JPWO2020059824A1 - A boron-containing conjugated polyene compound and a method for producing the same, and a method for producing the conjugated polyene compound. - Google Patents

Abstract

A conjugated di (or poly) having a first raw material compound having a carbon-carbon triple bond and a 1,3-butadiene-4,4-diyl group containing two carbon-carbon double bonds in the group. A step of reacting a second raw material compound having an en skeleton in the presence of a metal catalyst to obtain a boron-containing conjugated polyene compound having a conjugated polyene skeleton containing three or more carbon-carbon double bonds is provided. 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 di (or poly) ene skeleton, and the boron-containing conjugated polyene compound is a compound. A method for producing a boron-containing conjugated polyene compound having a boron-containing group bonded to a carbon atom constituting a conjugated polyene skeleton.

Description

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

A conjugated polyene skeleton in which carbon-carbon double bonds and single bonds are alternately repeated is a structure often found in physiologically active substances such as antifungal drugs and vitamins. In addition, various applications of conjugated polyene skeletons to electronic material applications have been studied. Therefore, a method of introducing a conjugated polyene skeleton into a target compound has been studied conventionally.

For example, in Non-Patent Document 1, haloalkenylboronic acid protected by a specific protective group is used to form polyenylboronic acid having a boronic acid group on a conjugated polyene skeleton, and the polyenylboronic acid is formed by a cross-coupling reaction. A method of utilizing enylboronic acid for the synthesis of a physiologically active substance is disclosed.

Journal of the American Chemical Society, 2008, 130, p. 466-468

An object of the present invention is to provide a novel boron-containing conjugated polyene compound having a conjugated polyene skeleton and a boron-containing group bonded thereto and useful for synthesizing physiologically active substances, electronic material substances, etc., and a method for producing the same. And. 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.

One aspect of the present invention relates to a method for producing a boron-containing conjugated polyene compound. This production method has a first raw material compound having a carbon-carbon triple bond, a 1,3-butadiene-4,4-diyl group, and a conjugate containing two carbon-carbon double bonds in the group. A second raw material compound having a di (or poly) ene skeleton is reacted in the presence of a metal catalyst to obtain a boron-containing conjugated polyene compound having a conjugated polyene skeleton containing three or more carbon-carbon double bonds. Provide a step to obtain. Further, in this production method, at least one of the first raw material compound and the second raw material compound is a boron-containing bond bonded to a carbon atom constituting the triple bond or the conjugated di (or poly) ene skeleton. Has a group. As a result, the boron-containing conjugated polyene compound has a boron-containing group bonded to a carbon atom constituting the 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-mentioned 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). Further, the boron-containing conjugated polyene compound can also be applied to applications such as electronic materials as a π-conjugated compound having a boron-containing group.

［式（１−１）中、Ｂ^１は含ホウ素基を示し、Ｒ^１は一価の基を示す。］

［式（１−２−１）中、ｎは０以上の整数を示し、Ｒ^２及びＲ^３はそれぞれ独立に水素原子又は一価の基を示す。ｎが１以上のとき、複数のＲ^２は互いに同一でも異なっていてもよい。また、複数のＲ^３は互いに同一でも異なっていてもよい。Ｒ^２同士、Ｒ^３同士、並びに、Ｒ^２及びＲ^３は、互いに結合して環を形成していてもよい。］

［式（１−３−１）中、Ｂ^１、Ｒ^１、ｎ、Ｒ^２及びＲ^３はそれぞれ前記と同義である。なお、波線は、波線に結合する二重結合がシス及びトランスのいずれであってもよいことを示す。］In one embodiment, the first raw material compound may be a compound represented by the following formula (1-1), and the second raw material compound may be represented by the following formula (1-2-1). It may be a compound, and the boron-containing conjugated polyene compound may be a compound represented by the following formula (1-3-1).

[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 independently represent a hydrogen atom or a monovalent group. When n is 1 or more, the plurality of R ^2s may be the same or different from each other. Further, the plurality of R ^3s may be the same or different from each other. R ^{2 to} each other, R ^{3 to} each other, and R ² and R ³ may be connected to each other to form a ring. ]

[In equation (1-3-1), B ¹ , R ¹ , n, R ² and R ³ have the same meanings as described above. The wavy line indicates that the double bond bonded to the wavy line may be either cis or trans. ]

In the above embodiment, at least one of the R ³ in the above 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. This boron-containing conjugated polyene compound can be suitably used for the production of polymer compounds by cross-coupling polymerization, etc., in addition to the above-mentioned uses.

［式（１−１）中、Ｂ^１は含ホウ素基を示し、Ｒ^１は一価の基を示す。］

［式（１−２−２）中、ｎ^１は０以上の整数を示し、ｎ^２は０又は１を示し、Ｒ^２は水素原子又は一価の基を示す。ｎ^１が１以上のとき、複数のＲ^２は互いに同一でも異なっていてもよい。但し、ｎ^１が１以上のとき、ｎ^２は１である。Ｒ^２同士は、互いに結合して環を形成していてもよい。］

［式（１−３−２）中、Ｂ^１、Ｒ^１、ｎ^１、ｎ^２及びＲ^２はそれぞれ前記と同義である。２つのＢ^１は互いに同一でも異なっていてもよい。また、２のＲ^１は互いに同一でも異なっていてもよい。なお、波線は、波線に結合する二重結合がシス及びトランスのいずれであってもよいことを示す。］In another aspect, the first raw material compound may be a compound represented by the following formula (1-1), and the second raw material compound may be represented by the following formula (1-2-2). The above-mentioned boron-containing 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. This boron-containing conjugated polyene compound can be suitably used for the production of polymer compounds by cross-coupling polymerization, etc., in addition to the above-mentioned uses.

[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 greater than ^{or equal to 0, n 2} represents 0 or 1, and R ² represents a hydrogen atom or a monovalent group. When n ¹ is 1 or more, the plurality of R ^2s may be the same or different from each other. However, when n ¹ is 1 or more, n ² is 1. R ² to each other may be bonded to each other to form a ring. ]

[In equation (1-3-2), B ¹ , R ¹ , n ¹ , n ² and R ² have the same meanings as described above. Two B ¹ represents may be the same or different from each other. Further, R ¹ of 2 may be the same as or different from each other. The wavy line indicates that the double bond bonded to the wavy line may be either cis or trans. ]

In each of the above embodiments, the R ¹ may be a silyl group, in which case the production method ^{replaces the R 1} in the boron-containing conjugated polyene compound with a hydrogen atom to form a second boron-containing conjugated polyene. A step of obtaining a compound may be further provided. Thus, no boron-containing conjugated polyene compound substituent (s) at substitutable position of R ¹ (i.e., boron-containing conjugated polyene compound R ¹ is a hydrogen atom) can be easily obtained.

［式（２−１）中、Ｒ^４及びＲ^５はそれぞれ独立に一価の基を示す。］

［式（２−２）中、ｍは０以上の整数を示し、Ｒ^６及びＲ^７はそれぞれ独立に水素原子又は一価の基を示す。但し、２つのＲ^７のうち少なくとも一つは含ホウ素基である。ｍが１以上のとき、複数のＲ^６は互いに同一でも異なっていてもよい。また、２つのＲ^７は互いに同一でも異なっていてもよい。Ｒ^６同士、Ｒ^７同士、並びに、Ｒ^６及びＲ^７は、互いに結合して環を形成していてもよい。］

［式（２−３）中、Ｒ^４、Ｒ^５、ｍ、Ｒ^６及びＲ^７はそれぞれ前記と同義である。なお、波線は、波線に結合する二重結合がシス及びトランスのいずれであってもよいことを示す。］In still another aspect, the first raw material compound may be a compound represented by the following formula (2-1), and the second raw material compound may be represented by the following formula (2-2). The boron-containing conjugated polyene compound may be a compound represented by the following formula (2-3).

