetate (1.55 g) and 1-(tert-butyl)-4-vinylbenzene (112 mg, 0.698 mmol, 20% recycled yield) could also be isolated. The formation of 0.148 g (0.506 mmol, 29% recycled yield) of (E)-1,2-bis(4-(tert-butyl)phenyl)ethene was also confirmed.

[0188] (E)-3-(4-(tert-butyl)phenyl)prop-2-ene-1,1-diyl diacetate [ka]

[0189] Deprotection was carried out according to J. Indian Chem. Soc., Vol. 76, November-December 1999 (titanium isopropoxide).

[0190] [Example 22] Cross metathesis of 2-methyl-1-(4-vinylphenyl)propan-2-ol with 3,3-diethoxyprop-1-ene to produce (E)-1-(4-(3,3-diethoxyprop-1-en-1-yl)phenyl)-2-methylpropan-2-ol To a stirred solution of 2-methyl-1-(4-vinylphenyl)propan-2-ol (1.0 g, 5.67 mmol) and 3,3-diethoxyprop-1-ene (2.2 g, 17.02 mmol) in EtOAc (10 ml) at 50° C., 133.6 mg (3 mol%) of GreenCat ((1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), Apeiron CAS 1448663-06-6) was added in small portions (1 mol% per hour x 3 times) over 3 hours. After the last addition, the mixture was cooled to room temperature and stirred overnight. Then, 246 mg of SnatchCat® (1,4-bis(2-isocyanopropyl)piperazine, CAS 51641-96-4) was added and the mixture was stirred at room temperature for 30 min. The mixture was filtered through a silica pad and the solvent was evaporated under reduced pressure (50 mbar, 50° C.). The crude product (3.05 g) was purified by column chromatography (40 g cartridge, cyclohexane 98 / MTBE 2 to cyclohexane 9 / AcOEt 1) to give 0.86 g (3.1 mmol, 54% yield) of (E)-1-(4-(3,3-diethoxyprop-1-en-1-yl)phenyl)-2-methylpropan-2-ol. It was also possible to isolate unreacted 3,3-diethoxyprop-1-ene (0.5 g), 2-methyl-1-(4-vinylphenyl)propan-2-ol (0.140 g, 0.79 mmol, 14% recycled yield) and (E)-1,1,4,4-tetraethoxybut-2-ene (630 mg). Also isolated was 180 mg (0.77 mmol, 27% recycled yield) of (E)-1,1'-(ethene-1,2-diylbis(4,1-phenylene))bis(2-methylpropan-2-ol).

[0191] (E)-1-(4-(3,3-diethoxyprop-1-en-1-yl)phenyl)-2-methylpropan-2-ol [ka]

[0192] (E)-1,1'-(ethene-1,2-diylbis(4,1-phenylene))bis(2-methylpropan-2-ol) [ka]

[0193] (E)-1-(4-(3,3-diethoxyprop-1-en-1-yl)phenyl)-2-methylpropan-2-ol can be deprotected in the presence of AcOH / water (room temperature, 30 min) to give (E)-3-(4-(2-hydroxy-2-methylpropyl)phenyl)acrylaldehyde in quantitative yield.

[0194] (E)-3-(4-(2-hydroxy-2-methylpropyl)phenyl)acrylaldehyde [ka]

