JP4856452B2 - Catalyst for carbon-carbon bond generation reaction and method for generating carbon-carbon bond using the same - Google Patents

Description

  The present invention relates to a catalyst for carbon-carbon bond formation reaction by 1,4-addition of an aromatic boronic acid compound to a conjugated enone compound, and a method for generating a carbon-carbon bond using the same.

  1,4-addition is a carbon-carbon bond forming reaction widely used in organic synthesis. Examples of carbon-carbon bond formation by 1,4-addition of an aromatic boronic acid compound to a conjugated enone compound are already known (Non-Patent Documents 1 to 4). However, these are examples using a homogeneous catalyst and are accompanied by a problem that it is difficult to separate the catalyst and the product.

  On the other hand, a solid catalyst for carbon-carbon bond reaction by 1,4-addition of an aromatic boronic acid compound to a conjugated enone compound, in which the catalyst and the product are easily separated, is known. For example, a carrier in which 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl is bonded to a polystyrene-poly (ethylene glycol) copolymer resin as a carrier, and 2,4-pentanedionatodiethylene rhodium is used. It is known that a solid catalyst in which rhodium is supported on a carrier by using a catalyst acts as a solid catalyst for a carbon-carbon bond reaction by 1,4-addition of an aromatic boronic acid compound to a conjugated enone compound (non- Patent Document 5). However, with this solid catalyst, the catalyst and the product can be easily separated by filtration, but there is a problem that the support is very expensive.

  Therefore, as a catalyst for carbon-carbon bond formation reaction by 1,4-addition of an aromatic boronic acid compound to a conjugated enone compound, a solid catalyst that can be easily separated from the product and can be used industrially at low cost. Development of the catalyst used was desired.

C. S. Cho, S. Motofusa, K. Ohe, S. Uemura and S. C. Shim, J. Org. Chem., 1995, 60, 883 M. Sasaki, H. Hayashi and N. Miyaura, Organometallics, 1997, 16, 4229 Y. Takaya, M. Ogasawara and T. Hayashi, J. Am. Chem. Soc., 1998, 120, 5579 T. Hayashi, K. Ueyama, N. Tokunaga and K. Yoshida, J. Am. Chem. Soc., 2003, 125, 11508 Y. Otomaru, T. Senda and T. Hayashi, Org. Lett., 2004, 6, 3357

  The present invention is a solid catalyst for carbon-carbon bond formation reaction by 1,4-addition of an aromatic boronic acid compound to a conjugated enone compound. An object of the present invention is to provide a catalyst using such a support. Moreover, this invention aims at providing the production | generation method of the carbon-carbon bond using this solid catalyst for carbon-carbon bond production | generation reaction.

  As a result of intensive studies of hydrotalcite-based solid catalysts as solid catalysts, the present inventors have found that when a solid catalyst having rhodium supported on a hydrotalcite support is used, 1,4 to conjugated enone compounds of aromatic boronic acid compounds can be obtained. -It discovered that the carbon-carbon bond formation reaction by addition advances, and came to complete this invention.

That is, the present invention is based first on 1,4-addition of an aromatic boronic acid compound to a conjugated enone compound comprising a hydrotalcite carrier and rhodium supported on the hydrotalcite carrier. A catalyst for carbon-carbon bond generation reaction is provided. In a preferred embodiment of the catalyst for carbon-carbon bond generation reaction of the present invention, the hydrotalcite carrier is represented by the following general formula (I):
[Mg _8-z Al _z (OH) ₁₆ ] ^{z +} [X ^n- _{z / n} ] ・ mH ₂ O (I)
(In the formula, Z is a real number of 0 ≦ Z ≦ 4, X ⁿ⁻ represents an anion having an n-valent charge, n is a natural number of 1 ≦ n ≦ 3, and m is 0 ≦ m ≦ 12. Real number.)
It is a hydrotalcite represented by In another preferred embodiment of the catalyst for carbon-carbon bond generation reaction of the present invention, the aromatic boronic acid compound has the following general formula (II):

