CN112714767A - Boron-containing conjugated polyene compound, process for producing the same, and process for producing conjugated polyene compound - Google Patents

Abstract

A method for producing a boron-containing conjugated polyene compound, comprising the steps of: a first raw material compound having a carbon-carbon triple bond; The second raw material compound of the conjugated bis(or poly) alkene skeleton of two carbon-carbon double bonds in the group is reacted in the presence of a metal catalyst to obtain a conjugated polyolefin containing more than 3 carbon-carbon double bonds. The process of the boron-containing conjugated polyene compound of an olefinic skeleton, wherein at least one of the first raw material compound and the second raw material compound has a carbon atom bonded to a triple bond or a conjugated bis(or poly)ene skeleton. The boron-containing group, the boron-containing conjugated polyene compound has a boron-containing group bonded to a carbon atom constituting the skeleton of the conjugated polyene.

Description

Boron-containing conjugated polyene compound, method for producing the same, and method for producing a conjugated polyene compound

technical field

The present invention relates to a boron-containing conjugated polyene compound, a method for producing the same, and a method for producing a conjugated polyene compound.

Background technique

A conjugated polyene skeleton in which carbon-carbon double bonds and single bonds are alternately repeated is a common structure in physiologically active substances such as antifungal drugs and vitamins. In addition, various applications of conjugated polyene skeletons in electronic material applications have also been investigated. Therefore, methods for introducing a conjugated polyene skeleton into a target compound have been studied for a long time.

For example, Non-Patent Document 1 discloses a method in which a boronic acid polyene ester having a boronic acid group on a conjugated polyene skeleton is formed using a boronic acid haloalkenyl ester protected by a specific protecting group, and cross-coupling This boronic acid polyene ester is used in the synthesis of physiologically active substances by a combined reaction.

prior art literature

Non-patent literature

Non-Patent Document 1: Journal of American Chemical Society, 2008, 130, p.466-468

SUMMARY OF THE INVENTION

The problem to be solved by the invention

An object of the present invention is to provide a novel boron-containing conjugated polyene compound, which has a conjugated polyene skeleton and a boron-containing group bonded thereto, and is useful in the synthesis of physiologically active substances, electronic material substances, and the like, and production thereof method. Another object of the present invention is to provide a method for producing a conjugated polyene compound using the above-mentioned boron-containing conjugated polyene compound.

means of solving problems

One aspect of the present invention relates to a method for producing a boron-containing conjugated polyene compound. This production method includes a step of making a first raw material compound having a carbon-carbon triple bond and a 1,3-butadiene-4,4-diyl group having two carbon-carbon groups included in the group. The second raw material compound of the double-bonded conjugated di(or poly)ene skeleton is reacted in the presence of a metal catalyst to obtain a boron-containing conjugated polyene having a conjugated polyene skeleton containing three or more carbon-carbon double bonds compound. In addition, in this production method, at least one of the first raw material compound and the second raw material compound has a boron-containing group bonded to a carbon atom constituting the triple bond or the conjugated bis(or poly)ene skeleton. . Thus, the above-mentioned boron-containing conjugated polyene compound has a boron-containing group bonded to a carbon atom constituting the above-mentioned conjugated polyene skeleton.

According to the above production method, a boron-containing conjugated polyene compound having a conjugated polyene skeleton and a boron-containing group bonded to the conjugated polyene skeleton can be easily obtained. According to the above-described boron-containing conjugated polyene compound, the conjugated polyene skeleton can be easily introduced into the target compound by a reaction starting from a boron-containing group (eg, a cross-coupling reaction). In addition, the above-mentioned boron-containing conjugated polyene compound can also be used in applications such as electronic materials as a π-conjugated compound having a boron-containing group.

In one embodiment, the first raw material compound may be a compound represented by the following formula (1-1), the second raw material compound may be a compound represented by the following formula (1-2-1), and the boron-containing conjugated The polyene compound may be a compound represented by the following formula (1-3-1).

[Chemical formula 1]

[In formula (1-1), B ¹ represents a boron-containing group, and R ¹ represents a monovalent group. ]

[Chemical formula 2]

[In formula (1-2-1), n represents an integer of 0 or more, and R ² and R ³ each independently represent a hydrogen atom or a monovalent group. When n is 1 or more, a plurality of R ² may be the same or different from each other. In addition, a plurality of R ³ may be the same or different from each other. R ² , R ³ , and R ² and R ³ may be bonded to each other to form a ring. ]

[Chemical formula 3]

[In formula (1-3-1), each of B ¹ , R ¹ , n, R ² and R ³ has the same meaning as described above. In addition, the wavy line shows that the double bond bonded to the wavy line may be either cis or trans. ]

In the above-mentioned form, at least one of the above-mentioned R ³ in the above-mentioned formula (1-2-1) may be a boron-containing group. In this case, a boron-containing conjugated polyene compound having boron-containing groups at both ends of the conjugated polyene skeleton can be obtained. The boron-containing conjugated polyene compound can be suitably used for the production of a polymer compound by cross-coupling polymerization in addition to the above-mentioned uses.

In another embodiment, the first raw material compound may be a compound represented by the following formula (1-1), the second raw material compound may be a compound represented by the following formula (1-2-2), and the boron-containing co-polymer The conjugated polyene compound may be a compound represented by the following formula (1-3-2). In this case, a boron-containing conjugated polyene compound having boron-containing groups at both ends of the conjugated polyene skeleton can be obtained. The boron-containing conjugated polyene compound can be suitably used for the production of a polymer compound by cross-coupling polymerization in addition to the above-mentioned uses.

[Chemical formula 4]

[In formula (1-1), B ¹ represents a boron-containing group, and R ¹ represents a monovalent group. ]

[Chemical formula 5]

[In formula (1-2-2), n ¹ represents an integer of 0 or more, n ² represents 0 or 1, and R ² represents a hydrogen atom or a monovalent group. When n ¹ is 1 or more, a plurality of R ² may be the same or different from each other. However, when n ¹ is 1 or more, n ² is 1. R ² may be bonded to each other to form a ring. ]

[Chemical formula 6]

[In formula (1-3-2), each of B ¹ , R ¹ , n ¹ , n ² and R ² has the same meaning as described above. The two B ^1s may be the same or different from each other. In addition, the two R ^1s may be the same or different from each other. In addition, the wavy line shows that the double bond bonded to the wavy line may be either cis or trans. ]

In each of the above aspects, the R ¹ may be a silyl group, and in this case, the production method may further include a step of substituting the R ¹ in the boron-containing conjugated polyene compound with a hydrogen atom to obtain a second Boron-containing conjugated polyene compounds. Thereby, a boron-containing conjugated polyene compound having no substituent at the substitution position of R ¹ (that is, a boron-containing conjugated polyene compound in which R ¹ becomes a hydrogen atom) can be easily obtained.

Furthermore, in another embodiment, the first raw material compound may be a compound represented by the following formula (2-1), the second raw material compound may be a compound represented by the following formula (2-2), and the boron-containing co-polymer The conjugated polyene compound may be a compound represented by the following formula (2-3).

[Chemical formula 7]

[In formula (2-1), R ⁴ and R ⁵ each independently represent a monovalent group. ]

[Chemical formula 8]

[In formula (2-2), m represents an integer of 0 or more, and R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent group. Wherein, at least one of the two R ⁷ is a boron-containing group. When m is 1 or more, a plurality of R ⁶ may be the same or different from each other. In addition, the two R ^7s may be the same or different from each other. R ⁶ , R ⁷ , and R ⁶ and R ⁷ may bond to each other to form a ring. ]

[Chemical formula 9]

[In formula (2-3), each of R ⁴ , R ⁵ , m, R ⁶ and R ⁷ has the same meaning as described above. In addition, the wavy line shows that the double bond bonded to the wavy line may be either cis or trans. ]

In the above aspect, the value of the Hammett substituent constant σ _p of the above R ⁴ is larger than the value of the Hammett substituent constant σ _p of the above R ⁵ .

In addition, in the above-mentioned aspect, the above-mentioned R ⁵ may be a silyl group, and in this case, the above-mentioned production method may further include a step of substituting the above-mentioned R ⁵ in the above-mentioned boron-containing conjugated polyene compound with a hydrogen atom to obtain the first Two boron-containing conjugated polyene compounds. Thereby, a boron-containing conjugated polyene compound having no substituent at the substitution position of R ⁵ (that is, a boron-containing conjugated polyene compound in which R ⁵ becomes a hydrogen atom) can be easily obtained.

In each of the above aspects, the metal catalyst may contain at least one selected from the group consisting of ruthenium (Ru), rhodium (Rh), cobalt (Co), and nickel (Ni).

In each of the above-mentioned forms, the above-mentioned metal catalyst may be a ruthenium catalyst.

In each of the above methods, the above-mentioned ruthenium catalyst can form zero-valent ruthenium in the reaction system.

Another aspect of the present invention relates to a boron-containing conjugated polyene compound represented by the following formula (1-3-1A), the following formula (1-3-2A) or the following formula (2-3A).

[Chemical formula 10]

[In formula (1-3-1), B ¹ represents a boron-containing group, R ¹¹ represents a hydrogen atom or a monovalent group, n represents an integer of 0 or more, and R ² and R ³ each independently represent a hydrogen atom or a valence group. When n is 1 or more, a plurality of R ² may be the same or different from each other. In addition, a plurality of R ³ may be the same or different from each other. R ² , R ³ , and R ² and R ³ may be bonded to each other to form a ring. In addition, the wavy line shows that the double bond bonded to the wavy line may be either cis or trans. ]

[Chemical formula 11]

[In formula (1-3-2), B ¹ represents a boron-containing group, R ¹¹ represents a hydrogen atom or a monovalent group, n ¹ represents an integer of 0 or more, n ² represents 0 or 1, and R ² represents a hydrogen atom or a monovalent group. However, when n ¹ is 1 or more, n ² is 1. When n ¹ is 1 or more, a plurality of R ² may be the same or different from each other. R ² may be bonded to each other to form a ring. In addition, the two B ^1s may be the same or different from each other. In addition, the wavy line shows that the double bond bonded to the wavy line may be either cis or trans. ]

[Chemical formula 12]

[In formula (2-3), R ⁴ represents a monovalent group, R ¹⁵ represents a hydrogen atom or a monovalent group, m represents an integer of 0 or more, and R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent group group. Wherein, at least one of the two R ⁷ is a boron-containing group. When m is 1 or more, a plurality of R ⁶ may be the same or different from each other. In addition, the two R ^7s may be the same or different from each other. R ⁶ , R ⁷ , and R ⁶ and R ⁷ may bond to each other to form a ring. In addition, the wavy line shows that the double bond bonded to the wavy line may be either cis or trans. ]

Still another aspect of the present invention relates to a method for producing a conjugated polyene compound comprising the step of: a first step of obtaining a reaction for obtaining the above-mentioned boron-containing conjugated polyene compound by the above-mentioned method for producing a boron-containing conjugated polyene compound liquid; and a second step of adding a coupling reaction catalyst and a third raw material compound having a reactive group capable of coupling reaction with the boron-containing group to the reaction liquid to carry out a coupling reaction.