Claims

1. A process for preparing a compound of formula 【Chemical 1】 [wherein, m is 0 or 1; R ａ is a C １－４ alkyl group, a trimethylsilyl group, a C(=O)-R ｃ group, a C(=O)-OR ｃ group, a CH ２ (OR ｃ ) group, a CH(OR ｃ )CH ３ group, where R ｃ is a C １－４ alkyl group; R ｂ is a C １－４ alkyl group, a C(=O)-R ｃ group, where R ｃ is a C １－４ alkyl group; or R ａ and R ｂ together represent a C ２－６ alkanediyl group, and X is of formula a), b) or c) [[Chemical 2]] is in the form of any one of the stereoisomers of the group, where each R １ , R ２ , R ３ , R ４ , R ５ , R ６ and R ７ are, independently of one another, a hydrogen atom, a C １－６ alkyl group or a C ２－６ alkenyl group, and each of these groups may optionally be substituted by a hydroxy group or a C １－３ alkoxy group; or two of the groups among R １ , R ２ , R ３ , R ４ , R ５ , R ６ and R ７ join together to form a C ３－８ cycloalkyl group or a C ５－８ cycloalkenyl group, and each of these groups may optionally be substituted by a hydroxy group, a C １－３ alkyl group or a C １－３ alkoxy group, and the other groups have the same meaning as defined above; each R ８ , R ９ and R １０ are, independently of one another, a hydrogen atom, a C １－６ alkyl group or a C ２－６ alkenyl group, and each of these groups may optionally be substituted by a hydroxy group or a C １－３ alkoxy group; or two of the groups among R ８ , R ９ , R １０ join together to form a C ３－８ cycloalkyl group or a C ５－８ cycloalkenyl group, and each of these groups may optionally be substituted by a hydroxy group, a C １－３ alkyl group or a C １－３ alkoxy group, and the other groups have the same meaning as defined above; n is 0 or 1, and Y is a -CH=CR １１ - group, a -CHR １２ -CHR １１ - group or a -CH ２ -C(OH)R １１ - group, where R １１ is a hydrogen atom or a methyl group or an ethyl group, and R １２ is a hydroxy group or an acetate group; provided that when X is a group of formula b), m is 1] in the form of any one stereoisomer thereof or a mixture thereof, the process comprising a cross-metathesis step between any one stereoisomer of a compound of formula (IIa), (IIb) or (IIc) and any one stereoisomer of a compound of formula (III) or a mixture thereof in the presence of a metathesis catalyst. [Chemical Formula 3] [wherein each R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , n and Y have the same meanings as defined above] 【Chemical 4】 [Wherein, m is 0 or 1 when the cross-metathesis step is carried out with a compound of formula (IIa) or (IIc), m is 1 when the cross-metathesis step is carried out with a compound of formula (IIb), R ａ is a C １－４ alkyl group, a trimethylsilyl group, a C(=O)-R ｃ group, a C(=O)-OR ｃ group, a CH ２ (OR ｃ ) group, a CH(OR ｃ )CH ３ group, wherein R ｃ is a C １－４ alkyl group; R ｂ is a C １－４ alkyl group, a C(=O)-R ｃ group, wherein R ｃ is a C １－４ alkyl group; or R ａ and R ｂ together represent a C ２－６ alkanediyl group, and R ｄ is a hydrogen atom or a CH(OR ａ )(OR ｂ ) ｍ group, wherein m, R ａ and R ｂ have the same meanings as defined above]

2. R ３ 、 R ４ 、 R ５ 、 R ６ 、 R ７ 、 R ８ and R ９ are, independently of one another, a hydrogen atom or a C １－３ alkyl group, the method according to claim 1.

3. The process according to claim 1 or 2, wherein X is a group of formula a) or c).

4. The compound of formula (I) is in the form of any one stereoisomer thereof or a mixture thereof of the compound of formula [Chemical Formula 5] [wherein, m, R ａ , R ｂ , R １ and R ２ have the same meanings as defined in claim 1] The compound of formula (II) is in the form of any one stereoisomer thereof or a mixture thereof of the compound of formula [Chemical Formula 6] [wherein each R １ and R ２ has the same meaning as defined in claim 1]