（式中、R¹、R²、R³、R⁴およびR⁵は、独立に水素原子、アルキル基、アルコキシ基、ニトロ基またはハロゲン原子を表し、ただし、R¹およびR²、R²およびR³、R³およびR⁴、またはR⁴およびR⁵が結合してアルキレン基、アルケニレン基またはベンゾアルケニレン基を形成してもよい。）
で表される化合物であり、前記共役エノン化合物は下記一般式（ＩＩＩ）：

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group or a halogen atom, provided that R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , or R ⁴ and R ⁵ may combine to form an alkylene group, an alkenylene group or a benzoalkenylene group.)
The conjugated enone compound is represented by the following general formula (III):

（式中、R⁶およびR⁷は、独立に、水素原子、アルキル基、アルケニル基またはアリール基を表し、ただし、R⁶およびR⁷が結合してアルキレン基、アルケニレン基、またはベンゾアルケニレン基を形成してもよく、R⁷を炭素原子に直接結合させる波線で表わされた結合は、R⁷が水素原子でない場合に、炭素−炭素二重結合の両端の炭素原子に結合した水素原子、-COR⁶で表される基、およびR⁷で表される基の立体配置がＥ配置でもＺ配置でもよいことを表わす。）
で表される化合物である。

(In the formula, R ⁶ and R ⁷ independently represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, provided that R ⁶ and R ⁷ are bonded to form an alkylene group, an alkenylene group or a benzoalkenylene group. A bond represented by a wavy line that directly bonds R ⁷ to a carbon atom may form a hydrogen atom bonded to carbon atoms at both ends of a carbon-carbon double bond, when R ⁷ is not a hydrogen atom; (This means that the configuration of the group represented by -COR ⁶ and the group represented by R ⁷ may be either E configuration or Z configuration.)
It is a compound represented by these.

  Secondly, the present invention provides a carbon-carbon bond characterized in that 1,4-addition of an aromatic boronic acid compound to a conjugated enone compound is carried out in the presence of the catalyst for carbon-carbon bond generation reaction. A generation method is provided. In a preferred embodiment of the method for producing a carbon-carbon bond of the present invention, the aromatic boronic acid compound is a compound represented by the general formula (II), and the conjugated enone compound is represented by the general formula (III). Wherein the 1,4-addition product is represented by the following general formula (IV):

（式中、R¹、R²、R³、R⁴、R⁵、R⁶およびR⁷は前記のとおりである。）
で表わされる化合物である。

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as described above.)
It is a compound represented by these.

  The catalyst of the present invention is a solid catalyst exhibiting excellent catalytic activity in a carbon-carbon bond formation reaction by 1,4-addition of an aromatic boronic acid compound to a conjugated enone compound. Since this catalyst is a solid catalyst and the addition product and the catalyst can be easily separated, the reaction process, reaction apparatus, reaction management and the like can be facilitated. Furthermore, since this catalyst uses a hydrotalcite support that can be used at low cost, it is advantageous for industrial use. Further, this catalyst has a slight decrease in catalytic activity after being separated and recovered after the reaction, and can be reused repeatedly.

  Hereinafter, the present invention will be described in more detail. In the present invention, “room temperature” means 15-25 ° C.

<Catalyst for carbon-carbon bond formation reaction>
The catalyst for carbon-carbon bond generation reaction of the present invention is a solid catalyst comprising a hydrotalcite carrier and rhodium supported on the hydrotalcite carrier, and is a conjugated enone compound of an aromatic boronic acid compound. It can be used for a carbon-carbon bond formation reaction by 1,4-addition.

-Carrier-
The support of the catalyst for carbon-carbon bond generation reaction of the present invention is a hydrotalcite support. The hydrotalcite carrier may be used alone or in combination of two or more.

Hydrotalcite Hydrotalcite is a kind of basic layered clay compound, and has properties such as surface basicity, surface adsorption capacity, anion exchange capacity of the intermediate layer and cation exchange capacity of the basic layer. It is a material that is attracting attention. Hydrotalcite can be easily obtained industrially. In addition, the physical property of the hydrotalcite used as a support | carrier in the catalyst for carbon-carbon bond production | generation reaction of this invention is not limited.