In one approach, the reactive group described above may be a halogen group.

In one embodiment, the first step may be a step of generating the boron-containing conjugated polyene compound in a reaction system of the reaction in the presence of the metal catalyst, and the second step may be adding the above-mentioned boron-containing conjugated polyene compound to the reaction system. The step of coupling the reaction catalyst and the above-mentioned third raw material compound.

effect of invention

According to the present invention, there can be provided a novel boron-containing conjugated polyene compound having a conjugated polyene skeleton and a boron-containing group bonded thereto, and useful in the synthesis of physiologically active substances, electronic material substances, and the like, and a method for producing the same . Moreover, according to this invention, the manufacturing method of the conjugated polyene compound using the said boron-containing conjugated polyene compound can be provided.

Detailed ways

Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

<Method for producing boron-containing conjugated polyene compound>

The method for producing a boron-containing conjugated polyene compound according to the present embodiment includes a polyene formation step of forming a first raw material compound having a carbon-carbon triple bond and a 1,3-butanediene A second starting compound having an alkene-4,4-diyl group and having a conjugated bis(or poly)ene skeleton containing two carbon-carbon double bonds in the group is reacted in the presence of a metal catalyst to obtain a A boron-containing conjugated polyene compound containing a conjugated polyene skeleton of three or more carbon-carbon double bonds. Here, at least one of the first raw material compound and the second raw material compound has a boron-containing group bonded to a carbon atom constituting a triple bond or a conjugated bis(or poly)ene skeleton, whereby the boron-containing conjugated The polyene compound has a boron-containing group bonded to carbon atoms constituting the skeleton of the conjugated polyene.

According to the production method according to the present embodiment, a boron-containing conjugated polyene compound having a conjugated polyene skeleton and a boron-containing group bonded to the conjugated polyene skeleton can be easily obtained. According to such a boron-containing conjugated polyene compound, the conjugated polyene skeleton can be easily introduced into the target compound by a reaction starting from a boron-containing group (for example, a cross-coupling reaction). In addition, the boron-containing conjugated polyene compound can also be used in applications such as electronic materials as a π-conjugated compound having a boron-containing group.

In the present specification, the boron-containing group may be an atomic group remaining after removing one functional group on the boron atom in the boron compound. That is, the boron-containing group may be a monovalent group that is bonded to a bonding target through a boron atom.

The boron-containing group is not particularly limited, and can be appropriately selected within the range in which the reaction of the first raw material compound and the second raw material compound proceeds. As the boron-containing group, for example, a boryl group, a dihydroxyboron group, a boronic acid group, and a derivative group thereof can be mentioned.

Boronyl represents a group represented by -BH ₂ . As a derivative group of a borane group, a diorganoboryl group is mentioned, for example.

For example, the diorganoboronyl group may be a group represented by -B(R ²¹ ) ₂ . R ²¹ represents a monovalent group. Two R ²¹ 's may be the same or different, and may be linked to each other to form a ring together with a boron atom. R ²¹ may be, for example, a monovalent organic group, an optionally substituted alkyl group, or an optionally substituted aryl group.

The alkyl group in R ²¹ may be linear, branched, or cyclic. The number of carbon atoms of the alkyl group in R ²¹ is not particularly limited, and may be, for example, 1 to 8.

The aryl group in R ²¹ represents an atomic group remaining after removing a hydrogen atom on one aromatic ring from an aromatic compound. The aromatic ring possessed by the aromatic compound may be a monocyclic ring, a condensed ring, or a heterocyclic ring. As an aromatic compound, benzene, naphthalene, furan, pyrrole, thiophene, pyridine etc. are mentioned, for example.

The substituent which the alkyl group and the aryl group in R ²¹ may have will not be particularly limited as long as the reaction of the first raw material compound and the second raw material compound proceeds. As this substituent, a hydroxyl group, a carbonyl group, a formyl group, a hydroxycarbonyl group, an ester group, an amino group, a thiol group, etc. are mentioned, for example.

Specific examples of the diorganoboryl group include diphenylboranyl, dicyclohexyl, bicyclo[3.3.1]nonane-1,5-diyl, bis(3-methyl-2- butyl) etc.

The dihydroxyboron group represents a group represented by -B(OH) ₂ . As a derivative group of a dihydroxyboron group, a boronate ester group, a protected dihydroxyboron group, etc. are mentioned, for example.

The boronic acid ester group may be, for example, a group represented by -B(OR ²² ) ₂ . R ²² represents a monovalent group. The two R ²² may be the same or different, and may be linked to each other to form a ring together with a boron atom and an oxygen atom. R ²² may be, for example, a monovalent organic group, an optionally substituted alkyl group, or an optionally substituted aryl group. As an alkyl group, an aryl group, and the substituent which these may have in R ²² , the same group as the alkyl group, an aryl group in R ²¹ , and the substituent which these may have can be illustrated.

As a specific example of a borate group, a diisopropyl borate group, a di-tert-butyl borate group, etc. are mentioned, for example.

The protected dihydroxyboron group is not particularly limited, and may be, for example, a group protected by a method known as protection of a dihydroxyboron group.

As a protected dihydroxyboron group, for example, a group formed by a reaction of a difunctional compound such as a diol, a diamine, and a dicarboxylic acid with a dihydroxyboron group is mentioned. As a diol, pinacol, neopentyl glycol, catechol, pinanediol (pinanendiol), 1, 2- dicyclohexyl diol etc. are mentioned, for example. As a diamine, 1, 8- diaminonaphthalene etc. are mentioned, for example. As a dicarboxylic acid, N-methyliminodiacetic acid etc. are mentioned, for example.

Moreover, boronic acid groups, such as a triol boronic acid group, can also be illustrated as a protected dihydroxyboron group. A triol boronic acid group can be formed by the reaction of a triol with a dihydroxyboron group. As a triol, trimethylolethane (1,1,1- tris (hydroxymethyl) ethane) etc. are mentioned, for example. The counter cation of the boronic acid group is not particularly limited, and examples thereof include sodium ion (Na ⁺ ), potassium ion (K ⁺ ), organic phosphonium ion (PR ₄ ⁺ ), and the like.

As a boronic acid group, in addition to the above-mentioned triol boronic acid group, a trifluoroboronic acid group (-BF ₃ ^- ) and the like can be exemplified. The counter cation of the boronic acid group is not particularly limited, and examples thereof include sodium ion (Na ⁺ ), potassium ion (K ⁺ ), organic phosphonium ion (PR ₄ ⁺ ), and the like.

The metal catalyst is a catalyst capable of forming a boron-containing conjugated polyene compound by the reaction of a first raw material compound and a second raw material compound, that is, a catalyst capable of forming a carbon-carbon triple bond with 1,3-butadiene-4,4- What is necessary is just a catalyst that forms a conjugated triene skeleton by the reaction of diradicals.

As the metal catalyst, a catalyst containing at least one selected from the group consisting of ruthenium (Ru), rhodium (Rh), cobalt (Co), and nickel (Ni) is preferable, and a ruthenium catalyst is more preferable.

The ruthenium catalyst is preferably a catalyst capable of forming zero-valent ruthenium (Ru(0)) in the reaction system from the viewpoint that the first raw material compound and the second raw material compound can efficiently react by the reaction mechanism described later. . That is, the above-mentioned polyene formation step may be a step of reacting the first raw material compound and the second raw material compound in the presence of Ru(0).

An example of the reaction mechanism of the polyene formation step will be described below. In the following examples, the compound represented by the formula (1-1) described later was used as the first raw material compound, butadiene was used as the second raw material compound, and [(naphthalene)(1,5) was used as the metal catalyst. -cyclooctadiene)ruthenium(0)] to illustrate the reaction mechanism, but the present invention is not limited to these. In addition, the reaction mechanism of the polyene formation step is not limited to the following examples.

[Chemical formula 13]

In the above reaction mechanism, first, naphthalene is dissociated from the ruthenium complex, and the first raw material compound and the second raw material compound are respectively coordinated to ruthenium (0) (the above-mentioned A). Next, the above-mentioned B is formed by an oxidative coupling reaction, and the above-mentioned C is formed by the β hydride desorption. Furthermore, the above-mentioned D in which the conjugated triene is coordinated to ruthenium is formed by reductive detachment. In the above-mentioned example, butadiene has two reaction sites, and therefore, under the same mechanism, another molecule of the first raw material compound reacts to form the above-mentioned E to which the conjugated tetraene is coordinated. Finally, the conjugated tetraene is dissociated from ruthenium, whereby a boron-containing conjugated polyene compound can be obtained. In addition, in the case where the second raw material compound has only one reaction site, the boron-containing conjugated polyene compound is dissociated from ruthenium in the above-mentioned step D.

As a catalyst which can form Ru(0) in a reaction system, the zerovalent ruthenium complex which has Ru(0), the divalent ruthenium complex which has Ru(II), etc. are mentioned, for example.

Examples of the zerovalent ruthenium complex include [(naphthalene)(1,5-cyclooctadiene)ruthenium(0)], [(butadiene)(1,5-cyclooctadiene)(acetonitrile) ) ruthenium (0)] and so on.

As a divalent ruthenium complex, [bis(acetylacetone)(1,5-cyclooctadiene)ruthenium(II)], [tetrachlorobis(anisole)diruthenium], etc. are mentioned, for example. The divalent ruthenium complex can be reduced in the reaction system to form Ru(0). The divalent ruthenium complex may be reduced by the reaction with the reaction substrate (the first raw material compound and/or the second raw material compound), by the reaction of the ruthenium complexes with each other, or by adding another is reduced by the reaction of the reducing agent. Examples of the reducing agent include butyllithium, lithium aluminum hydride, sodium naphthalene, a combination of sodium carbonate and isopropanol, and the like.