[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. Provided that at least one of the two R ⁷ are boron-containing groups. When m is 1 or more, the plurality of R ^6s may be the same or different from each other. Further, two R ⁷ may be the same or different from each other. R ⁶ to each other, ^{R 7} together, and, ^{R 6} and ^{R 7} may be bonded to each other to form a ring. ]

[In equation (2-3), R ⁴ , R ⁵ , m, R ⁶ and R ⁷ have the same meanings as described above. The wavy line indicates that the double bond bonded to the wavy line may be either cis or trans. ]

In the above embodiment, the value of the substituent constant σ _p ^{of Hammett of R 4} may be larger than the value of the substituent constant σ _p ^{of Hammett of R 5.}

Further, in the above embodiment, the above R ⁵ may be a silyl group, and at this time, in the above production method, the above R ⁵ in the above boron-containing conjugated polyene compound is replaced with a hydrogen atom, and the second boron-containing conjugated polyene is used. A step of obtaining a compound may be further provided. Thus, no boron-containing conjugated polyene compound substituent (s) at substitutable position of R ⁵ (i.e., boron-containing conjugated polyene compounds R ⁵ is a hydrogen atom) can be easily obtained.

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

In each of the above embodiments, the metal catalyst may be a ruthenium catalyst.

In each of the above embodiments, the ruthenium catalyst may form zero-valent ruthenium in the reaction system.

［式（１−３−１）中、Ｂ^１は含ホウ素基を示し、Ｒ^１１は水素原子又は一価の基を示し、ｎは０以上の整数を示し、Ｒ^２及びＲ^３はそれぞれ独立に水素原子又は一価の基を示す。ｎが１以上のとき、複数のＲ^２は互いに同一でも異なっていてもよい。また、複数のＲ^３は互いに同一でも異なっていてもよい。Ｒ^２同士、Ｒ^３同士、並びに、Ｒ^２及びＲ^３は、互いに結合して環を形成していてもよい。なお、波線は、波線に結合する二重結合がシス及びトランスのいずれであってもよいことを示す。］

［式（１−３−２）中、Ｂ^１は含ホウ素基を示し、Ｒ^１１は水素原子又は一価の基を示し、ｎ^１は０以上の整数を示し、ｎ^２は０又は１を示し、Ｒ^２は水素原子又は一価の基を示す。但し、ｎ^１が１以上のとき、ｎ^２は１である。ｎ^１が１以上のとき、複数のＲ^２は互いに同一でも異なっていてもよい。Ｒ^２同士は、互いに結合して環を形成していてもよい。また、２つのＢ^１は互いに同一でも異なっていてもよい。なお、波線は、波線に結合する二重結合がシス及びトランスのいずれであってもよいことを示す。］

［式（２−３）中、Ｒ^４は一価の基を示し、Ｒ^１５は水素原子又は一価の基を示し、ｍは０以上の整数を示し、Ｒ^６及びＲ^７はそれぞれ独立に水素原子又は一価の基を示す。但し、２つのＲ^７のうち少なくとも一つは含ホウ素基である。ｍが１以上のとき、複数のＲ^６は互いに同一でも異なっていてもよい。また、２つのＲ^７は互いに同一でも異なっていてもよい。Ｒ^６同士、Ｒ^７同士、並びに、Ｒ^６及びＲ^７は、互いに結合して環を形成していてもよい。なお、波線は、波線に結合する二重結合がシス及びトランスのいずれであってもよいことを示す。］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).

[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 are independent of each other. Indicates a hydrogen atom or a monovalent group. When n is 1 or more, the plurality of R ^2s may be the same or different from each other. Further, the plurality of R ^3s may be the same or different from each other. R ^{2 to} each other, R ^{3 to} each other, and R ² and R ³ may be connected 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. ]

[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 greater than ^{or equal to 0, and n 2} represents 0 or 1. Shown, 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, the plurality of R ^2s may be the same or different from each other. R ² to each other may be bonded to each other to form a ring. Moreover, two B ¹ represents may 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. ]

[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 are independent of each other. Indicates a hydrogen atom or a monovalent group. Provided that at least one of the two R ⁷ are boron-containing groups. When m is 1 or more, the plurality of R ^6s may be the same or different from each other. Further, two R ⁷ may be the same or different from each other. R ⁶ to each other, ^{R 7} together, and, ^{R 6} and ^{R 7} may 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. ]

Yet another aspect of the present invention is a first step of obtaining a reaction solution containing the boron-containing conjugated polyene compound by the method for producing the boron-containing conjugated polyene compound, and a coupling reaction catalyst in the reaction solution. The present invention relates to a method for producing a conjugated polyene compound, which comprises a third raw material compound having a reactive group capable of a coupling reaction with the boron-containing group, and a second step of adding and carrying out a coupling reaction.

In one embodiment, the reactive group may be a halogeno group.

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

According to the present invention, a novel boron-containing conjugated polyene compound having a conjugated polyene skeleton and a boron-containing group bonded thereto and useful for synthesizing a physiologically active substance, an electronic material substance, or the like and a method for producing the same are provided. .. Further, according to the present invention, there is provided a method for producing a conjugated polyene compound using the above-mentioned boron-containing conjugated polyene compound.

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 has a first raw material compound having a carbon-carbon triple bond and a 1,3-butadiene-4,4-diyl group, and 2 in the group. A second raw material compound having a conjugated di (or poly) ene skeleton containing one carbon-carbon double bond is reacted in the presence of a metal catalyst to form a conjugate containing three or more carbon-carbon double bonds. The present invention comprises a polyene forming step of obtaining a boron-containing conjugated polyene compound having a polyene skeleton. 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 di (or poly) ene skeleton. As a result, the boron-containing conjugated polyene compound has a boron-containing group bonded to a carbon atom constituting the conjugated polyene skeleton.

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). Further, the boron-containing conjugated polyene compound can also be applied to 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 the remaining atomic group from which one functional group on the boron atom in the boron compound has been removed. That is, the boron-containing group may be a monovalent group that is bonded to the bonding target via a boron atom.

The boron-containing group is not particularly limited, and can be appropriately selected as long as the reaction between the first raw material compound and the second raw material compound proceeds. Examples of the boron-containing group include a boryl group, a borono group, a borate group, and a derivative group thereof.

The boryl group represents a group represented by _{-BH 2.} Examples of the derivative group of the boryl group include a diorganovoryl group.

The diorganovoril group may be, for example, a group represented by ^{−B (R 21} ) _2. R ²¹ represents a monovalent group. The two R ^21s may be the same or different, and may be linked to each other to form a ring with a boron atom. R ²¹ may be, for example, a monovalent organic group, an alkyl group which may have a substituent, or an aryl group which may have a substituent.

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 the remaining atomic group obtained by removing one hydrogen atom on the aromatic ring from the aromatic compound. The aromatic ring contained in the aromatic compound may be a monocyclic ring, a condensed ring, or a heterocyclic ring. Examples of the aromatic compound include benzene, naphthalene, furan, pyrrole, thiophene, pyridine and the like.

The ^{substituents that the alkyl group and the aryl group in R 21} may have are not particularly limited as long as the reaction between the first raw material compound and the second raw material compound proceeds. Examples of the substituent include a hydroxy group, a carbonyl group, a formyl group, a hydroxycarbonyl group, an ester group, an amino group, a thiol group and the like.

Specific examples of the diorganovoryl group include a diphenylboryl group, a dicyclohexyl group, a bicyclo [3.3.1] nonane-1,5-diyl group, a disiamil group and the like.

The borono group represents a group represented by −B (OH) _2. Examples of the derivative group of the borono group include, for example, a boronat group, a protected borono group and the like.

The boronato group may be, for example, a group represented by ^{−B (OR 22} ) _2. R ²² represents a monovalent group. The two R ^22s may be the same or different, and may be linked to each other to form a ring with a boron atom and an oxygen atom. R ²² may be, for example, a monovalent organic group, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Examples of the alkyl group, the aryl group and the substituent which they may have in R ²² include the same alkyl group, the aryl group and the substituent which they may have in R ²¹ .

Specific examples of the boronat group include a diisopropyl boronat group, a ditert-butyl boronat group and the like.