Particularly preferred examples of the hydrotalcite carrier of the present invention include the following general formula (I):
[Mg _8-z Al _z (OH) ₁₆ ] ^{z +} [X ^n- _{z / n} ] ・ mH ₂ O (I)
(In the formula, Z is a real number of 0 ≦ Z ≦ 4, X ⁿ⁻ represents an anion having an n-valent charge, n is a natural number of 1 ≦ n ≦ 3, and m is 0 ≦ m ≦ 12. Real number.)
Hydrotalcite represented by

  In the general formula (I), Z is preferably a real number of 0.5 to 3, more preferably a real number of 1 to 2.5.

In the general formula (I), the type of anion represented by X ⁿ⁻ is not particularly limited. Examples of anions include halide ions such as fluoride ions, chloride ions, bromide ions, iodide ions; carbonate ions, bicarbonate ions, sulfate ions, hydrogen sulfate ions, nitrate ions, perchlorate ions, phosphate ions. Oxygen acid ions such as phosphate hydrogen ion and dihydrogen phosphate ion; organic carboxylate ions such as formate ion, acetate ion and benzoic acid; complex ions such as hexacyanoferrate (III) ion and hexachloroplatinum (IV) ion Is mentioned. Of these, halide ions or oxyacid ions are preferred, and carbonate ions are more preferred.

  In the general formula (I), n represents the valence of the charge of the anion and is a natural number of 1 to 3.

  In the general formula (I), m is preferably a real number of 0 to 8, more preferably a real number of 0 to 4.

-Catalyst preparation method (support of rhodium on hydrotalcite support)-
The rhodium can be supported on the hydrotalcite carrier by bringing the hydrotalcite carrier into contact with a solution containing rhodium.

  Specifically, the catalyst for the carbon-carbon bond generation reaction of the present invention, for example, dissolves a rhodium compound in a solvent, adds a hydrotalcite carrier to the resulting solution, and stirs to carry the rhodium compound on the carrier. Then, it can be obtained by solid-liquid separation and drying. This supporting reaction is typically performed at a temperature of 15 to 40 ° C. for 1 to 16 hours. In this manner, a catalyst for carbon-carbon bond generation reaction in which rhodium is supported on a hydrotalcite carrier is usually obtained.

  The solvent used for the supporting reaction is not particularly limited as long as it dissolves the rhodium compound, but ethanol, methanol, water, or a mixture thereof is preferable.

  The rhodium compound is not particularly limited as long as it is soluble in the solvent used in the supporting reaction step. For example, rhodium salts such as rhodium chloride, bromide, nitrate, sulfate, perchlorate and acetate; hexaammine Rhodium chloride, bis (ethylenediamine) rhodium chloride, tris (2,4-pentandionato) rhodium, dichlorobis (1,5-cyclooctadiene) dirhodium, dichlorobis {(2,2,1) -bicyclohepta 2,5-diene} dirhodium, (2,4-pentanedionato) dicarbonylrhodium, (2,4-pentanedionato) diethylenerhodium, hydridocarbonyltristriphenylphosphinerhodium, and the like can be used. Chloride and bromide, and dichlorobis (1,5-cyclooctadiene) Indium is preferable.

  The supported amount of rhodium per 1 g of the carrier is not particularly limited, but is preferably 1.0 μmol to 2 mmol, more preferably 100 μmol to 2 mmol in terms of rhodium element.

<Carbon-carbon bond formation reaction by 1,4-addition of aromatic boronic acid compound to conjugated enone compound>
A carbon-carbon bond can be generated by adding 1,4-addition of an aromatic boronic acid compound to a conjugated enone compound in a wet manner in the presence of the catalyst for carbon-carbon bond generation reaction. “Wet” generally means “in the presence of a solvent”, preferably “in a solvent”.