In addition, the kind of ruthenium catalyst is not limited to the said thing, What is necessary is just a catalyst which can form a metal intercalation cyclization complex (metallacycle). For example, the ruthenium catalyst may be a catalyst that forms tetravalent ruthenium (Ru(IV)) upon formation of a metal intercalation cyclization complex. That is, the ruthenium catalyst may be a catalyst capable of forming a metal intercalation cyclization complex containing tetravalent ruthenium (Ru(IV)) in the reaction system.

Moreover, as a metal catalyst, a rhodium catalyst, a cobalt catalyst, a nickel catalyst, etc. can also be used.

The rhodium catalyst is preferably a catalyst capable of forming monovalent rhodium (Rh(I)) in the reaction system. As such a catalyst, the monovalent rhodium complex which has Rh(I), the trivalent rhodium complex which has Rh(III), etc. are mentioned, for example. The trivalent rhodium complex may be used in combination with a reducing agent. As the reducing agent, the same reducing agent as described above can be exemplified.

The cobalt catalyst is preferably a catalyst capable of forming monovalent cobalt (Co(I)) or zero-valent cobalt (Co(0)) in the reaction system. As such a catalyst, the divalent cobalt complex etc. which have Co(II) are mentioned, for example. The divalent cobalt complex may be used in combination with a reducing agent. As the reducing agent, the same reducing agent as described above can be exemplified.

The nickel catalyst is preferably a catalyst capable of forming zero-valent nickel (Ni(0)) in the reaction system. As such a catalyst, the zerovalent nickel complex which has Ni (0), the divalent nickel complex which has Ni (II), etc. are mentioned, for example. The divalent nickel complex may be used in combination with a reducing agent. As the reducing agent, the same reducing agent as described above can be exemplified. Moreover, as a reducing agent, zinc etc. can also be used suitably.

The amount of the metal catalyst is not particularly limited, but may be, for example, 0.1 mol % or more, preferably 1 mol % or more, and more preferably 5 mol % or more with respect to the first raw material compound. In addition, the amount of the metal catalyst may be, for example, 30 mol % or less, preferably 20 mol % or less, and more preferably 15 mol % or less with respect to the first raw material compound.

In the polyene formation step, the reaction of the first raw material compound and the second raw material compound may be carried out without a solvent or in an organic solvent. The type of the organic solvent is not particularly limited, as long as it is a solvent capable of dissolving the first raw material compound and the second raw material compound. Examples of the organic solvent include diethyl ether, tetrahydrofuran, acetone, hexane, benzene, toluene, methylene chloride, dimethyl sulfoxide, etc. From the viewpoint of not easily inhibiting the reaction between the first raw material compound and the second raw material compound, Preferred are tetrahydrofuran, benzene, toluene and the like.

The amount of the organic solvent is not particularly limited, but may be, for example, 100 parts by mass or more, preferably 1,000 parts by mass or more, for example, 100,000 parts by mass or less, relative to 100 parts by mass of the total of the first raw material compound and the second raw material compound, Preferably it is 10000 mass parts or less.

In the polyene formation step, the reaction temperature is not particularly limited, but may be, for example, 0 to 100° C. or room temperature. In addition, the reaction time is not particularly limited, and can be appropriately adjusted according to the type of the reaction substrate and the catalyst, the desired yield, and the like. The reaction time may be, for example, 0.1 to 72 hours, preferably 1 to 24 hours.

Hereinafter, preferred embodiments of the production method according to the present embodiment will be described.

(the first way)

In the first aspect, the first raw material compound is a compound represented by the following formula (1-1) (hereinafter also referred to as compound (1-1).), and the second raw material compound is the following formula (1-2-1). ) (hereinafter also referred to as compound (1-2-1).). In the first aspect, a compound represented by the following formula (1-3-1) (hereinafter also referred to as compound (1-3-1)) can be obtained by using such a first raw material compound and a second raw material compound. ).

[Chemical formula 14]

[Chemical formula 15]

[Chemical formula 16]

In formula (1-1), B ¹ represents a boron-containing group, and R ¹ represents a monovalent group.

In formula (1-2-1), n represents an integer of 0 or more, and R ² and R ³ each independently represent a hydrogen atom or a monovalent group. When n is 1 or more, a plurality of R ² may be the same or different from each other. In addition, a plurality of R ³ may be the same or different from each other. R ² , R ³ , and R ² and R ³ may be bonded to each other to form a ring.

In formula (1-3-1), B ¹ , R ¹ , n, R ² and R ³ have the same meanings as described above, respectively. In addition, the wavy line in the formula means that the double bond bonded to the wavy line may be either cis or trans. That is, the compound represented by the formula (1-3-1) may be a compound represented by the following formula (1-3-1a), a compound represented by the following formula (1-3-1b), or a mixture thereof. In the first aspect, among the following compounds, the compound represented by the formula (1-3-1a) tends to be obtained in large quantities.

[Chemical formula 17]

[Chemical formula 18]

The monovalent group in R ¹ is not particularly limited, and can be appropriately selected within the range in which the reaction of the compound (1-1) and the compound (1-2-1) proceeds. The monovalent group in R ¹ may be, for example, a monovalent organic group.

R ¹ may be, for example, an optionally substituted alkyl group, an optionally substituted aryl group, a boron-containing group, a silyl group, or the like.

The alkyl group in R ¹ may be linear, branched, or cyclic. The number of carbon atoms of the alkyl group in R ¹ is not particularly limited, and may be, for example, 1 to 8.

The aryl group in R ¹ represents the atomic group remaining after removing one hydrogen atom on the aromatic ring from the aromatic compound. The aromatic ring possessed by the aromatic compound may be a monocyclic ring, a condensed ring, or a heterocyclic ring. As an aromatic compound, benzene, naphthalene, thiophene, etc. are mentioned.

The substituents which the alkyl group and the aryl group in R ¹ may have are not particularly limited as long as the reaction of the first raw material compound and the second raw material compound proceeds. As this substituent, an aryl group, an alkyloxy group, an aryloxy group, a hydroxyl group, a formyl group, a carbonyl group, an amino group, a halogen group, etc. are mentioned, for example.

The silyl group in R ¹ may be a group represented by -Si(R ³¹ ) ₃ . R ³¹ represents a monovalent group. The three R ³¹ may be the same or different from each other, and may be connected to each other to form a ring together with the silicon atom. R ³¹ may be, for example, a monovalent organic group, an optionally substituted alkyl group, or an optionally substituted aryl group. As an alkyl group, an aryl group, and the substituent which these may have in R ³¹ , the same group as the alkyl group, an aryl group, and the substituent which these may have in the above-mentioned R ²¹ can be illustrated.

When R ¹ is a boron-containing group, a boron-containing conjugated polyene compound having a plurality of boron-containing groups bonded to carbon atoms constituting the conjugated polyene skeleton can be obtained.

In the first aspect, when R ¹ is a hydrogen atom, the reaction between the compound (1-1) and the compound (1-2-1) is difficult to proceed. On the other hand, when R ¹ is a silyl group, the reactivity between the compound (1-1) and the compound (1-2-1) is good, and the compound (1-3-1) can be obtained regioselectively. Then, a boron-containing conjugated polyene compound in which R ¹ in the compound (1-3-1) is substituted with a hydrogen atom can be obtained by a desilylation reaction. In addition, in this case, when R< ² > is a hydrogen atom, the conjugated polyene skeleton which does not have a substituent in a side chain can be formed.

The desilylation reaction is not particularly limited, and a known method can be applied. For example, the desilylation reaction can be carried out using tetra-n-butylammonium fluoride (TBAF) as a reactant. In addition, when a reaction does not progress easily, you may add the copper iodide (I) of a catalyst amount.

R ¹ may be a group whose value of Hammett's substituent constant σ _p is smaller than the value of Hammett's substituent constant σ _p of B ¹ . In the first aspect, the substituent (B ¹ ) having a large value of the substituent constant σp tends to react easily so as to be located at the terminal of the conjugated polyene skeleton.

n is an integer of 0 or more, and the upper limit thereof is not particularly limited. n may be, for example, 0-8, preferably 0-2.

The monovalent group in R ² is not particularly limited, and can be appropriately selected within the range in which the reaction of the compound (1-1) and the compound (1-2-1) proceeds. The monovalent group in R ² may be, for example, a monovalent organic group or a halogen group.

R ² may be, for example, a hydrogen atom, a halogen group, an alkyl group, an aryl group, a group represented by -C(=O)R ⁴¹ , a group represented by -C(=O)OR ⁴² , a boron-containing group, a methyl group A silyl group, etc., these groups may have a substituent.

The halogen group in R ² can be fluoro (-F), chloro (-Cl), bromo (-Br) or iodo (-I), preferably fluoro (-F), chloro (- Cl) or bromo (-Br).

The alkyl group, the aryl group, and the substituent which these may have in R ² are exemplified by the same groups as the alkyl group, the aryl group in R ²¹ described above, and the substituent which these may have.

R ⁴¹ represents a hydrogen atom or a monovalent group. R ⁴¹ may be, for example, a hydrogen atom or a monovalent organic group, a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group.

R ⁴² represents a hydrogen atom or a monovalent group. R ⁴² may be, for example, a hydrogen atom or a monovalent organic group, a hydrogen atom, an alkyl group that may have a substituent or an aryl group that may have a substituent, or an alkyl group that may have a substituent or an alkyl group that may have a substituent aryl group.

Examples of the alkyl groups, aryl groups, and substituents which may be possessed by R ⁴¹ and R ⁴² include the same groups as the alkyl groups, aryl groups, and substituents which may be possessed by the above-mentioned R ²¹ groups.

The monovalent group in R ³ is not particularly limited, and can be appropriately selected within the range in which the reaction of the compound (1-1) and the compound (1-2-1) proceeds. The monovalent group in R ³ may be, for example, a monovalent organic group or a halogen group.

R ³ can be, for example, a hydrogen atom, a halogen group, an alkyl group, an aryl group, a group represented by -C(=O)R ⁴¹ , a group represented by -C(=O)OR ⁴² , a boron-containing group, a methyl group A silyl group, etc., these groups may have a substituent. As each group in R ³ , the same groups as those in each group in R ² described above can be exemplified.

When at least one of R ² and R ³ is a boron-containing group, a boron-containing conjugated polyene compound having a plurality of boron-containing groups bonded to carbon atoms constituting the conjugated polyene skeleton can be obtained .