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

Examples of the protected borono group include a group formed by the reaction of a bifunctional compound such as a diol, diamine or dicarboxylic acid with a borono group. Examples of the diol include pinacol, neopentyl glycol, catechol, pinandiol, 1,2-dicyclohexyldiol and the like. Examples of the diamine include 1,8-diaminonaphthalene and the like. Examples of the dicarboxylic acid include N-methyliminodiacetic acid and the like.

Further, as the protected borono group, a borate group such as a triol borate group can also be exemplified. The triol boronate group is formed by the reaction of triol with a borono group. Examples of the triol include trimethylolethane (1,1,1-tris (hydroxymethyl) ethane) and the like. The counter cation of the borate group is not particularly limited, and may be, for example, sodium ion (Na ⁺ ), potassium ion (K ⁺ ), organophosphonium ion (PR ₄ ⁺ ), or the like.

The borate group, in addition to the triol borate group as described above, trifluoroborate acrylate group (-BF 3 ^_-) and the like. The counter cation of the borate group is not particularly limited, and may be, for example, sodium ion (Na ⁺ ), potassium ion (K ⁺ ), organophosphonium ion (PR ₄ ⁺ ), or the like.

The metal catalyst is a catalyst capable of forming a boron-containing conjugated polyene compound by the reaction of the first raw material compound and the second raw material compound, that is, a carbon-carbon triple bond and a 1,3-butadiene-4,4-diyl group. Any catalyst can be used as long as it can form a conjugated triene skeleton by the reaction of.

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 can form 0-valent ruthenium (Ru (0)) in the reaction system from the viewpoint that the first raw material compound and the second raw material compound can be efficiently reacted by the reaction mechanism described later. It is preferably a catalyst. That is, the polyene forming 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 forming step will be described below. In the following examples, the first raw material compound is a compound represented by the formula (1-1) described later, the second raw material compound is butadiene, and the metal catalyst is [(naphthalene) (1,5-cyclooctadiene). ) Ruthenium (0)] is used to describe the reaction mechanism, but the present invention is not limited thereto. Further, the reaction mechanism of the polyene forming step is not limited to the following examples.

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 coordinated on ruthenium (0), respectively (A above). Then, the oxidative coupling reaction forms the B, and the β-hydride elimination forms the C. Further, reductive elimination forms the D with a conjugated triene coordinated on ruthenium. In the above example, since butadiene has two reaction points, another molecule of the first raw material compound reacts by the same mechanism to form the above-mentioned E in which the conjugated tetraene is coordinated. Finally, the conjugated tetraene dissociates from the ruthenium to obtain a boron-containing conjugated polyene compound. When the second raw material compound has only one reaction point, the boron-containing conjugated polyene compound is dissociated from the ruthenium at the stage D.

Examples of the catalyst capable of forming Ru (0) in the reaction system include a zero-valent ruthenium complex having Ru (0) and a divalent ruthenium complex having Ru (II).

Examples of the zero-valent ruthenium complex include [(naphthalene) (1,5-cyclooctadiene) ruthenium (0)], [(butadiene) (1,5-cyclooctadiene) (acetonitrile) ruthenium (0)] and the like. Can be mentioned.

Examples of the divalent ruthenium complex include [bis (acetylacetonato) (1,5-cyclooctadiene) ruthenium (II)] and [tetrachlorodi (anisole) diruthenium]. The divalent ruthenium complex may be reduced in the reaction system to form Ru (0). The divalent ruthenium complex may be reduced by a reaction with a reaction substrate (a first raw material compound and / or a second raw material compound), may be reduced by a reaction between ruthenium complexes, and may be reduced with a separately added reducing agent. It may be reduced by the reaction of. Examples of the reducing agent include butyllithium, lithium aluminum hydride, sodium naphthalene, and a combination of sodium carbonate and isopropyl alcohol.

The type of ruthenium catalyst is not limited to the above, and any catalyst that can form a metallacycle may be used. For example, the ruthenium catalyst may be a catalyst that forms tetravalent ruthenium (Ru (IV)) during metallacycle formation. That is, the ruthenium catalyst may be a catalyst capable of forming a metallacycle containing tetravalent ruthenium (Ru (IV)) in the reaction system.

Further, as the metal genus catalyst, a rhodium catalyst, a cobalt catalyst, a nickel catalyst and the like can also be used.

As the rhodium catalyst, a catalyst capable of forming monovalent rhodium (Rh (I)) in the reaction system is preferable. Examples of such a catalyst include a monovalent rhodium complex having Rh (I), a trivalent rhodium complex having Rh (III), and the like. The trivalent rhodium complex may be used in combination with a reducing agent. Examples of the reducing agent include the same as above.

As the cobalt catalyst, a catalyst capable of forming monovalent cobalt (Co (I)) or 0-valent cobalt (Co (0)) in the reaction system is preferable. Examples of such a catalyst include a divalent cobalt complex having Co (II) and the like. The divalent cobalt complex may be used in combination with a reducing agent. Examples of the reducing agent include the same as above.

As the nickel catalyst, a catalyst capable of forming zero-valent nickel (Ni (0)) in the reaction system is preferable. Examples of such a catalyst include a zero-valent nickel complex having Ni (0), a divalent nickel complex having Ni (II), and the like. The divalent nickel complex may be used in combination with a reducing agent. Examples of the reducing agent include the same as above. Further, as the reducing agent, zinc or the like can also be preferably used.

The amount of the metal catalyst is not particularly limited, and 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. 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 forming step, the reaction between 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, and any solvent may be used as long as it can dissolve the first raw material compound and the second raw material compound. Examples of the organic solvent include diethyl ether, tetrahydrofuran, acetone, hexane, benzene, toluene, dichloromethane, dimethyl sulfoxide and the like, and from the viewpoint of not easily inhibiting the reaction between the first raw material compound and the second raw material compound. Tetrahydrofuran, benzene, toluene and the like are preferable.

The amount of the organic solvent is not particularly limited, and may be, for example, 100 parts by mass or more, preferably 1000 parts by mass or more, for example, with respect to 100 parts by mass of the total of the first raw material compound and the second raw material compound. It may be 100,000 parts by mass or less, preferably 10,000 parts by mass or less.

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

Hereinafter, a preferred embodiment of the manufacturing method according to the present embodiment will be described.

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

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

In the formula (1-2-1), n represents an integer of 0 or more, and R ² and R ³ independently represent a hydrogen atom or a monovalent group. When n is 1 or more, the plurality of R ^2s may be the same or different from each other. Further, the plurality of R ^3s may be the same or different from each other. R ^{2 to} each other, R ^{3 to} each other, and R ² and R ³ may be connected 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. The wavy line in the equation indicates 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) is a compound represented by the following formula (1-3-1a), a compound represented by the following formula (1-3-1b), or these. Can be a mixture of. In the first aspect, among the following compounds, many compounds represented by the formula (1-3-1a) tend to be obtained.

The monovalent group in R ¹ is not particularly limited, and can be appropriately selected as long as the reaction between 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 alkyl group which may have a substituent, an aryl group which may have a substituent, a boron-containing group, a silyl group and 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 remaining atomic group obtained by removing one hydrogen atom on the aromatic ring from the aromatic compound. The aromatic ring contained in the aromatic compound may be a monocyclic ring, a condensed ring, or a heterocyclic ring. Examples of the aromatic compound include benzene, naphthalene, thiophene and the like.

The ^{substituents that the alkyl group and the aryl group in R 1} may have are not particularly limited as long as the reaction between the first raw material compound and the second raw material compound proceeds. Examples of the substituent include an aryl group, an alkyloxy group, an aryloxy group, a hydroxyl group, a formyl group, a carbonyl group, an amino group, a halogeno group and the like.

The silyl group in R ¹ may be the group represented by ^{−Si (R 31} ) _3. R ³¹ represents a monovalent group. The three R ^31s may be the same or different from each other and may be linked to each other to form a ring with a silicon atom. R ³¹ may be, for example, a monovalent organic group, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Examples of the alkyl group, the aryl group and the substituent which they may have in R ³¹ include the same alkyl group, the aryl group and the substituent which they may have in R ²¹ described above.