5. R １ is C １－４ an alkyl group or C ２－４ an alkenyl group, the method according to claim 1 or 2.

6. R １ The method according to claim 1 or 2, wherein R is a methyl group.

7. R ２ is a hydrogen atom, C １－３ alkyl group or C ２－３ alkenyl group, the method according to claim 1 or 2.

8. R ２ The method according to claim 1 or 2, wherein R is a methyl group.

9. R ｄ The method according to claim 1 or 2, wherein R is a hydrogen atom and m is 1.

10. The process according to claim 1 or 2, wherein the metathesis catalyst is a ruthenium-based catalyst.

11. The metathesis catalyst is 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), (1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)diiodo(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), (1,3-dimesitylimidazolidin-2-ylidene)dichloro(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolinylidene](2-isopropoxyphenylmethylene)ruthenium(II), benzylidene-bis(tricyclohexylphosphine)dichlororuthenium, dichloro[1,3-bis(2,6-isopropylphenyl)-2-imidazolinylidene](2-isopropoxyphenylmethylene)ruthenium(II), [1,3-bis(2,6-di-i-propylphenyl)imidazolidin-2-ylidene](2-i-propoxy-5-nitrobenzylidene)ruthenium(II) diiodide, [1,3-bis(2,6-di-i-propylphenyl)imidazolidin-2-ylidene](2-i-propoxy-5-nitrobenzylidene)ruthenium(II) dichloride, (1,3-dimesitylimidazolidin-2-ylidene)diiodo(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), bis(1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene)(3-phenyl-1H-inden-1-ylidene)ruthenium(II) dichloride, (1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene)dichloro(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), (1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene)diiodo(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), dichloro[1,3-bis(2-methylphenyl)-2-imidazolinylidene](2-isopropoxyphenylmethylene)ruthenium(II), 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methylene ruthenium(II) dichloride (supported on resin), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitrophenolyl]-[3-phenyl-1H-inden-1-ylidene]ruthenium(II) chloride, dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][[5-[(dimethylamino)sulfonyl]-2-(1-methylethoxy-O)phenyl]methylene-C]ruthenium(II), dichloro[1-(2,6-diisopropylphenyl)-2,2,4-trimethyl-4-phenyl-5-pyrrolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene]dichloro[(2-isopropoxy)(5-trifluoroacetamido)benzylidene]ruthenium(II), dichloro[1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), dichloro[1-(2,4,6-trimethylphenyl)-2,2,4-trimethyl-4-phenyl-5-pyrrolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), dichloro[1-(2,6-diisopropylphenyl)-2,2,4-trimethyl-4-phenyl-5-pyrrolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), dichloro[1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene][(2-isopropoxy)(5-pentafluorobenzoylamino)benzylidene]ruthenium(II), dichloro[1,3-bis(2,4,6-(Trimethylphenyl)-2-imidazolidinylidene]{[5-(2-Ethoxy-2-oxoethanamide)]-2-isopropoxybenzylidene}ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][(2-isopropoxy)(5-pentafluorobenzoylamino)benzylidene]ruthenium(II), (1,3-bis(2,6-diisopropylphenyl)imidazolidine-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-3-methyl-1-oxobutan-2-yl)oxy)benzylidene)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)(pyridyl)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][(2-isopropoxy)(5-trifluoroacetamide)benzylidene]ruthenium(II), dichloro[1,3-bis(2,6-diisopropylphenyl)imidazolidine-2-ylidene][(5-isobutoxycarbonylamino)-(2-isopropoxy)benzylidene]ruthenium(II), and dichloro[1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)(triphenylphosphine)ruthenium(II), the method according to claim 1 or 2, selected from the group consisting of.,

12. The process further comprises converting the compound of formula (I) into any one stereoisomer thereof or a mixture thereof of the compound of formula (V) 【Chemical Formula 7】 [wherein X is a group of formula a) or b) having the same meaning as defined in claim 1] The process according to claim 1 or 2.

13. When m is 1, the preparation of the compound of formula (V) comprises a deprotection step and a hydrogenation step, the process according to claim 12.

14. When m is 0, the preparation of the compound of formula (V) comprises an isomerization step and a deprotection step, the process according to claim 12.