When at least one of R ³ is a boron-containing group, a boron-containing conjugated polyene compound having a boron-containing group at both ends of the conjugated polyene skeleton can be obtained. Such a boron-containing conjugated polyene compound can be suitably used for the production of a polymer compound by cross-coupling polymerization, and the like.

(Second way)

In the second aspect, the first raw material compound is a compound represented by the formula (1-1) (compound (1-1)), and the second raw material compound is a compound represented by the following formula (1-2-2) (hereinafter also referred to as called compound (1-2-2).). In the second aspect, the compound (1-2-2) has two reaction points with the compound (1-1). Therefore, in the second aspect, a compound represented by the following formula (1-3-2) having at least two boron-containing groups derived from compound (1-1) (hereinafter also referred to as compound (1-1)) can be obtained 3-2).).).).).

[Chemical formula 19]

[Chemical formula 20]

[Chemical formula 21]

In formula (1-1), B ¹ represents a boron-containing group, and R ¹ represents a monovalent group.

In formula (1-2-2), n ¹ represents an integer of 0 or more, n ² represents 0 or 1, and R ² represents a hydrogen atom or a monovalent group. When n ¹ is 1 or more, a plurality of R ² may be the same or different from each other. However, when n ¹ is 1 or more, n ² is 1. R ² may be bonded to each other to form a ring.

In formula (1-3-2), B ¹ , R ¹ , n ¹ , n ² and R ² have the same meanings as described above, respectively. The two B ^1s may be the same or different from each other. In addition, the two R ^1s may be the same or different from each other. In addition, the wavy line shows that the double bond bonded to the wavy line may be either cis or trans. That is, the compound represented by the formula (1-3-2) may be a compound represented by the following formula (1-3-2a), a compound represented by the following formula (1-3-2b), a compound represented by the following formula (1-3) A compound represented by -2c), a compound represented by the following formula (1-3-2d), or a mixture thereof. In the second aspect, there is a tendency that the compound represented by the formula (1-3-1a) is obtained the most among the following compounds.

[Chemical formula 22]

[Chemical formula 23]

[Chemical formula 24]

[Chemical formula 25]

R ¹ in formula (1-1) may be the same as R ¹ in formula (1-1) in the first embodiment.

R ² in the formula (1-2-2) may be the same as R ² in the formula (1-2-1) in the first mode.

n ¹ is an integer of 0 or more, and the upper limit thereof is not particularly limited. n ¹ may be, for example, 0 to 8, and preferably 0 to 1.

When n ¹ is 0, n ² is 0 or 1, and when n is 1 or more, n ² is 1.

(third way)

In the third aspect, the first raw material compound is a compound represented by the following formula (2-1), and the second raw material compound is a compound represented by the following formula (2-2). In the third aspect, a compound represented by the following formula (2-3) (hereinafter also referred to as compound (2-3)) can be obtained by using such a first raw material compound and a second raw material compound.

[Chemical formula 26]

[Chemical formula 27]

[Chemical formula 28]

In formula (2-1), R ⁴ and R ⁵ each independently represent a monovalent group.

In formula (2-2), m represents an integer of 0 or more, and R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent group. Wherein, at least one of the two R ⁷ is a boron-containing group. When m is 1 or more, a plurality of R ⁶ may be the same or different from each other. In addition, the two R ^7s may be the same or different from each other. R ⁶ , R ⁷ , and R ⁶ and R ⁷ may bond to each other to form a ring.

In formula (2-3), R ⁴ , R ⁵ , m, R ⁶ and R ⁷ have the same meanings as described above, respectively. In addition, the wavy line shows that the double bond bonded to the wavy line may be either cis or trans. That is, the compound represented by the formula (2-3) may be a compound represented by the following formula (2-3a), a compound represented by the following formula (2-3b), or a mixture thereof. In the third aspect, among the following compounds, the compound represented by the formula (2-3a) tends to be obtained in large quantities.

[Chemical formula 29]

[Chemical formula 30]

The monovalent group in R ⁴ and R ⁵ is not particularly limited, and can be appropriately selected within the range in which the reaction of compound (2-1) and compound (2-2) proceeds. As the monovalent group in R ⁴ and R ⁵ , the same groups as described above for R ¹ can be exemplified.

In the third aspect, the value of the Hammett substituent constant σ _p of R ⁴ is larger than the value of the Hammett substituent constant σ _p of R ⁵ . In the third aspect, the substituent (R ⁴ ) having a large value of the substituent constant σ _p tends to be easily reacted so as to be located at the terminal of the conjugated polyene skeleton.

m is an integer of 0 or more, and the upper limit thereof is not particularly limited. m may be, for example, 0-8, preferably 0-2.

The monovalent group in R ⁶ is not particularly limited, and can be appropriately selected within the range in which the reaction of the compound (2-1) and the compound (2-2) proceeds. As R ⁶ , the same groups as the above-mentioned R ² can be exemplified.

The monovalent group in R ⁷ is not particularly limited, and can be appropriately selected within the range in which the reaction of the compound (2-1) and the compound (2-2) proceeds. As R ⁷ , the same groups as the above-mentioned R ³ can be exemplified. Wherein, at least one of the two R ⁷ is a boron-containing group.

<Boron-containing conjugated polyene compound>

The boron-containing conjugated polyene compound according to the present embodiment is a compound produced by the above-described production method, and has a conjugated polyene skeleton including three or more carbon-carbon double bonds, and a conjugated polyene bonded to constitute the conjugated polyene Boron-containing groups on carbon atoms of the backbone.

Preferred embodiments of the boron-containing conjugated polyene compound according to the present embodiment will be described below.

(the first way)

The boron-containing conjugated polyene compound according to the first aspect is a compound represented by the following formula (1-3-1A).

[Chemical formula 31]

In formula (1-3-1A), B ¹ , n, R ² and R ³ have the same meanings as B ¹ , n, R ² and R ³ in the above formula (1-3-1). In addition, R ¹¹ represents a hydrogen atom or a monovalent group, and examples of the monovalent group in R ¹¹ include the same groups as those for R ¹ described above.

For the compound in which R ¹¹ is a hydrogen atom, for example, after the compound (1-1) in which R ¹ is a silyl group and the compound (1-2-1) are reacted, the silyl group in R ¹ can be desilylated by a desilylation reaction. Manufactured by substituting a hydrogen atom for the radical.

(Second way)

The boron-containing conjugated polyene compound according to the second aspect is a compound represented by the following formula (1-3-2A).

[Chemical formula 32]

In formula (1-3-2A), B ¹ , n ¹ , n ² and R ² have the same meanings as B ¹ , n ¹ , n ² and R ² in the above formula (1-3-2). In addition, R ¹¹ represents a hydrogen atom or a monovalent group, and examples of the monovalent group in R ¹¹ include the same groups as those for R ¹ described above.

For the compound in which R ¹¹ is a hydrogen atom, for example, the compound (1-1) in which R ¹ is a silyl group and the compound (1-2-2) can be reacted, and then the silyl group in R 1 can be converted to the silyl group of R ¹ by a desilylation reaction. Manufactured by substituting a hydrogen atom for the radical.

(third way)

The boron-containing conjugated polyene compound according to the third aspect is a compound represented by the following formula (2-3A).

[Chemical formula 33]

In formula (2-3A), R ⁴ , m, R ⁶ and R ⁷ have the same meanings as R ⁴ , m, R ⁶ and R ⁷ in the above formula (2-3). In addition, R ¹⁵ represents a hydrogen atom or a monovalent group, and examples of the monovalent group in R ¹⁵ include the same groups as those for R ⁵ described above.

For the compound in which R ¹⁵ is a hydrogen atom, the silyl group of R ⁵ can be substituted by a desilylation reaction after the compound (2-1) in which R ⁵ is a silyl group and the compound (2-2) are reacted, for example. Made for hydrogen atoms.

The boron-containing conjugated polyene compound according to the present embodiment has a conjugated polyene skeleton and a boron-containing group bonded to the conjugated polyene skeleton. Therefore, according to the boron-containing conjugated polyene compound according to the present embodiment, the conjugated polyene skeleton can be easily introduced into the target compound by the reaction (eg, cross-coupling reaction) starting from the boron-containing group. In this use, the boron-containing group is preferably a dihydroxyboron group or a derivative group thereof.

In addition, the boron-containing conjugated polyene compound according to the present embodiment can also be used in applications such as electronic materials as a π-conjugated compound having a boron-containing group. In this use, the boron-containing group is preferably a boryl group or a derivative group thereof.

In addition, the boron-containing conjugated polyene compound according to the present embodiment may have two or more boron-containing groups, and in this case, it can be suitably used for cross-coupling-based polymerization (for example, with a dihalogenated aromatic compound). Polymerization) in the production of polymer compounds, etc. In this use, the boron-containing group is preferably a dihydroxyboron group or a derivative group thereof.

The boron-containing conjugated polyene compound and the method for producing the same have been described above, but the present invention is not limited to these.

For example, one aspect of the present invention relates to a method for producing a conjugated polyene compound using the above-mentioned boron-containing conjugated polyene compound.

A method for producing a conjugated polyene according to an embodiment includes the following steps: a first step of obtaining a reaction solution containing a boron-containing conjugated polyene compound by the above-described method for producing a boron-containing conjugated polyene compound; and, a second step In the second step, a coupling reaction is performed by adding a coupling reaction catalyst and a third raw material compound having a reactive group capable of coupling reaction with the boron-containing group to the reaction solution.

The first step may be, for example, a step of producing the above-mentioned boron-containing conjugated polyene compound in the reaction system by the reaction of the first raw material compound and the second raw material compound in the presence of a metal catalyst. The second step may be a step of adding a coupling reaction catalyst and a third raw material compound to the reaction system. According to such a one-pot reaction, the target conjugated polyene compound can be efficiently produced.

In this way, in the above-described method for producing a boron-containing conjugated polyene compound, the subsequent coupling reaction can be carried out in one pot without recovering the boron-containing conjugated polyene compound from the reaction system after the reaction. This point can be said to be a great advantage of the above-mentioned method for producing a boron-containing conjugated polyene compound.

The coupling reaction catalyst is not particularly limited, and can be appropriately selected from known coupling reaction catalysts and used. Specific examples of the coupling reaction catalyst include known catalysts (for example, palladium catalysts, nickel catalysts, iron complexes such as [Pd(PPh ₃ ) ₄ ]) used in the Suzuki-Miyaura coupling reaction. catalysts, etc.), immobilized catalysts (eg, immobilized palladium catalysts, immobilized nickel catalysts, immobilized iron catalysts, etc.), metal particulate catalysts (eg, palladium particulate catalysts, nickel particulate catalysts, iron particulate catalysts, etc.), and the like.