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, by the desilylation reaction, a ^{boron-containing conjugated polyene compound in which R 1} in the compound (1-3-1) is replaced with a hydrogen atom can be obtained. At this time, if R ² is a hydrogen atom, a conjugated polyene skeleton having no substituent in the side chain can be formed.

The desilylation reaction is not particularly limited, and a known method may be applied. For example, the desilylation reaction can be carried out using tetra-n-butylammonium fluoride (TBAF) as a reactant. If the reaction is difficult to proceed, a catalytic amount of copper (I) iodide may be added.

R ^1, the value of the substituent constant sigma _p of Hammett may be a smaller group than the value of the substituent constant sigma _p of Hammett of ^{B 1.} In the first aspect, the reaction tends to proceed so that the substituent (B ¹ _{) having a larger value of the substituent constant σ p} is located at the end of the conjugated polyene skeleton.

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

Monovalent radicals in R ² is not particularly limited, can be appropriately selected within a range that the reaction proceeds with a compound (1-1) and the compound (1-2-1). Monovalent group in R ² may be, for example, monovalent organic group or a halogeno group.

R ² is, for example, a hydrogen atom, a halogeno group, an alkyl group, an aryl group, -C (= ^O) groups represented by ^{R 41,} -C (= O) group represented by ^{OR 42,} boron-containing group, It may be a silyl group or the like, and these groups may have a substituent.

Halogeno group in R ² is a fluoro group (-F), chloro group (-Cl), it can be a bromo group (-Br), or iodine radical (-I), preferably fluoro group (-F), chloro group It is (-Cl) or a bromo group (-Br).

Examples of the alkyl group and aryl group in R ² and the substituents they may have include the same alkyl group and aryl group in ^{R 21 and the substituents they 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, and may be a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent.

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

Examples of the alkyl group, aryl group and substituents they may have in R ⁴¹ and R ⁴² include the same alkyl group, aryl group and substituents they may have in R ^{21 described above.} ..

The monovalent group in R ³ is not particularly limited, and can be appropriately selected as long as the reaction between 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 halogeno group.

R ³ is, for example, a hydrogen atom, a halogeno 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, and the like. It may be a silyl group or the like, and these groups may have a substituent. As each group in ^{R 3} , the same group as 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 boron-containing groups at both ends of the conjugated polyene skeleton can be obtained. Such a boron-containing conjugated polyene compound can be suitably used for producing a polymer compound by cross-coupling polymerization or the like.

(Second aspect)
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 the following formula (1-2-2). ) (Hereinafter, also referred to as compound (1-2-2)). In the second aspect, compound (1-2-2) has two reaction points with compound (1-1). Therefore, in the second aspect, the compound represented by the following formula (1-3-2) having at least two boron-containing groups derived from the compound (1-1) (hereinafter, the compound (1-3-2)). ) Can also be obtained.

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 greater than ^{or equal to 0, n 2} represents 0 or 1, and R ² represents a hydrogen atom or a monovalent group. When n ¹ is 1 or more, the plurality of R ^2s may be the same or different from each other. However, when n ¹ is 1 or more, n ² is 1. R ² to each other 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. Two B ¹ represents may be the same or different from each other. Further, R ¹ of 2 may be the same as or different from each other. The wavy line indicates 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) is a compound represented by the following formula (1-3-2a), a compound represented by the following formula (1-3-2b), and a compound represented by the following formula (1-3-2b). It may be a compound represented by 1-3-2c), a compound represented by the following formula (1-3-2d), or a mixture thereof. In the second aspect, among the following compounds, the compound represented by the formula (1-3-2a) tends to be obtained most.

R ¹ in the formula (1-1) may be the same as ^{R 1} in the formula (1-1) in the first aspect.

^{R 2} in the formula (1-2-2) may be the same as ^{R 2} in the formula (1-2-1) in the first aspect.

n ¹ is an integer of 0 or more, and its upper limit is not particularly limited. n ¹ may be, for example, 0 to 8, 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 aspect)
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, by using such a first raw material compound and a second raw material compound, a compound represented by the following formula (2-3) (hereinafter, also referred to as compound (2-3)). Can be obtained.

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. Provided that at least one of the two R ⁷ are boron-containing groups. When m is 1 or more, the plurality of R ^6s may be the same or different from each other. Further, two R ⁷ may be the same or different from each other. R ⁶ to each other, ^{R 7} together, and, ^{R 6} and ^{R 7} may be bonded 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 above. The wavy line indicates 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, many compounds represented by the formula (2-3a) tend to be obtained.

The monovalent group in R ⁴ and R ⁵ is not particularly limited, and can be appropriately selected as long as the reaction between compound (2-1) and compound (2-2) proceeds. As the monovalent group in ^{R 4} and R ⁵ , the same group ^{as R 1 described above can be exemplified.}

In the third aspect, the value of the substituent constant σ _p ^{of Hammett of R 4} is larger than the value of the substituent constant σ _p ^{of Hammett of R 5.} In the third aspect, the reaction tends to proceed so that the substituent (R ⁴ _{) having a larger value of the substituent constant σ p} is located at the end of the conjugated polyene skeleton.

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

The monovalent group in R ⁶ is not particularly limited, and can be appropriately selected as long as the reaction between the compound (2-1) and the compound (2-2) proceeds. As R ⁶ , the same group as R ^{2 described above can be exemplified.}

The monovalent group in R ⁷ is not particularly limited, and can be appropriately selected as long as the reaction between the compound (2-1) and the compound (2-2) proceeds. As R ⁷ , the same group as R ^{3 described above can be exemplified.} Provided that at least one of the two R ⁷ are boron-containing groups.

<Boron-containing conjugated polyene compound>
The boron-containing conjugated polyene compound according to the present embodiment is a compound produced by the above-mentioned production method, and comprises a conjugated polyene skeleton containing three or more carbon-carbon double bonds and a carbon atom constituting the conjugated polyene skeleton. It has a boron-containing group bonded to.

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

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

Wherein ^{(1-3-1A), B 1, n} , R 2 and ^{R 3} have the same meaning as ^B 1, n, ^{R 2} and ^{R 3} in the above formula (1-3-1). Further, R ¹¹ represents a hydrogen atom or a monovalent group, and as the monovalent group in ^{R 11} , the same group ^{as R 1 described above can be exemplified.}

For a compound in which R ¹¹ is a hydrogen atom, for example, ^{a compound (1-1) in which R 1} is a silyl group is reacted with a compound (1-2-1), and then the silyl group of ^{R 1 is desilylated.} It can be produced by substituting a hydrogen atom with a reaction.

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

Wherein ^{(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). Further, R ¹¹ represents a hydrogen atom or a monovalent group, and as the monovalent group in ^{R 11} , the same group ^{as R 1 described above can be exemplified.}

For a compound in which R ¹¹ is a hydrogen atom, for example, ^{a compound (1-1) in which R 1} is a silyl group is reacted with a compound (1-2-2), and then the silyl group of ^{R 1 is desilylated.} It can be produced by substituting a hydrogen atom with a reaction.

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

Wherein ^{(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). Further, R ¹⁵ represents a hydrogen atom or a monovalent group, and as the monovalent group in ^{R 15} , the same group ^{as R 5 described above can be exemplified.}

For a compound in which R ¹⁵ is a hydrogen atom, for example, ^{a compound (2-1) in which R 5} is a silyl group is reacted with a compound (2-2), and then ^{the silyl group of R 5} is desilylated by a desilylation reaction. It can be produced by substituting with a hydrogen atom.

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 a reaction starting from a boron-containing group (for example, a cross-coupling reaction). In this application, the boron-containing group is preferably a borono group or a derivative group thereof.

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

Further, the boron-containing conjugated polyene compound according to the present embodiment can have two or more boron-containing groups, and in this case, a polymer compound by cross-coupling polymerization (for example, polymerization with a dihalogenated aromatic compound). Can be suitably used for the production of In this application, the boron-containing group is preferably a borono group or a derivative group thereof.