15. Formula 【Chemical 8】 [wherein X is in the form of any one stereoisomer of a group of formula b) or d) 【Chemical Formula 9】 wherein p is 0 when the dotted line is a carbon-carbon double bond, and p is 1 when the dotted line is a carbon-carbon single bond; Each R １ 、R ２ 、R ３ 、R ４ 、R ５ 、R ６ and R ７ are, independently of one another, a hydrogen atom, a C １－６ alkyl group or a C ２－６ alkenyl group, and each of these groups may optionally be substituted by a hydroxy group or a C １－３ alkoxy group; or two of the groups of R １ 、R ２ 、R ３ 、R ４ 、R ５ 、R ６ and R ７ combine to form a C ３－８ cycloalkyl group or a C ５－８ cycloalkenyl group, and each of these groups may optionally be substituted by a hydroxy group, a C １－３ alkyl group or a C １－３ alkoxy group, and the other groups have the same meaning as defined above; Each R ８ , R ９ and R １０ are, independently of one another, a hydrogen atom, a C １－６ alkyl group or a C ２－６ alkenyl group, and each of these groups may optionally be substituted by a hydroxy group or a C １－３ alkoxy group; or two of the groups R ８ , R ９ and R １０ together form a C ３－８ cycloalkyl group or a C ５－８ cycloalkenyl group, and each of these groups may optionally be substituted by a hydroxy group, a C １－３ alkyl group or a C １－３ alkoxy group, and the other groups have the same meaning as defined above; n is 0 or 1; Y is -CH=CR １１ - group, -CHR １２ -CHR １１ - group or -CH ２ -C(OH)R １１ - group, and R １１ is a hydrogen atom or a methyl group or an ethyl group, and R １２ is a hydroxy group or an acetate group; Z is a CHO group, CH ２ OH group, or CH(OR ａ )(OR ｂ ) ｍ group when X is of formula (d), where m is 0 or 1 and R ａ is a C １－４ alkyl group, trimethylsilyl group, C(=O)-R ｃ group, C(=O)-OR ｃ group, CH ２ (OR ｃ ) group, CH(OR ｃ )CH ３ group, where R ｃ is a C １－４ alkyl group; R ｂ is a C １－４ alkyl group, C(=O)-R ｃ group, where R ｃ is a C １－４ alkyl group or; or R ａ and R ｂ together represent a C ２－６ alkanediyl group or; or Z is a CH(OR ａ )(OR ｂ ) group when X is of formula b), where R ａ and R ｂ are, independently of one another, a methyl group or a C ３－４ alkyl group, a C(=O)-R ｃ group, where R ｃ is a C １－４ alkyl group; or R ａ and R ｂ together represent a C ３－６ alkanediyl group; However, when X is a group of formula (d), R １ R ２ R ３ R ４ R ５ R ６ and R ７ at least one of the groups is a C １－６ alkyl group or a C ２－６ alkenyl group, and each of these groups may optionally be substituted with a hydroxy group or a C １－３ alkoxy group; when X is a group of formula (d) and six of the groups R １ R ２ R ３ R ４ R ５ R ６ and R ７ are hydrogen atoms, the non-hydrogen atoms among R １ R ２ R ３ R ４ R ５ R ６ and R ７ are not methyl groups; when X is a group of formula (d) and R ２ R ３ R ４ R ５ R ６ and R ７ are hydrogen atoms, R １ is in the form of any one of the stereoisomers of the compound that is not a prop-1-en-2-yl group or a mixture thereof, provided that 3-(4-(tert-butyl)cyclohex-1-en-1-yl)acrylaldehyde, 3-(4-(tert-butyl)-1-hydroxycyclohexyl)acrylaldehyde, 1-(tert-butyl)-4-(3,3-diethoxyprop-1-en-1-yl)benzene, 2-(4-(tert-butyl)styryl)-1,3-dioxolane, 3-(4-(tert-butyl)-1-hydroxycyclohexyl)allyl acetate, 3-(2-allyl-1-hydroxycyclohexyl)allyl acetate, 4-(tert-butyl)-1-(3-hydroxyprop-1-en-1-yl)cyclohexan-1-ol, 2-allyl-1-(3-hydroxyprop-1-en-1-yl)cyclohexan-1-ol, 2-(4-isopropylstyryl)-1,3-dioxolane, 2-(4-isopropylstyryl)-4-methyl-1,3-dioxolane, 3-(2-(buta-1,3-dien-1-yl)-1-hydroxycyclohexyl)acrylaldehyde, 3-(5,5-dimethylcyclohex-1-en-1-yl)acrylaldehyde, 3-((1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-en-3-yl)acrylaldehyde, (1R,2S,5R)-1-(3-(tert-butoxy)prop-1-en-1-yl)-2-isopropyl-5-methylcyclohexan-1-ol, 2-allyl-1-(3-hydroxyprop-1-en-1-yl)cyclohexan-1-ol, (3,3-dimethoxyprop-1-en-1-yl)benzene are excluded.

Images