The reactive group possessed by the third raw material compound is not particularly limited as long as it is a functional group capable of coupling reaction with a boron-containing group, but is preferably a halogen group from the viewpoint of excellent substrate selectivity and reactivity.

The reaction conditions for the coupling reaction are not particularly limited, and can be appropriately selected from known reaction conditions for the coupling reaction.

Example

(Example 1-1)

The synthesis of the boron-containing conjugated polyene compound (A-1) was carried out by the following method.

[Chemical formula 34]

Specifically, diisopropyl 1-pentynylboronic acid (20.3 μL, 0.0884 mmol) and (E)-methyl 2,4-pentadienoate (10.3 μL, 0.0881 mmol) were dissolved in benzene-d ₆ (0.6 mL), [Ru(naphthalene)(cod)] (2.99 mg, 0.00886 mmol) was further added. The reaction was carried out at room temperature. As a result, the boron-containing conjugated polyene compound (A-1) was produced in a yield of 54% in a reaction time of 4 hours. After 24 hours, the boron-containing conjugated polyene compound was produced. (A-1) was produced in a yield of 89%. In addition, the formation of a boron-containing conjugated polyene compound was confirmed by ¹ H-NMR measurement. The measurement results are as follows.

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 0.98 (t, J=7.4 Hz, 3H), 1.13 (d, J=6.2 Hz, 12H), 1.55 (sext, J=7.7 Hz, 2H) ), 2.59(t, J=7.7Hz, 2H), 3.45(s, 3H), 4.43(sept, J=6.2Hz, 2H), 5.54(s, 1H), 5.91(d, J=15.6Hz, 1H) ), 6.28 (d, J=15.1Hz, 1H), 6.29 (dd, J=15.1, 11.0Hz, 1H), 7.52 (dd, J=15.6, 11.0Hz, 1H).

(Example 1-2)

The synthesis of the boron-containing conjugated polyene compound (A-1) was carried out by the following method.

[Chemical formula 35]

Specifically, diisopropyl 1-pentynylboronic acid (20.5 μL, 0.0894 mmol) and (E)-methyl 2,4-pentadienoate (10.4 μL, 0.0895 mmol) were dissolved in dichloromethane- To d ₂ (0.6 mL), [Ru(naphthalene)(cod)] (2.94 mg, 0.00873 mmol) was further added. The reaction was carried out at room temperature, and as a result, the boron-containing conjugated polyene compound (A-1) was produced in a yield of 50% in a reaction time of 7 hours.

(Example 2)

The synthesis of the boron-containing conjugated polyene compound was carried out by the following method.

[Chemical formula 36]

Specifically, diisopropyl 1-pentynylboronic acid (20.5 μL, 0.0895 mmol) and 1,3-pentadiene (9.0 μL, 0.089 mmol) were dissolved in benzene-d ₆ (0.6 mL), and further [Ru(naphthalene)(cod)] (6.07 mg, 0.00180 mmol) was added. The reaction was carried out at 70° C. for 1 hour, and as a result, a boron-containing conjugated polyene compound (A-2) was obtained in a yield of 27%. In addition, as a result of carrying out the same reaction at room temperature, after 28 hours, the target object was obtained in a yield of 36%.

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 0.94 (d, J=6.0 Hz, 3H), 1.15 (t, J=6.4 Hz, 3H), 1.17 (d, J=6.2 Hz, 12H) ), 1.55(m, 2H), 2.80(t, J=7.7Hz, 2H), 4.45(sept, J=6.0Hz, 2H), 5.58(s, 1H), 5.60(dqd, J=15.8, 6.0, 4.4Hz, 1H), 5.99 (dd, J=15.2, 10.4Hz, 1H), 6.28 (d, J=14.7Hz, 1H), 6.48 (ddd, J=14.7, 10.6, 4.4Hz, 1H).

(Example 3)

The synthesis of the boron-containing conjugated polyene compound was carried out by the following method.

[Chemical formula 37]

Specifically, 3-hexyne (6.5 μL, 0.057 mmol) and 2-{(E)-1,3-butadienyl}-4,4,5,5-tetramethyl-1,3, 2-dioxaborolane (11.5 μL, 0.0575 mmol) was dissolved in benzene-d ₆ (0.6 mL), to which was further added [Ru(naphthalene)(cod)] (1.93 mg, 0.00572 mmol) . After 25 minutes at room temperature, the boron-containing conjugated polyene compound (A-3) was produced in a yield of 89%.

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 0.81 (t, J=7.4 Hz, 3H), 0.89 (t, J=7.4 Hz, 3H), 1.11 (s, 12H), 1.90 (quint , J=7.4Hz, 2H), 2.06 (q, J=7.4Hz, 2H), 5.28 (t, J=7.4Hz, 1H), 5.93 (d, J=17.8Hz, 1H), 6.24 (d, J =15.5Hz, 1H), 6.35 (dd, J=15.5, 9.8Hz, 1H), 7.53 (dd, J=17.5, 9.7Hz, 1H).

¹³ C{ ¹ H} NMR (100 MHz, [D ₆ ]benzene, rt): δ 13.84(s), 14.14(s), 21.69(s), 19.94(s), 24.92(s), 82.99 (s), 120(br), 127-128 (obscured by overlapping with C ₆ D ₆ ), 126.01(s), 137.01(s), _140.64 (s), _151.49 (s).

HRMS(APCI): m/z calcd for C ₁₆ H ₂₈ BO ₂ +H ⁺ : 263.2180[M+H] ⁺ ; found: 263.2177.

(Example 4)

The synthesis of the boron-containing conjugated polyene compound was carried out by the following method.

[Chemical formula 38]

Specifically, diphenylacetylene (32.09 mg, 0.180 mmol) was dissolved in benzene-d ₆ (0.6 mL), to which was added 2-{(E)-1,3-butadienyl}-4 ,4,5,5-tetramethyl-1,3,2-dioxaborolane (36.0 μL, 0.180 mmol), and then [Ru(naphthalene)(cod)] (6.07 mg, 0.0180 mmol) was added. mmol). The reaction was completed after 5 minutes at room temperature, and the boron-containing conjugated polyene compound (A-4) was obtained in a yield of 63%.

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 1.07 (s, 12H), 5.65 (d, J=17.2 Hz, 1H), 6.16 (dd, J=14.9, 10.9 Hz, 1H), 6.47 (s, 1H), 6.61 (d, J=14.9Hz, 1H), 7.00-7.02 (m, 5H), 7.04-7.10 (m, 5H) 7.50 (dd, J=17, 10Hz, 1H, partially overlapped partially obscured by overlap).

¹³ C{ ¹ H} NMR (100 MHz, C ₆ D ₆ , rt): δ 24.55(s), 24.86(s), 77.61(s), 82.02(s), 122(br), 127.40(s), 128 (obscured by overlapping with _C6D6 ), 129.17(s), _129.70 (s), _129.91 (s), _133.67 (s), 133.89(s), 137.08(s) , 138.45(s), 141.85(s), 141.98(s, 3CH), 150.41(s, 5-CH).

MS (EI): m/z=358 (M+).

HRMS(APCI): m/z calcd for C ₂₄ H ₂₇ BO ₂ +H ⁺ : 359.2181[M+H] ⁺ ; found: 359.2183.

(Example 5)

The synthesis of the boron-containing conjugated polyene compound was carried out by the following method.

[Chemical formula 39]

Specifically, 2-{(E)-1,3-butadienyl}-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (40.4 μL , 0.2244 mmol) was dissolved in benzene-d ₆ (0.6 mL), to which was added diisopropyl 1-pentynylboronate (51.0 μL, 0.222 mmol), followed by [Ru(naphthalene)(cod) ] (7.59 mg, 0.0225 mmol). The reaction was carried out at room temperature for 3 hours, and as a result, a boron-containing conjugated polyene compound (A-5) was obtained in a yield of 38%.

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 0.96 (t, J=8Hz, 3H), 1.10 (s, 12H), 1.16 (d, J=7Hz, 12H), 1.56-1.61 (m , 2H), 2.60-2.64(m, 2H), 4.42(sept, J=7Hz, 2H), 5.51(s, 1H), 5.92(d, J=17Hz, 1H), 6.34(d, J=15Hz, 1H), 6.52 (dd, J=15, 11Hz, 1H), 7.45 (dd, J=17, 11Hz, 1H).

¹³ C{ ¹ H} NMR (100 MHz, C ₆ D ₆ , rt): δ 14.46(s), 23.87(s), 24.86(s), 24.91(s), 32.78(s), 65.56(s), 83.05(s), 122(br), 126.01(s), 131.45(s), 142.42(s), 150.92(s), 156.18(s).

(Example 6)

The synthesis of the boron-containing conjugated polyene compound was carried out by the following method.

[Chemical formula 40]

Specifically, 1-phenyl-1-propyne (22.5 μL, 182 μmol) and 2-{(E)-1,3-butadienyl}-4,4,5,5-tetramethyl -1,3,2-Dioxaborolane (36.0 μL, 180 μmol) was dissolved in benzene-d ₆ (0.6 mL), to which was further added [Ru(naphthalene)(cod)] (6.07 mg, 18.0 μmol ). The reaction was carried out at room temperature for 1 hour to obtain a boron-containing conjugated polyene compound (A-6) in a yield of 61%.

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 1.12 (s, 12H), 1.75 (d, J=1.16 Hz, 3H), 5.96 (d, J=17.7 Hz, 1H), 6.35-6.44 (m, 2H), 6.41 (s, 1H), 6.97-7.02 (m, 2H), 7.10-7.15 (m, 3H), 7.53 (ddd, J=17.6, 8.3, 1.5Hz, 1H).

¹³ C{ ¹ H} NMR (100 MHz, C ₆ D ₆ , rt): δ 13.78(s), 24.94(s), 83.08(s), 121(br), 127.00(s), 129.60(s), 130.68(s), 134.09(s), 136.01(s), 138.00(s), 142.08(s, 4-CH), 150.96(s, 5-CH). 6-CH may not be observed by HMQC due to broadening to (was not observed by probably dueto broadening).

HRMS(APCI): m/z calcd for C ₁₉ H ₂₅ BO ₂ +H ⁺ : 297.2024[M+H] ⁺ ; found: 297.2010.