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

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.

The method for producing a conjugated polyene according to one embodiment includes a first step of obtaining a reaction solution containing a boron-containing conjugated polyene compound by the above-mentioned method for producing a boron-containing conjugated polyene compound, and a coupling reaction catalyst for the reaction solution. A second step of adding the above-mentioned third raw material compound having a reactive group capable of coupling reaction with the boron-containing group and carrying out the coupling reaction is provided.

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

As described above, in the above-mentioned 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 and used from known coupling reaction catalysts. Specific examples of the coupling reaction catalyst include _{known catalysts used in the Suzuki-Miyaura coupling reaction such as [Pd (PPh 3} ) ₄ ] (for example, palladium catalyst, nickel catalyst, iron complex catalyst, etc.). Immobilization catalysts (for example, immobilized palladium catalysts, immobilized nickel catalysts, immobilized iron catalysts, etc.), metal fine particle catalysts (for example, palladium fine particle catalysts, nickel fine particle catalysts, iron fine particle catalysts, etc.) and the like can be mentioned.

The reactive group of 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 it is a halogeno group from the viewpoint of excellent substrate selectivity and reactivity. Is preferable.

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

(Example 1-1)
A boron-containing conjugated polyene compound (A-1) was synthesized by the following method.

Specifically, benzene-d ₆ (0. It was dissolved in 6 mL), and [Ru (naphthalene) (cod)] (2.99 mg, 0.00886 mmol) was further added. When the reaction was carried out at room temperature, the boron-containing conjugated polyene compound (A-1) was produced in a yield of 54% at a reaction time of 4 hours and in a yield of 89% after 24 hours. The formation of the boron-containing conjugated polyene compound ^{was confirmed by 1} H-NMR measurement. The measurement results were 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 = 7.7 Hz, 2H), 3.45 (s, 3H), 4.43 (sept, J = 6) .2 Hz, 2H), 5.54 (s, 1H), 5.91 (d, J = 15.6 Hz, 1H), 6.28 (d, J = 15.1 Hz, 1H), 6. 29 (dd, J = 15.1, 11.0 Hz, 1H), 7.52 (dd, J = 15.6, 11.0 Hz, 1H).

(Example 1-2)
A boron-containing conjugated polyene compound (A-1) was synthesized by the following method.

Specifically, diisopropyl 1-pentynylboronic acid (20.5 μL, 0.0894 mmol) and methyl (E) -2,4-pentadienoate (10.4 μL, 0.0895 mmol) were added to methylene chloride-d ₂ (0). It was dissolved in (0.6 mL), and [Ru (naphthalene) (cod)] (2.94 mg, 0.00873 mmol) was further added. When the reaction was carried out at room temperature, a boron-containing conjugated polyene compound (A-1) was produced in a yield of 50% with a reaction time of 7 hours.

(Example 2)
A boron-containing conjugated polyene compound was synthesized by the following method.

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). [Ru (naphylene) (cod)] (6.07 mg, 0.00180 mmol) was further added. When the reaction was carried out at 70 ° C. for 1 hour, a boron-containing conjugated polyene compound (A-2) was obtained in a yield of 27%. When the same reaction was carried out at room temperature, the desired product was obtained in a yield of 36% after 28 hours.
^{1 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 = 7.7 Hz, 2H), 4.45 (sept, J = 6) .0 Hz, 2H), 5.58 (s, 1H), 5.60 (dqd, J = 15.8, 6.0, 4.4 Hz, 1H), 5.99 (dd, J = 15. 2,10.4 Hz, 1H), 6.28 (d, J = 14.7 Hz, 1H), 6.48 (ddd, J = 14.7, 10.6, 4.4 Hz, 1H).

(Example 3)
A boron-containing conjugated polyene compound was synthesized by the following method.

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 [Ru (naphthalene) (cod)] (1.93 mg, 0.00572 mmol) was further added. After 25 minutes at room temperature, a 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 = 7.4 Hz, 2H), 2.06 (q, J = 7.4 Hz, 2H), 5.28 (t, J = 7) .4 Hz, 1H), 5.93 (d, J = 17.8 Hz, 1H), 6.24 (d, J = 15.5 Hz, 1H), 6.35 (dd, J = 15.5) , 9.8 Hz, 1H), 7.53 (dd, J = 17.5, 9.7 Hz, 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 (obcured by overwrapping 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)
A boron-containing conjugated polyene compound was synthesized by the following method.

Specifically, diphenylacetylene (32.09 mg, 0.180 mmol _{) was dissolved in benzene-d 6} (0.6 mL), and 2-{(E) -1,3-butadienyl} -4,4 5,5-tetramethyl-1,3,2-dioxaborolane (36.0 μL, 0.180 mmol) was added, followed by the addition of [Ru (naphthalene) (cod)] (6.07 mg, 0.0180 mmol). The reaction was completed after 5 minutes at room temperature, and a boron-containing conjugated polyene compound (A-4) was obtained in a yield of 63%.
^{1 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 = 14.9 Hz, 1H), 7.00-7.02 (m, 5H) , 7.04-7.10 (m, 5H) 7.50 (dd, J = 17, 10 Hz, 1H, partly 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 (obcured by overlapping with C ₆ D ₆ ), 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)
A boron-containing conjugated polyene compound was synthesized by the following method.

Specifically, 2-{(E) -1,3-butadieneyl} -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (40.4 μL, 0.2244 mmol) was added to benzene-d ₆ Dissolve in (0.6 mL), add diisopropyl 1-pentynylboronic acid (51.0 μL, 0.222 mmol), and then add [Ru (naphthalene) (cod)] (7.59 mg, 0.0225 mmol). Further added. When the reaction was carried out at room temperature for 3 hours, a boron-containing conjugated polyene compound (A-5) was obtained in a yield of 38%.
^{1 1} H NMR (400 MHz, C ₆ D ₆ , rt.): δ 0.96 (t, J = 8 Hz, 3H), 1.10 (s, 12H), 1.16 (d, J = 7) Hz, 12H), 1.56-1.61 (m, 2H), 2.60-2.64 (m, 2H), 4.42 (sept, J = 7 Hz, 2H), 5.51 (s) , 1H), 5.92 (d, J = 17 Hz, 1H), 6.34 (d, J = 15 Hz, 1H), 6.52 (dd, J = 15, 11 Hz, 1H), 7. 45 (dd, J = 17, 11 Hz, 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)
A boron-containing conjugated polyene compound was synthesized by the following method.

Specifically, 1-phenyl-1-propine (22.5 μL, 182 μmol) and 2-{(E) -1,3-butadieneyl} -4,4,5,5-tetramethyl-1,3,2- Dioxabololane (36.0 μL, 180 μmol) _{was dissolved in benzene-d 6} (0.6 mL), to which [Ru (naphthalene) (cod)] (6.07 mg, 18.0 μmol) was further added. When the reaction was carried out at room temperature for 1 hour, a boron-containing conjugated polyene compound (A-6) was obtained in a yield of 61%.
^{1 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, 1.5 Hz, 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 was not observed by HMQC probable due to bordering.
HRMS (APCI): m / z calcd for C ₁₉ H ₂₅ BO ₂ + H ⁺ : 297.2020 [M + H] ⁺ ; found: 297.2010.

(Example 7)
A boron-containing conjugated polyene compound was synthesized by the following method.