  In a preferred embodiment of the present invention, an aromatic boronic acid compound represented by the above general formula (II) in the presence of the carbon-carbon bond generation reaction catalyst is represented by the above general formula (III). A carbon-carbon bond can be produced by 1,4-addition to an enone compound. As a result, the carbon-carbon bond production | generation reaction product represented by the said general formula (IV) can be manufactured.

  For example, in the carbon-carbon bond formation reaction by 1,4-addition of phenylboronic acid to 2-cyclohexen-1-one, the yield of 3-phenylcyclohexanone is obtained by using the rhodium-supported hydrotalcite catalyst of the present invention. Can be obtained at 99% or more. The direct product of the 1,4-addition is 3-phenyl-1-cyclohexen-1-ol, but instead of this enol-type compound, a keto-type 3-phenyl which is a tautomer. Cyclohexanone can be obtained as the final product.

In the above general formulas (II) and (IV), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are preferably independently a hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n An alkyl group having 1 to 6 carbon atoms such as -butyl group, n-pentyl group, n-hexyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n-pentyloxy group, an alkoxy group having 1 to 6 carbon atoms such as an n-hexyloxy group; a nitro group; or a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, provided that R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , or R ⁴ and R ⁵ may combine to form an alkylene group, an alkenylene group or a benzoalkenylene group.

Preferable examples of the alkylene group include alkylene groups having 2 to 10 carbon atoms such as an ethylene group, a propylene group, and a butylene group. Preferred examples of the alkenylene group include —CH═CH—, —CH═CH—CH ₂ —, —CH ₂ —CH═CH—CH ₂ —, —CH ₂ —CH═CH—CH ₂ —CH ₂ —. Examples thereof include alkenylene groups having 2 to 10 carbon atoms such as CH ₂ —CH ₂ —CH ₂ —CH ₂ —CH ₂ —. Preferable examples of the benzoalkenylene group include benzoalkenylene groups having 6 to 10 carbon atoms.

  The benzoalkenylene group is the following general formula (V):

（式中、pは０〜１の整数、qは０〜３の整数）
で表される二価の炭化水素基を意味する。

(Wherein p is an integer from 0 to 1, q is an integer from 0 to 3)
The divalent hydrocarbon group represented by these.

In the general formulas (III) and (IV), R ⁶ and R ⁷ are preferably independently a hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, an alkyl group having 1 to 6 carbon atoms such as n-hexyl group; an alkenyl group having 2 to 6 carbon atoms such as vinyl group, propylene group, butylene group, pentylene group and hexylene group; phenyl group and o-tolyl group An aryl group having 6 to 10 carbon atoms such as m-tolyl group and p-tolyl group, where R ⁶ and R ⁷ are bonded to form an alkylene group, an alkenylene group or a benzoalkenylene group. Good.

Preferable examples of the alkylene group include alkylene groups having 2 to 10 carbon atoms such as an ethylene group, a propylene group, and a butylene group. Preferred examples of the alkenylene group include —CH═CH—, —CH═CH—CH ₂ —, —CH ₂ —CH═CH—CH ₂ —, —CH ₂ —CH═CH—CH ₂ —CH ₂ —. Examples thereof include alkenylene groups having 2 to 10 carbon atoms such as CH ₂ —CH ₂ —CH ₂ —CH ₂ —CH ₂ —. Preferable examples of the benzoalkenylene group include benzoalkenylene groups having 6 to 10 carbon atoms.

  The amount of the aromatic boronic acid compound added is preferably 0.8 to 3.0 mol, more preferably 0.9 to 2.0 mol, with respect to 1 mol of the conjugated enone compound.

  The catalyst of the present invention is preferably used in the range of 0.01 to 20 mol%, more preferably in the range of 0.1 to 10 mol%, in terms of rhodium element with respect to the conjugated enone compound which is one of the reactants. Even more preferably, it is used in the range of 0.5 to 5 mol%.

  The solvent used for the carbon-carbon bond generation reaction is not particularly limited as long as it dissolves the aromatic boronic acid compound and the conjugated enone compound, which are reactants, but ethanol, 1,4-dioxane, 1,5-cyclohexane. An organic solvent such as octadiene or dimethyl ether; or a combination thereof is preferable, and a mixed solvent of 1,4-dioxane and 1,5-cyclooctadiene is particularly preferable.