(Example 7)

The synthesis of the boron-containing conjugated polyene compound was carried out by the following method.

[Chemical formula 41]

Specifically, 1-phenyl-2-trimethylsilyl-acetylene (34.0 μL, 176 μmol) and 2-{(E)-1,3-butadienyl}-4,4,5 ,5-Tetramethyl-1,3,2-dioxolaborane (19.0 μL, 95.0 μmol) was dissolved in benzene-d ₆ (0.6 mL), to which was further added [Ru(naphthalene)(cod) ] (3.20 mg, 9.48 μmol). The reaction was carried out at room temperature for 30 minutes, and as a result, a boron-containing conjugated polyene compound (A-7) was obtained in a yield of 41%. In this reaction, 1-phenyl-2-trimethylsilyl-acetylene reacts regioselectively, and as an initial product, a product whose stereoselectivity of the terminal phenyl group is a Z body is obtained. However, by standing in a solution at room temperature after that, isomerization proceeds, and the stereoselectivity of the phenyl group is E-form.

Trimethyl((1Z,3E,5E)-1-phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)hexa -1,3,5-Trien-2-yl)silane

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 0.20 (s, 9H), 1.08 (s, 12H), 5.91 (d, J=17Hz, 1H), 6.54 (d, J=16Hz, 1H) ), 6.66 (dd, J=16, 10Hz, 1H), 6.9 (s, 1H, obscured by overlap), 7.0-7.1 (m, 3H), 7.2 (d, J=7Hz, 12H) 7.44 (dd, J=17.2, 10.3Hz, 1H).

¹³ C{ ¹ H} NMR (100 MHz, C ₆ D ₆ , rt): δ 0.45 (s), 24.88 (s), 83.02 (s), 120.92 (br), 128 (overlapped with C ₆ D ₆ with C ₆ D ₆ )), 129.93(s), 134.85(s), 137.70(s), 138.14(s), 140.84(s), 141.78(s), 142.91(s), 151.33(s).

HRMS(APCI): m/z calcd for C ₂₁ H ₃₁ BO ₂ Si+H ⁺ : 355.2263[M+H] ⁺ ; found: 355.2263.

Trimethyl((1E,3E,5E)-1-phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)hexa -1,3,5-Trien-2-yl)silane

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 0.21 (s, 9H), 1.08 (s, 12H), 5.91 (d, J=18Hz, 1H), 6.66 (dd, J=15, 10Hz) , 1H), 6.9 (1H, obscured by overlap), 7.0-7.1 (m, 3H), 7.05 (d, J=15Hz, 1H), 7.44 (dd, J=18, 10Hz, 1H, partially obscured by overlap ( partly obscured by overlap)).

(Example 8)

The synthesis of the boron-containing conjugated polyene compound was carried out by the following method.

[Chemical formula 42]

Specifically, diisopropyl 2-phenylethynylborate (24.5 μL, 0.101 mmol) and (E)-methyl 2,4-pentadienoate (11.5 μL, 0.0987 mmol) were dissolved in benzene-d ₆ (0.5 mL) was further added with [Ru(naphthalene)(cod)] (3.43 mg, 0.0102 mmol). The reaction was carried out at 30°C. As a result, the boron-containing conjugated polyene compounds (A-101) and (A-102) were obtained in a yield of 52% (production ratio 37/67) in a reaction time of 2 hours. generate. In addition, the formation of a boron-containing conjugated polyene compound was confirmed by ¹ H-NMR measurement. The measurement results are as follows.

(A-101)

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 0.95 (d, ³ _{JH, H} = 6.3 Hz, 12H), 3.36 (s, 3H), 4.37 (sept, ³ J _{H, H} = 5.8 Hz, 2H), 5.59 (d, ³ J _{H, H} = 15.5 Hz, 1 H), 5.82 (s, 1 H, obscured by overlapping with reactant), 6.09 (dd, ³ J _{H, H} =15.5, 11.5Hz, 1H), 6.43-6.54(m), 7.18-7.28(m), 7.50(dd, ³ _{JH, H} = 15.5, 10.9Hz, 1H).

(A-102)

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 1.04 (d, ³ _{JH, H} = 5.7 Hz, 12H), 3.45 (s, 3H), 4.37 (sept, ³ J _{H, H} = 5.8 Hz, 2H), 5.96(d, ^3JH _{, H} =15.5Hz, 1H), 6.43-6.54(m, 2H), 6.68(s, 1H), 7.02(t, ^3JH _{, H} =6.9Hz, 1H), 7.18-7.28(m), 7.58(dd, ^3JH , _H =15.5, 10.9Hz, 1H).

(Example 9)

The synthesis of the boron-containing conjugated polyene compound was carried out by the following method.

[Chemical formula 43]

Specifically, dimethyl 2-phenylethynylborate (24.5 μL, 0.101 mmol) and (E)-methyl 2,4-pentadienoate (11.5 μL, 0.0987 mmol) were dissolved in benzene-d ₆ (0.5 mL), [Ru(naphthalene)(cod)] (3.43 mg, 0.0102 mmol) was further added. The reaction was carried out at 30°C for 1 hour and further at 50°C for 2 hours. As a result, the boron-containing conjugated polyene compounds (A-103) and (A-104) were obtained in a yield of 68% (production ratio 19/81) generated. In addition, the formation of a boron-containing conjugated polyene compound was confirmed by ¹ H-NMR measurement. The measurement results are as follows.

(A-103)

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 3.22 (s, 3H), 3.35 (s, 6H), 5.62 (d, ³ J _{H, H} = 15.5 Hz, 1H), 5.70 (s, 1H), 6.12(dd, ^3JH , _H =15.5, 11.0Hz, 1H), 6.45(d, ^3JH , _H =15.5Hz, 1H), 7.28-7.30(m), 7.49(dd, ^3J _{H, H} = 15.5, 11.0 Hz, 1H).

(A-104)

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 3.23 (s, 3H), 3.32 (s, 6H), 5.82 (d, ³ J _{H, H} = 15.5 Hz, 1H), 6.28 (dd, ³ J _{H, H} = 15.5, 10.9 Hz, 1H), 6.46 (d, ³ J _{H, H} = 15.5 Hz, 1 H), 6.70 (s, 1 H), 7.28-7.30 (m), 7.55 (dd, ³ J _{H, H} = 15.5, 10.9 Hz, 1H).

(Example 10)

The synthesis of the boron-containing conjugated polyene compound was carried out by the following method.

[Chemical formula 44]

Specifically, 2-phenylethynylboronic acid pinacol ester (40.62 μL, 0.1781 mmol) and (E)-methyl 2,4-pentadienoate (21.0 μL, 0.180 mmol) were dissolved in benzene-d ₆ (0.6 mL) was further added with [Ru(naphthalene)(cod)] (7.12 mg, 0.0211 mmol). The reaction was carried out at 30°C. As a result, the boron-containing conjugated polyene compound (A-105) was produced in a yield of 47% in a reaction time of 2 hours.

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 1.02 (s, 12H), 3.45 (s, 3H), 6.07 (d, ³ J _{H, H} = 14.9 Hz, 1H), 6.55 (d, ³ J _{H, H} = 15.5Hz, 1H), 6.80 (dd, ³ J _{H, H} = 15.2, 10.9 Hz, 1H), 6.80 (s, 1H), 7.00-7.13 (m, 3H), 7.39-7.40 ( m, 1H), 7.61 (dd, ³ J _{H, H} = 15.2, 10.9 Hz, 1H).

¹³ C{ ¹ H} NMR (100 MHz, C ₆ D ₆ , rt): δ 24.9(s), 51.0(s), 83.9(s), 120.5(s), 128.9(s), 129.1(s), 138.7(s), 145.7(s), 147.1(s), 147.3(s), 167.1(s).

HRMS(APCI): m/z calcd for C ₂₀ H ₂₅ BO ₄ +H ⁺ : 341.1922[M+H] ⁺ ; found: 341.1914.

(Example 11)

The synthesis of the boron-containing conjugated polyene compound was carried out by the following method.

[Chemical formula 45]

Specifically, 1-pentynylboronic acid pinacol ester (38.5 μL, 0.180 mmol) and (E)-methyl 2,4-pentadienoate (21.0 μL, 0.180 mmol) were dissolved in benzene-d ₆ (0.6 mL), [Ru(naphthalene)(cod)] (6.04 mg, 0.0179 mmol) was further added. The reaction was carried out at 30°C for 26 hours and at 50°C for 2 hours. As a result, the boron-containing conjugated polyene compounds (A-106) and (A-107) were obtained in a yield of 42% (produced than 42/58).

(A-106)

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 1.01 (t, ³ _{JH, H} = 7.44 Hz, 3H), 1.06 (s, 12H), 1.51 (sext, ³ J _{H, H} = 7.44 Hz, 2H), 2.71 (t, ^3JH , _H =7.44Hz, 2H), 3.43(s, 3H), 5.71(s, 3H), 5.87(d, ^3JH _{, H} =15.5Hz, 1H) , 6.15-6.25 (m, 2H), 7.38 (dd, ³ J _{H, H} = 15.2, 9.76 Hz, 1H).

¹³ C{ ¹ H} NMR (100 MHz, C ₆ D ₆ , rt): δ 14.13(s), 23.81(s), 24.81(s), 32.19(s), 51.04(s), 83.24(s), 122.04(s), 124(br, coalesced with base line), 127-129( _{3 -} CH, obscured by overlapping with _C6D6 ), _145.02 (s ), 145.37(s), 159.11(s), 166.95(s).

(A-107)

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 0.88 (t, ³ _{JH, H} =7.48 Hz, 3H), 1.01 (s, 12H), 1.36 (sext, ³ _{JH, H} =7.44 Hz, 2H), 2.46(q, ^3JH , _H =7.44Hz, 2H), 3.43(s, 3H), 6.06(d, ^3JH _{, H} =14.7Hz, 1H), 6.20(t, ^3J _{H, H} = 7.44 Hz, 1H), 6.49 (d, ³ J _{H, H} = 15.4 Hz, 1 H), 6.97 (dd, ³ J _{H, H} = 15.2, 11.4 Hz, 1 H), 7.64 (dd, ³ J _{H, H} = 15.5, 11.4 Hz, 1H).