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-dioxabololane (19.0 μL, 95.0 μmol) _{was dissolved in benzene-d 6} (0.6 mL), to which [Ru (naphthalene) (cod)] (3.20 mg, 9.48 μmol) was further added. .. When the reaction was carried out at room temperature for 30 minutes, a boron-containing conjugated polyene compound (A-7) was obtained in a yield of 41%. In this reaction, 1-phenyl-2-trimethylsilyl-acetylene reacted regioselectively to obtain a Z-form product having a stereoselectivity of the terminal phenyl group as an initial product. However, after that, isomerization proceeded by leaving it in a solution at room temperature, and an E-form product having a stereoselectivity of a phenyl group was obtained.
Trimethyl ((1Z, 3E, 5E) -1-phenyl-6- (4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) hexa-1,3,5-triene- 2-Il) Silane
^{1 1} H NMR (400 MHz, C ₆ D ₆ , rt.): δ 0.20 (s, 9H), 1.08 (s, 12H), 5.91 (d, J = 17 Hz, 1H), 6.54 (d, J = 16 Hz, 1H), 6.66 (dd, J = 16, 10 Hz, 1H), 6.9 (s, 1H, obscured by overlap), 7.0-7.1 (M, 3H), 7.2 (d, J = 7 Hz, 12H) 7.44 (dd, J = 17.2, 10.3 Hz, 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} ), 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- (4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) hexa-1,3,5-triene- 2-Il) Silane
^{1 1} H NMR (400 MHz, C ₆ D ₆ , rt.): δ 0.21 (s, 9H), 1.08 (s, 12H), 5.91 (d, J = 18 Hz, 1H), 6.66 (dd, J = 15, 10 Hz, 1H), 6.9 (1H, obscured by overlap), 7.0-7.1 (m, 3H), 7.05 (d, J = 15 Hz) , 1H), 7.44 (dd, J = 18,10 Hz, 1H, partly obscured by overlap).

(Example 8)
A boron-containing conjugated polyene compound was synthesized by the following method.

Specifically, benzene-d ₆ (0. It was dissolved in 5 mL), and [Ru (naphthalene) (cod)] (3.43 mg, 0.0102 mmol) was further added. When the reaction was carried out at 30 ° C., boron-containing conjugated polyene compounds (A-101) and (A-102) were produced in a yield of 52% (production ratio 37/67) at a reaction time of 2 hours. The formation of the boron-containing conjugated polyene compound ^{was confirmed by 1} H-NMR measurement. The measurement results were as follows.
(A-101)
^{1 1} H NMR (400 MHz, C ₆ D ₆ , rt.): δ 0.95 (d, ³ J _{H, H} = 6.3 Hz, 12 H), 3.36 (s, 3 H), 4.37 ( ^{_{sept, 3 J H, H =}} 5.8Hz, 2H), 5.59 (d, 3 J H, H = 15.5Hz, 1H), 5.82 (s, 1H, obscured by overlapping with reactant), 6 .09 (dd, ³ _{JH, H} = 15.5, 11.5 Hz, 1H), 6.43-6.54 (m), 7.18-7.28 (m), 7.50 (dd, ³ J _{H, H} = 15.5, 10.9 Hz, 1 H).
(A-102)
^{1 1} H NMR (400 MHz, C ₆ D ₆ , rt.): δ 1.04 (d, ³ J _{H, H} = 5.7 Hz, 12 H), 3.45 (s, 3 H), 4.37 ( ^{_{sept, 3 J H, H =}} 5.8Hz, 2H), 5.96 (d, 3 J H, H = 15.5Hz, 1H), 6.43-6.54 (m, 2H), 6.68 (S, 1H), 7.02 (t, ³ J _{H, H} = 6.9 Hz, 1 H), 7.18-7.28 (m), 7.58 (dd, ³ J _{H, H} = 15. 5,10.9Hz, 1H).

(Example 9)
A boron-containing conjugated polyene compound was synthesized by the following method.

Specifically, dimethyl 2-phenylethynylboronic acid (24.5 μL, 0.101 mmol) and methyl (E) -2,4-pentadienoate (11.5 μL, 0.0987 mmol) were added to benzene-d ₆ (0. It was dissolved in 5 mL), and [Ru (naphthalene) (cod)] (3.43 mg, 0.0102 mmol) was further added. When the reaction was carried out at 30 ° C. for 1 hour and further at 50 ° C. for 2 hours, boron-containing conjugated polyene compounds (A-103) and (A-104) were produced in a yield of 68% (production ratio 19/81). The formation of the boron-containing conjugated polyene compound ^{was confirmed by 1} H-NMR measurement. The measurement results were as follows.
(A-103)
^{1 1} H NMR (400 MHz, C ₆ D ₆ , rt.): δ 3.22 (s, 3H), 3.35 (s, 6H), 5.62 (d, ³ _{JH, H} = 15. _{^{5Hz, 1H), 5.70 (s}} , 1H), 6.12 (dd, 3 J H, H = 15.5,11.0Hz, 1H), 6.45 (d, 3 J H, H = 15 ^{.5Hz, 1H), 7.28-7.30 (m} ), 7.49 (dd, 3 J H, H = 15.5,11.0Hz, 1H).
(A-104)
^{1 1} H NMR (400 MHz, C ₆ D ₆ , rt.): δ 3.23 (s, 3H), 3.32 (s, 6H), 5.82 (d, ³ _{JH, H} = 15. _{^{5Hz, 1H), 6.28 (dd}} , 3 J H, H = 15.5,10.9Hz, 1H), 6.46 (d, 3 J H, H = 15.5Hz, 1H), 6.70 (S, 1H), 7.28-7.30 (m), 7.55 (dd, ³ _{JH, H} = 15.5, 10.9 Hz, 1 H).

(Example 10)
A boron-containing conjugated polyene compound was synthesized by the following method.

Specifically, 2-phenylethynylboronic acid pinacol ester (40.62 μL, 0.1781 mmol) and methyl (E) -2,4-pentadienoate (21.0 μL, 0.180 mmol) were added to benzene-d ₆ (0). It was dissolved in (0.6 mL), and [Ru (naphthalene) (cod)] (7.12 mg, 0.0211 mmol) was further added. When the reaction was carried out at 30 ° C., a boron-containing conjugated polyene compound (A-105) was produced in a yield of 47% with a reaction time of 2 hours.
^{1 1} H NMR (400 MHz, C ₆ D ₆ , rt.): δ 1.02 (s, 12H), 3.45 (s, 3H), 6.07 (d, ³ _{JH, H} = 14. _{^{9Hz, 1H), 6.55 (d}} , 3 J H, H = 15.5Hz, 1H), 6.80 (dd, 3 J H, H = 15.2,10.9Hz, 1H), 6.80 (S, 1H), 7.00-7.13 (m, 3H), 7.39-7.40 (m, 1H), 7.61 (dd, ³ _{JH, H} = 15.2, 10. 9Hz, 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)
A boron-containing conjugated polyene compound was synthesized by the following method.

Specifically, 1-pentynylboronic acid pinacol ester (38.5 μL, 0.180 mmol) and methyl (E) -2,4-pentadienoate (21.0 μL, 0.180 mmol) were added to benzene-d ₆ (0). It was dissolved in (0.6 mL), and [Ru (naphthalene) (cod)] (6.04 mg, 0.0179 mmol) was further added. When the reaction was carried out at 30 ° C. for 26 hours and at 50 ° C. for 2 hours, boron-containing conjugated polyene compounds (A-106) and (A-107) were produced in a yield of 42% (production ratio 42/58).
(A-106)
^{1 1} H NMR (400 MHz, C ₆ D ₆ , rt.): δ 1.01 (t, ³ J _{H, H} = 7.44 Hz, 3 H), 1.06 (s, 12 H), 1.51 ( ^{_{sext, 3 J H, H =}} 7.44Hz, 2H), 2.71 (t, 3 J H, H = 7.44Hz, 2H), 3.43 (s, 3H), 5.71 (s, 3H _{^{), 5.87 (d, 3 J}} H, H = 15.5Hz, 1H), 6.15-6.25 (m, 2H), 7.38 (dd, 3 J H, H = 15.2, 9.76Hz, 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, coalesce with with base line), 127-129 (3-CH, obscured by overwrapping with C ₆ D ₆ ), 145 .02 (s), 145.37 (s), 159.11 (s), 166.95 (s).
(A-107)
^{1 1} H NMR (400 MHz, C ₆ D ₆ , rt.): δ 0.88 (t, ³ J _{H, H} = 7.48 Hz, 3 H), 1.01 (s, 12 H), 1.36 ( ^{_{sext, 3 J H, H =}} 7.44Hz, 2H), 2.46 (q, 3 J H, H = 7.44Hz, 2H), 3.43 (s, 3H), 6.06 (d, 3 J _{H, H} = 14.7 Hz, 1 H), 6.20 (t, ³ J _{H, H} = 7.44 Hz, 1 H), 6.49 (d, ³ J _{H, H} = 15.4 Hz, 1 H), 6.97 (dd, ³ _{JH, H} = 15.2, 11.4 Hz, 1 H), 7.64 (dd, ³ J _{H, H} = 15.5, 11.4 Hz, 1 H).
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 C 6 D 6), 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)
A boron-containing conjugated polyene compound was synthesized by the following method.

Specifically, 1-pentynylboronic acid pinacol ester (51.0 μL, 0.222 mmol) and 2-{(E) -1,3-butadienyl} -4,4,5,5-tetramethyl-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) was further added. When the reaction was carried out at room temperature, boron-containing conjugated polyene compounds (A-108) and (A-109) were produced in a yield of 34% (production ratio 25/75) at a reaction time of 3 hours.
(A-108)
^{1 1} H NMR (400 MHz, C ₆ D ₆ , rt.): δ 0.97 (t, ³ J _{H, H} = 7.4 Hz, 3 H), 1.05 (s, 12 H), 1.09 ( _{^{obscured by 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 = 17.2Hz, 1H), 6.27 (d, 3 J H, H = 15.5Hz, 1H), 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 resonance solvent were obcured by overwrapping with the resonances of A-108 and solvent.
(A-109)
^{1 1} H NMR (400 MHz, C ₆ D ₆ , rt.): δ 0.88 (t, ³ J _{H, H} = 7.4 Hz, 3 H), 1.01 (s, 12 H), 1.09 ( _{^{s, 12H), 1.36 (sext}} , 3 J H, H = 6.9Hz, 2H), 2.44 (q, 3 J H, H = 7.4Hz, 2H), 6.02 (dd, 3 J _{H, H} = 17.2 ^{Hz, 4} J _{H, H} = 1.7 Hz, 1 H), 6.13-6.20 (obcured by overwrapping with an impedance, 1 H), 6.55 (d, ³ J _{H, ^{H = 15.5Hz, 1H), 7.07}} (dd, 3 J H, H = 15.5,10.9Hz, 1H), 7.56 (ddd, 3 J H, H = 17.2,10. _{^{3Hz, 4 J H, H =}} 2.3Hz, 1H).
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)
A boron-containing conjugated polyene compound was synthesized by the following method.

Specifically, [Ru (acac) ₂ (1,5-cod)] (4.30 mg, 0.0106 mmol) was weighed into 25 mL Schlenk and replaced with nitrogen. Hexane (600 μL), Butadiene (6.2 μL, 0.0099 mmol), 3-hexyne (11.5 μL, 0.101 mmol), (E) -1- (4,5,5-tetramethyl-1,3,3) 2-dioxabolone-2-yl) butadiene (20.0 μL, 0.100 mmol) was added in that order, and the mixture was stirred at room temperature for 7 hours. Then, when the reaction solution was measured by GC-MS, the formation of the target product was confirmed. It was evaporated, dissolved in the total amount _{benzene-d 6,} was added dibenzyl (1.94mg, 10.6μmol). ¹ The yield of the target product was determined by 1 H NMR. The yield was 83%.

(Example 14)
A boron-containing conjugated polyene compound was synthesized by the following method.

_{Specifically, weigh 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) into 25 mL Schlenk. After substitution with nitrogen, CH ₃ CN (500 μL) was added, and the mixture was stirred for 10 minutes. After that, 3-hexyne (12.0 μL, 0.107 mmol), (E) -2- (buta-1,3-dienyl) -4,4,5,5-tetramethyl-1,3,2-dioxabolorane (20). 0.0 μL, 0.0990 mmol) and H ₂ O (70.0 μL) were added, and the mixture was stirred at room temperature. After reacting for 24 hours, the reaction solution was measured by GC-MS, and the formation of the target product was confirmed. The yield was about 4%.

(Example 15)
By the following method, a boron-containing conjugated polyene compound was synthesized and a subsequent cross-coupling reaction was carried out in one pot to synthesize a conjugated polyene compound.

Specifically, 1-pentynylboronic acid diisopropyl ester (22.5 μL, 0.0982 mmol) and methyl (E) -2,4-pentadienoate (11.5 μL, 0.0987 mmol) in benzene (500 μL). The reaction was carried out at room temperature for 24 hours in the presence of [Ru (naphthalene) (cod)] (3.35 mg, 0.00993 mmol). Subsequently, in the same solution, phenyl iodide (11.0 μL, 0.0987 mmol), a methanol solution of sodium methoxide (120 μL in methyl, 0.120 mmol), and [Pd (PPh ₃ ) ₄ ] (9.28 mg, 0. 00803 mmol) was added in this order and reacted at 50 ° C. for 15 minutes. The product was purified by recycling HPLC. The yield was 79% ((A-110) / (A-111) = 5/1).
(A-110)
^{1 1} H NMR (400 MHz, CDCl ₃ , rt.): δ 0.99 (t, ³ J _{H, H} = 7.4 Hz, 3 H), 1.56 (sext, ³ J _{H, H} = 7.4 Hz) ^{, 2H), 2.43 (m,} 2H), 3.74 (s, 3H), 5.91 (d, 3 J H, H = 15.5Hz, 1H), 6.40 (dd, 3 J H ^{_{, 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 = 15.5,10.9Hz, 1H).
¹³ C { ¹ H} NMR (100 MHz, CDCl ₃ , r.t.): 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, a boron-containing conjugated polyene compound was synthesized and a subsequent cross-coupling reaction was carried out in one pot to synthesize a conjugated polyene compound.

3-Hexin (20.0 μL, 0.175 mmol) and 2-{(E) -1,3-butadieneyl} -4,4,5-tetramethyl-1,3,2-dioxaborolane (36.0 μL,) 0.180 mmol) was reacted in benzene (500 μL) at room temperature for 5 minutes in the presence of [Ru (naphthalene) (cod)] (6.03 mg, 0.0178 mmol). Subsequently, in the same solution, phenyl iodide (20.0 μL, 0.179 mmol), a methanol solution of sodium methoxide (180.0 μL in methyl, 0.180 mmol), and [Pd (PPh ₃ ) ₄ ] (16.51 mg). , 0.01429 mmol) was added in this order, and the mixture was reacted at 50 ° C. for 2 hours. The product was purified by recycling HPLC. The yield was 62%.
^{1 1} H NMR (400 MHz, C ₆ D ₆ , rt.): δ 0.91 (t, ³ J _{H, H} = 7.44 Hz, 3 H), 1.05 (t, ³ J _{H, H} = 7) _{^{.48Hz, 3H; 10-Me)}} , 2.03 (quint, 3 J H, H = 7.44Hz, 2H), 2.24 (q, 3 J H, H = 7.44Hz, 2H), 5. 45 (t, ³ J _{H, H} = 7.44 Hz, 1 H), 6.27 (d, ³ J _{H, H} = 15.5 Hz, 1 H), 6.39 (dd, ³ J _{H, H} = 15. _{^{5,10.3Hz, 1H), 6.44 (d}} , 3 J H, H = 15.5Hz, 1H), 6.85 (dd, 3 J H, H = 15.5,10.3Hz, 1H) , 7.05 (t, 1H), 7.1-7.2 (overlapped with solvent), 7.30 (d, 3 J H, H = 7.5Hz, 2H).

(Example 17)
By the following method, a boron-containing conjugated polyene compound was synthesized and a subsequent cross-coupling reaction was carried out in one pot to synthesize a conjugated polyene compound.