¹³ C{ ¹ H} NMR (100 MHz, C ₆ D ₆ , rt): δ 13.95(s), 23.11(s), 24.74(s), 34.06(s), 50.91(s), 82.91(s), 119.75(s), 127-129 ( ₄ -CH obscured by overlapping with _C6D6 ), _146.56 (s), 147.25(s), 154.90(s), 167.27(s), ₆ -CB(pin) was not observed.

HRMS(APCI): m/z calcd for C ₁₇ H ₂₅ BO ₄ +H ⁺ : 307.2078[M+H] ⁺ ; found: 307.2082.

(Example 12)

The synthesis of the boron-containing conjugated polyene compound was carried out by the following method.

[Chemical formula 46]

Specifically, 1-pentynylboronic acid pinacol ester (51.0 μL, 0.222 mmol) and 2-{(E)-1,3-butadienyl}-4,4,5,5-tetra Methyl-1,3,2-dioxaborolane (40.4 μL, 0.224 mmol) was dissolved in benzene-d ₆ (0.6 mL), and [Ru(naphthalene)(cod)] (7.59 mg, 0.0225 mmol). The reaction was carried out at room temperature. As a result, the boron-containing conjugated polyene compounds (A-108) and (A-109) were produced in a yield of 34% (production ratio 25/75) in a reaction time of 3 hours. .

(A-108)

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 0.97 (t, ³ J _{H, H} = 7.4 Hz, 3H), 1.05 (s, 12H), 1.09 (obscured by A-109 overlapping with A-109)), 1.55(sext, ³ J _{H, H} =7.4Hz, 2H), 2.75(t, ³ J _{H, H} =7.4Hz, 2H), 5.70(s, 1H), 5.92(d , ³ J _{H, H} = 17.2 Hz, 1H), 6.27 (d, ³ J _{H, H} = 15.5 Hz, 1 H), 6.50 (dd, ³ J _{H, H} = 15.5, 10.3 Hz, 1 H), 7.36 (dd , ³ J _{H, H} = 17.2, 11.5 Hz, 1 H).

¹³ C{ ¹ H} NMR (100 MHz, C ₆ D ₆ , rt): δ 14.14(s), 23.91(s), 24.82(s), 32.28(s), 82.72(s), 83.05(s), 122(br), 132.64(s), 141.59(s), 150.82(s), 159.97(s), some resonances were obscured by overlapping with theresonances of A-108and solvent).

(A-109)

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 0.88 (t, ³ J _{H, H} = 7.4 Hz, 3H), 1.01 (s, 12H), 1.09 (s, 12H), 1.36 (sext, ³ J _{H, H} = 6.9 Hz, 2H), 2.44 (q, ³ J _{H, H} = 7.4 Hz, 2 H), 6.02 (dd, ³ J _{H, H} = 17.2 Hz, ⁴ J _{H, H} = 1.7 Hz, 1H), 6.13-6.20 (obscured by overlapping with an impurity, 1H), 6.55 (d, ³ _{JH, H} =15.5Hz, 1H), 7.07 (dd, ³ _{JH, H} = 15.5, 10.9 Hz, 1H), 7.56 (ddd, ³ J _{H, H} = 17.2, 10.3 Hz, ⁴ J _{H, H} = 2.3 Hz, 1 H).

¹³ C{ ¹ H} NMR (100 MHz, C ₆ D ₆ , rt): δ 13.99(s), 23.22(s), 24.61(s), 24.90(s), 34.09(s), 82.89(s), 83.14(s), 120(br), 132.23(s), 142.84(s), 151.8(s), 151.9(s).

HRMS (APCI): m/z calcd for C ₂₁ H ₃₆ B ₂ O ₄ +H ⁺ : 375.2880[M+H] ⁺ ; found: 365.2881.

(Example 13)

The synthesis of the boron-containing conjugated polyene compound was carried out by the following method.

[Chemical formula 47]

Specifically, [Ru(acac) ₂ (1,5-cod)] (4.30 mg, 0.0106 mmol) was measured in a 25 mL Schlenk flask, and nitrogen replacement was performed. Hexane (600 μL), BuLi (6.2 μL, 0.0099 mmol), 3-hexyne (11.5 μL, 0.101 mmol), (E)-1-(4,4,5,5-tetramethyl-1, 3,2-dioxaborolane-2-yl)butadiene (20.0 μL, 0.100 mmol) and stirred at room temperature for 7 hours. Then, the reaction liquid was measured by GC-MS, and as a result, the production of the target substance was confirmed. The solvent was distilled off, the whole was dissolved in benzene-d ₆ , and dibenzyl (1.94 mg, 10.6 μmol) was added. The yield of the target product was determined from ¹ H NMR. The yield was 83%.

(Example 14)

The synthesis of the boron-containing conjugated polyene compound was carried out by the following method.

[Chemical formula 48]

Specifically, CoBr ₂ (PPh ₃ ) ₂ (8.5 mg, 0.011 mmol), PPh ₃ (9.6 mg, 0.037 mmol), and Zn (53.5 mg, 0.820 mmol) were measured in a 25 mL Schlenk bottle, and nitrogen Displacement, then _CH3CN (500 [mu]L) was added and stirred for 10 minutes. Then, 3-hexyne (12.0 μL, 0.107 mmol), (E)-2-(but-1,3-dienyl)-4,4,5,5-tetramethyl-1,3,2 were added - Dioxaborolane (20.0 μL, 0.0990 mmol) and H ₂ O (70.0 μL) and stirred at room temperature. After the reaction was allowed to proceed for 24 hours, the reaction solution was measured by GC-MS. As a result, the production of the target product was confirmed. The yield was about 4%.

(Example 15)

By the following method, the synthesis of the boron-containing conjugated polyene compound and the subsequent cross-coupling reaction are performed in one pot to synthesize the conjugated polyene compound.

[Chemical formula 49]

Specifically, diisopropyl 1-pentynylboronate (22.5 μL, 0.0982 mmol) and (E)-methyl 2,4-pentadienoate (11.5 μL, 0.0987 mmol) were dissolved in benzene (500 μL) , in the presence of [Ru(naphthalene)(cod)] (3.35 mg, 0.00993 mmol) at room temperature for 24 hours. Next, benzene iodide (11.0 μL, 0.0987 mmol), a methanol solution of sodium methoxide (120 μL (120 μL in methanol), 0.120 mmol), and [Pd(PPh ₃ ) ₄ ] were sequentially added to the same solution. (9.28 mg, 0.00803 mmol) and allowed to react at 50°C for 15 minutes. The product was purified by recycle HPLC. The yield was 79% ((A-110)/(A-111)=5/1).

(A-110)

¹ H NMR (400 MHz, CDCl ₃ , rt): δ 0.99 (t, ³ J _{H, H} = 7.4 Hz, 3H), 1.56 (sext, ³ J _{H, H} = 7.4 Hz, 2H), 2.43 (m, 2H), 3.74(s, 3H), 5.91(d, ^3JH , _H =15.5Hz, 1H), 6.40(dd, ^3JH , _H =15.4, 10.9Hz, 1H), 6.62(s, 1H) , 6.64 (d, ³ J _{H, H} = 15Hz, 1H), 7.26-7.35 (m, 5H), 7.38 (dd, ³ J _{H, H} = 15.5, 10.9 Hz, 1H).

¹³ C{ ¹ H} NMR (100 MHz, CDCl ₃ , rt): δ 14.36(s), 22.44(s), 29.38(s), 51.53(s), 119.81(s), 125.45(s), 127.33( s), 128.40(s), 128.91(s), 135.64(s), 137.03(s), 140.18(s), 145.42(s), 145.67(s), 167.68(s).

HRMS (APCI): m/z calcd for C ₁₇ H ₂₀ O ₂ +H ⁺ : 257.1536[M+H] ⁺ ; found: 257.1528.

(Example 16)

By the following method, the synthesis of the boron-containing conjugated polyene compound and the subsequent cross-coupling reaction are performed in one pot to synthesize the conjugated polyene compound.

[Chemical formula 50]

Make 3-hexyne (20.0 μL, 0.175 mmol) and 2-{(E)-1,3-butadienyl}-4,4,5,5-tetramethyl-1,3,2-di Oxaborolane (36.0 μL, 0.180 mmol) in benzene (500 μL) in the presence of [Ru(naphthalene)(cod)] (6.03 mg, 0.0178 mmol) was reacted at room temperature for 5 minutes. Next, benzene iodide (20.0 μL, 0.179 mmol), a methanol solution of sodium methoxide (180.0 μL (180.0 μL in methanol), 0.180 mmol), and [Pd(PPh ₃ ) ₄ were sequentially added to the same solution. ] (16.51 mg, 0.01429 mmol), and reacted at 50°C for 2 hours. The product was purified by recycle HPLC. The yield was 62%.

¹ H NMR (400 MHz, C ₆ D ₆ , rt): δ 0.91 (t, ³ _{JH, H} = 7.44 Hz, 3H), 1.05 (t, ³ J _{H, H} = 7.48 Hz, 3H; 10-Me ), 2.03(quint, ^3JH _{, H} =7.44Hz, 2H), 2.24(q, ^3JH , _H =7.44Hz, 2H), 5.45(t, ^3JH , _H =7.44Hz, 1H), 6.27(d, ^3JH , _H =15.5Hz, 1H), 6.39(dd, ^3JH , _H =15.5, 10.3Hz, 1H), 6.44(d, ^3JH , _H =15.5Hz, 1H), 6.85 (dd, ³ J _{H, H} = 15.5, 10.3 Hz, 1H), 7.05 (t, 1 H), 7.1-7.2 (overlapped with solvent), 7.30 (d, ³ J _{H, H} = 7.5 Hz, 2H).

(Example 17)

By the following method, the synthesis of the boron-containing conjugated polyene compound and the subsequent cross-coupling reaction are performed in one pot to synthesize the conjugated polyene compound.

[Chemical formula 51]

Specifically, 1-pentynylboronic acid diisopropyl ester (22.5 μL, 0.0982 mmol) and (E)-1-(4,4,5,5-tetramethyl-1,3,2-dioxo Pentaboran-2-yl)butadiene (22.0 μL, 0.110 mmol), [Ru(naphthalene)(1,5-cod)] (3.34 mg, 0.00990 mmol) were reacted in benzene at 50°C for 3 hours . Vinyl bromide (15.0 μL, 0.212 mmol), sodium ethoxide in ethanol (240 μL in EtOH (240 μL in EtOH, 0.240 mmol) and [Pd(PPh ₃ ) ₄ ] (18.46 mg, 0.01597 mmol) were added at 50 The reaction was allowed to proceed at °C for 5 hours. As a result, compound (A-113) was produced in a yield of 46%.