Specifically, 1-pentynylboronic acid diisopropyl ester (22.5 μL, 0.0982 mmol) and (E) -1- (4,5,5-tetramethyl-1,3,2-dioxaborolane-2-) yl) Butadiene (22.0 μL, 0.110 mmol) and [Ru (naphthalene) (1,5-cod)] (3.34 mg, 0.00990 mmol) were reacted in benzene at 50 ° C. for 3 hours. Add vinyl bromide (15.0 μL, 0.212 mmol), ethanol solution of sodium ethoxide (240 μL in EtOH, 0.240 mmol) and [Pd (PPh ₃ ) ₄ ] (18.46 mg, 0.01597 mmol) to 50. The reaction was carried out at ° C. for 5 hours. As a result, compound (A-113) was produced in a yield of 46%.
^{1 1} H NMR (400 MHz, CDCl ₃ , rt.): δ 0.92 (t, ³ J _{H, H} = 7.4 Hz, 3 H), 1.46 (sext, ³ J _{H, H} = 7.4 Hz) _{^{, 2H), 2.33 (t,}} 3 J H, H = 7.4Hz, 2H), 5.09 (ddd, 3 J H, H = 10.3Hz, 2 J H, H = -1.0Hz, 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. ^{_{5Hz, 1H), 5.19 (dt}} , 3 J H, H = 17.8, 2 J H, H = 2.5Hz, 4 J H, H = 2.5Hz, 1H), 5.23 (ddd, ³ J _{H, H} = 17.8, ² J _{H, H} = -3.0, ⁴ J _{H, H} = -0.5 Hz, 1 H), 6.08 (ddt, ³ J _{H, H} = 10.5) , ⁴ J _{H, H} = -2.5, ⁴ J _{H, H} = -1.0 Hz, 1 H), 6.19 (dd, ³ J _{H, H} = 17.5 Hz, ⁴ J _{H, H} = -1 ^{_{.0Hz, 1H), 6.28 (ddd}} , 3 J H, H = 17.5,10.5Hz, 4 J H, H = -1.0Hz, 1H), 6.30 (ddd, 3 J H, ^{_{H = 16.0,10.5Hz, 4 J H,}} H = -1.0Hz, 1H), 6.32 (dd, 3 J H, H = 17.8,10.3Hz, 1H), 6.38 ( ^{Ddddd, 3} _{JH, H} = 16.0, 11.8, 10.3 Hz, ⁴ J _{H, H} = -1.0, -0.5 Hz, 1 H), 6.60 (dddd, ³ J _{H, H} = 17.8, 11.5, 10.3 Hz, 1 H).
¹³ C { ¹ H} NMR (100 MHz, CDCl ₃ , r.t.): 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)

A first raw material compound having a carbon-carbon triple bond and a conjugated di (or poly) having a 1,3-butadiene-4,4-diyl group and containing two carbon-carbon double bonds in the group. A step of reacting a second raw material compound having an en skeleton in the presence of a metal catalyst to obtain a boron-containing conjugated polyene compound having a conjugated polyene skeleton containing three or more carbon-carbon double bonds is provided.
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 di (or poly) ene skeleton.
A method for producing a boron-containing conjugated polyene compound, wherein the boron-containing conjugated polyene compound has a boron-containing group bonded to a carbon atom constituting the conjugated polyene skeleton. 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 method for producing a boron-containing conjugated polyene compound according to claim 1, wherein the boron-containing conjugated polyene compound is a compound represented by the following formula (1-3-1).

[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 independently represent a hydrogen atom or a monovalent group. When n is 1 or more, the plurality of R ^2s may be the same or different from each other. Further, the plurality of R ^3s may be the same or different from each other. R ^{2 to} each other, R ^{3 to} each other, and R ² and R ³ may be connected to each other to form a ring. ]

[In equation (1-3-1), B ¹ , R ¹ , n, R ² and R ³ have the same meanings as described above. The wavy line indicates that the double bond bonded to the wavy line may be either cis or trans. ] Among the R ³ in the formula (1-2-1), at least one of a boron-containing group, method for producing a boron-containing conjugated polyene compound as claimed in claim 2. 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 method for producing a boron-containing conjugated polyene compound according to claim 1, wherein the boron-containing conjugated polyene compound is a compound represented by the following formula (1-3-2).

[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 greater than ^{or equal to 0, n 2} represents 0 or 1, and R ² represents a hydrogen atom or a monovalent group. When n ¹ is 1 or more, the plurality of R ^2s may be the same or different from each other. However, when n ¹ is 1 or more, n ² is 1. R ² to each other may be bonded to each other to form a ring. ]

[In equation (1-3-2), B ¹ , R ¹ , n ¹ , n ² and R ² have the same meanings as described above. Two B ¹ represents may be the same or different from each other. Further, R ¹ of 2 may be the same as or different from each other. The wavy line indicates that the double bond bonded to the wavy line may be either cis or trans. ] The R ¹ is a silyl group and
The boron-containing conjugated polyene according to any one of claims 2 to 4, further comprising 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 compound. Method for producing a compound. 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 method for producing a boron-containing conjugated polyene compound according to claim 1, wherein the boron-containing conjugated polyene compound is a compound represented by the following formula (2-3).

[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. Provided that at least one of the two R ⁷ are boron-containing groups. When m is 1 or more, the plurality of R ^6s may be the same or different from each other. Further, two R ⁷ may be the same or different from each other. R ⁶ to each other, ^{R 7} together, and, ^{R 6} and ^{R 7} may be bonded to each other to form a ring. ]

[In equation (2-3), R ⁴ , R ⁵ , m, R ⁶ and R ⁷ have the same meanings as described above. The wavy line indicates that the double bond bonded to the wavy line may be either cis or trans. ] The method for producing a boron-containing conjugated polyene compound according to claim 6, wherein the value of the substituent constant σ _p ^{of Hammett of R 4} is larger than the value of the substituent constant σ _p ^{of Hammett of R 5.} The R ⁵ is a silyl group and
Said substituting R ⁵ a hydrogen atom in the boron-containing conjugated polyene compound, further comprising the step of obtaining a second boron-containing conjugated polyene compound, method for producing a boron-containing conjugated polyene compound according to claim 6 or 7. The inclusion according to any one of claims 1 to 9, wherein the metal catalyst comprises at least one selected from the group consisting of ruthenium (Ru), rhodium (Rh), cobalt (Co) and nickel (Ni). A method for producing a boron-conjugated polyene compound. The method for producing a boron-containing conjugated polyene compound according to claim 10, wherein the metal catalyst is a ruthenium catalyst. The method for producing a boron-containing conjugated polyene compound according to claim 10, wherein the ruthenium catalyst forms 0-valent ruthenium in the reaction system. 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).

[In formula (1-3-1A), 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 are independent of each other. Indicates a hydrogen atom or a monovalent group. When n is 1 or more, the plurality of R ^2s may be the same or different from each other. Further, the plurality of R ^3s may be the same or different from each other. R ^{2 to} each other, R ^{3 to} each other, and R ² and R ³ may be connected 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. ]

[In formula (1-3-2A), B ¹ represents a boron-containing group, R ¹¹ represents a hydrogen atom or a monovalent group, n ¹ represents an integer greater than ^{or equal to 0, and n 2} represents 0 or 1. Shown, 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, the plurality of R ^2s may be the same or different from each other. Moreover, two B ¹ represents may be the same or different from each other. R ² to each other may 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. ]

[In formula (2-3A), R ⁴ represents a monovalent group, R ¹⁵ represents a hydrogen atom or a monovalent group, m represents an integer greater than or ^{equal to 0, and R 6} and R ⁷ are independent of each other. Indicates a hydrogen atom or a monovalent group. Provided that at least one of the two R ⁷ are boron-containing groups. When m is 1 or more, the plurality of R ^6s may be the same or different from each other. Further, two R ⁷ may be the same or different from each other. R ⁶ to each other, ^{R 7} together, and, ^{R 6} and ^{R 7} may 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. ] The 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.
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 carry out the coupling reaction.
A method for producing a conjugated polyene compound. The method for producing a conjugated polyene compound according to claim 13, wherein the reactive group is a halogeno group. The first step is a step of producing the boron-containing conjugated polyene compound in the reaction system of the reaction in the presence of the metal catalyst.
The method for producing a conjugated polyene compound according to claim 13 or 14, wherein the second step is a step of adding the coupling reaction catalyst and the third raw material compound to the reaction system.