¹ H NMR (400 MHz, CDCl ₃ , rt): δ 0.92 (t, ³ _{JH, H} =7.4 Hz, 3H), 1.46 (sext, ³ _{JH, H} =7.4 Hz, 2H), 2.33 (t, ³ J _{H, H} = 7.4 Hz, 2H), 5.09 (ddd, ³ J _{H, H} = 10.3 Hz, ² J _{H, H} = -1.0 Hz, ⁴ J _{H, H} = -0.9 Hz, 1 H), 5.12 ( ddd, ³ J _{H, H} = 10.3 Hz, ² J _{H, H} = -3.0 Hz, ⁴ J _{H, H} = -0.5 Hz, 1 H), 5.19 (dt, ³ J _{H, H} = 17.8, ² J _{H, H} =2.5Hz, 4JH _{, H} =2.5Hz, 1H), 5.23 (ddd, ^3JH , _H ⁼ 17.8, ^2JH , _H =-3.0, 4JH, _H = ^-0.5Hz , 1H) , 6.08 (ddt, ^3JH , _H =10.5, 4JH, _H =-2.5, 4JH, _H = ^-1.0Hz , 1H), 6.19 (dd, ^3JH , _H ⁼ 17.5Hz, ^4J _{H, H} = -1.0 Hz, 1H), 6.28 (ddd, ³ J _{H, H} = 17.5, 10.5 Hz, ⁴ J _{H, H} = -1.0 Hz, 1 H), 6.30 (ddd, ³ J _{H, H} = 16.0 , 10.5Hz, 4JH, _H = ^-1.0Hz , 1H), 6.32 (dd, ^3JH , _H =17.8, 10.3Hz, 1H), 6.38 (ddddd, ^3JH _{, H} =16.0, 11.8, 10.3 Hz, ⁴ J _{H, H} = -1.0, -0.5 Hz, 1H), 6.60 (ddd, ³ J _{H, H} = 17.8, 11.5, 10.3 Hz, 1H).

¹³ C{ ¹ H} NMR (100 MHz, CDCl ₃ , rt): δ 14.22(s), 22.70(s), 28.89(s), 117.00(s), 117.92(s), 128.21(s), 132.32( s), 133.05(s), 133.97(s), 134.04(s), 137.02(s), 137.13(s), 140.63(s).

HRMS (APCI): m/z calcd for C ₁₃ H ₁₈ +H ⁺ : 175.1481[M+H] ⁺ ; found: 175.1474.

Claims (15)

1. A process for producing a boron-containing conjugated polyene compound, which comprises the steps of: reacting a first raw material compound having a carbon-carbon triple bond and a second raw material compound having 1, 3-butadiene-4, 4-diyl and having a conjugated di (or poly) ene skeleton containing two carbon-carbon double bonds in the group in the presence of a metal catalyst to obtain a boron-containing conjugated polyene compound having a conjugated polyene skeleton containing 3 or more carbon-carbon double bonds,

at least one of the first and second starting compounds having a boron-containing group bonded to a carbon atom constituting the triple bond or the conjugated di (or poly) ene backbone,

the boron-containing conjugated polyene compound has a boron-containing group bonded to a carbon atom constituting the conjugated polyene skeleton.

2. The process for producing a boron-containing conjugated polyene compound according to claim 1,

the first raw material compound is a compound represented by the following formula (1-1),

the second raw material compound is a compound represented by the following formula (1-2-1),

the boron-containing conjugated polyene compound is a compound represented by the following formula (1-3-1),

[ chemical formula 1]

In the formula (1-1), B¹Represents a boron-containing group, R¹Represents a monovalent group of a group having one valence,

[ chemical formula 2]

In the formula (1-2-1), n represents an integer of 0 or more, R²And R³Each independently represents a hydrogen atom or a monovalent group; when n is 1 or more, plural R²May be the same or different from each other; in addition, a plurality of R³May be the same or different from each other; r²Each other, R³Each other and R²And R³May be bonded to each other to form a ring,

[ chemical formula 3]

In the formula (1-3-1), B¹、R¹、n、R²And R³Each has the same meaning as described above, and the wavy line indicates that the double bond bonded to the wavy line may be either cis or trans.

3. The process for producing a boron-containing conjugated polyene compound according to claim 2, wherein R in the formula (1-2-1)³At least one is a boron-containing group.

4. The process for producing a boron-containing conjugated polyene compound according to claim 1,

the first raw material compound is a compound represented by the following formula (1-1),

the second raw material compound is a compound represented by the following formula (1-2-2),

the boron-containing conjugated polyene compound is a compound represented by the following formula (1-3-2),

[ chemical formula 4]

In the formula (1-1), B¹Represents a boron-containing group, R¹Represents a monovalent group of a group having one valence,

[ chemical formula 5]

In the formula (1-2-2), n¹Represents an integer of 0 or more, n²Represents 0 or 1, R²Represents a hydrogen atom or a monovalent group; n is¹When it is 1 or more, plural R²May be the same or different from each other; wherein n is¹When n is 1 or more, n²Is 1; r²May be bonded to each other to form a ring,

[ chemical formula 6]

In the formula (1-3-2), B¹、R¹、n¹、n²And R²Each has the same meaning as previously described; two B¹May be the same or different from each other; in addition, two R¹May be the same or different from each other; the wavy line indicates that the double bond bonded to the wavy line may be either cis or trans.

5. The method for producing a boron-containing conjugated polyene compound according to any one of claims 2 to 4,

the R is¹In the form of a silyl group, is,

the production process is also provided with the step of adding the R in the boron-containing conjugated polyene compound¹A step of substituting a hydrogen atom for the first boron-containing conjugated polyene compound.

6. The process for producing a boron-containing conjugated polyene compound according to claim 1,

the first raw material compound is a compound represented by the following formula (2-1),

the second raw material compound is a compound represented by the following formula (2-2),

the boron-containing conjugated polyene compound is a compound represented by the following formula (2-3),

[ chemical formula 7]

In the formula (2-1), R⁴And R⁵Each independently represents a monovalent group, and each independently represents a monovalent group,

[ chemical formula 8]

In the formula (2-2), m representsAn integer of 0 or more, R⁶And R⁷Each independently represents a hydrogen atom or a monovalent group; wherein two R are⁷At least one of which is a boron-containing group; when m is 1 or more, plural R⁶May be the same or different from each other; in addition, two R⁷May be the same or different from each other; r⁶Each other, R⁷Each other and R⁶And R⁷May be bonded to each other to form a ring,

[ chemical formula 9]

In the formula (2-3), R⁴、R⁵、m、R⁶And R⁷Each having the same meaning as described above; the wavy line indicates that the double bond bonded to the wavy line may be either cis or trans.

7. The process for producing a boron-containing conjugated polyene compound according to claim 6,

the R is⁴Hammett substituent constant σ of_pIs greater than the value of R⁵Hammett substituent constant σ of_pThe value of (2) is large.

8. The process for producing a boron-containing conjugated polyene compound according to claim 6 or 7, wherein,

the R is⁵In the form of a silyl group, is,

the preparation method is also provided with the step of adding the R in the boron-containing conjugated polyene compound⁵A step of substituting a hydrogen atom for the first boron-containing conjugated polyene compound.

9. The method for producing a boron-containing conjugated polyene compound according to any one of claims 1 to 9, wherein the metal catalyst contains at least one selected from the group consisting of ruthenium (Ru), rhodium (Rh), cobalt (Co) and nickel (Ni).

10. The process for producing a boron-containing conjugated polyene compound according to claim 10, wherein the metal catalyst is a ruthenium catalyst.

11. The process for producing a boron-containing conjugated polyene compound according to claim 10, wherein the ruthenium catalyst forms zero-valent ruthenium in the reaction system.

12. A boron-containing conjugated polyene compound represented by the following formula (1-3-1A), the following formula (1-3-2A) or the following formula (2-3A),

[ chemical formula 10]

In the formula (1-3-1A), B¹Represents a boron-containing group, R¹¹Represents a hydrogen atom or a monovalent group, n represents an integer of 0 or more, R²And R³Each independently represents a hydrogen atom or a monovalent group; when n is 1 or more, plural R²May be the same or different from each other; in addition, a plurality of R³May be the same or different from each other; r²Each other, R³Each other and R²And R³May be bonded to each other to form a ring; the wavy line indicates that the double bond bonded to the wavy line may be either cis or trans,

[ chemical formula 11]

In the formula (1-3-2A), B¹Represents a boron-containing group, R¹¹Represents a hydrogen atom or a monovalent group, n¹Represents an integer of 0 or more, n²Represents 0 or 1, R²Represents a hydrogen atom or a monovalent group; wherein n is¹When n is 1 or more, n²Is 1; n is¹When it is 1 or more, plural R²May be the same or different from each other; in addition, the first and second substrates are,two B¹May be the same or different from each other; r²May be bonded to each other to form a ring; the wavy line indicates that the double bond bonded to the wavy line may be either cis or trans,

[ chemical formula 12]

In the formula (2-3A), R⁴Represents a monovalent group, R¹⁵Represents a hydrogen atom or a monovalent group, m represents an integer of 0 or more, R⁶And R⁷Each independently represents a hydrogen atom or a monovalent group; wherein two R are⁷At least one of which is a boron-containing group; when m is 1 or more, plural R⁶May be the same or different from each other; in addition, two R⁷May be the same or different from each other; r⁶Each other, R⁷Each other and R⁶And R⁷May be bonded to each other to form a ring; the wavy line indicates that the double bond bonded to the wavy line may be either cis or trans.

13. A process for producing a conjugated polyene compound, which comprises the steps of:

a first step of obtaining a reaction solution containing the boron-containing conjugated polyene compound by the method for producing a boron-containing conjugated polyene compound according to any one of claims 1 to 11; and

and a second step of adding a coupling reaction catalyst and a third raw material compound having a reactive group capable of coupling reaction with the boron-containing group to the reaction solution to perform a coupling reaction.

14. The method for producing a conjugated polyene compound according to claim 13, wherein the reactive group is a halogen group.

15. The process for producing a conjugated polyene compound according to claim 13 or 14, wherein the first step is a step of producing the boron-containing conjugated polyene compound in a reaction system of a reaction in the presence of the metal catalyst,

the second step is a step of adding the coupling reaction catalyst and the third raw material compound to the reaction system.