  This carbon-carbon bond formation reaction is usually performed in an atmosphere of an inert gas such as nitrogen or argon in a temperature range of room temperature to 200 ° C. for about 1 to 24 hours.

  Specific examples of the aromatic boronic acid compound include phenylboronic acid, p-tolylboronic acid, p-anisboronic acid, m-anisboronic acid, p-nitrophenylboronic acid, and p-fluorophenylboronic acid.

  Specific examples of the conjugated enone compound include 2-cyclohexen-1-one, 2-cyclopenten-1-one, 3-buten-2-one, 3-nonen-2-one, and 1,3-diphenyl-2-propene. Examples include -1-one, 3-phenyl-2-propenal, and acrylaldehyde.

  Specific examples of the reaction product obtained by the method for producing a carbon-carbon bond of the present invention include 3-phenylcyclohexanone, 3-phenylcyclopentanone, 4-phenylbutan-2-one, 3-phenylnonane-2- ON, 1,3,3-triphenyl-1-propanone, 3,3-diphenylpropanal, 3- (p-tolyl) cyclohexanone, 3- (4-methoxyphenyl) cyclohexanone, 3- (3-methoxyphenyl) Examples include cyclohexanone, 3-phenylpropanal, 3- (4-fluorophenyl) cyclohexanone, and 3- (4-nitrophenyl) cyclohexanone.

  Each of the aromatic boronic acid compound and the conjugated enone compound may be used alone or in combination of two or more. When one or both of an aromatic boronic acid compound and a conjugated enone compound are used in combination of two or more, the resulting reaction product may be a mixture of two or more.

  Examples of the present invention and comparative examples are shown below, but the present invention is not limited to the following examples.

<Example 1>
(Preparation of rhodium-supported hydrotalcite catalyst)
A solution was obtained by dissolving 0.2 mmol of rhodium chloride hydrate (manufactured by NE Chemcat Co., Ltd.) in 200 ml of water. To this solution, 1.0 g of hydrotalcite (trade name: HT5-4, manufactured by Tomita Pharmaceutical Co., Ltd.) was added and stirred for 9 hours at room temperature to obtain a reaction mixture. This reaction mixture was filtered and dried to obtain 1.0 g of a rhodium-supported hydrotalcite catalyst. The supported amount of rhodium per gram of hydrotalcite support was 0.19 mol in terms of rhodium element.

<Example 2>
(Synthesis of 3-phenylcyclohexanone by carbon-carbon bond formation reaction by 1,4-addition of phenylboronic acid to 2-cyclohexen-1-one)
1,4-dioxane containing 0.07% by weight of 1,5-cyclooctadiene (hereinafter referred to as “mixed 1,4-dioxane solvent”) under a stream of argon, 1 mmol of phenylboronic acid and 1 mmol of 2-cyclohexen-1-one The solution was obtained by dissolving in 2 ml. To the obtained solution, 60 mg of the rhodium-supported hydrotalcite catalyst prepared in Example 1 was added, and the reaction was performed by stirring at 100 ° C. for 4 hours in an argon atmosphere. After completion of the reaction, the reaction mixture was cooled, and the catalyst was separated by filtration to obtain 3-phenylcyclohexanone dissolved in a mixed 1,4-dioxane solvent as a filtrate. The obtained filtrate was diluted with a mixed 1,4-dioxane solvent and subjected to gas chromatography (hereinafter referred to as “GC”) to measure the yield of 3-phenylcyclohexanone. The yield of 3-phenylcyclohexanone relative to the charged 2-cyclohexen-1-one was 99% or more.

<Example 3>
(Synthesis of 3-phenylcyclohexanone by carbon-carbon bond formation reaction by 1,4-addition of phenylboronic acid to 2-cyclohexen-1-one)
In Example 2, 3-phenylcyclohexanone was obtained in the same manner as in Example 2 except that ethanol containing 0.07% by weight of 1,5-cyclooctadiene was used instead of the mixed 1,4-dioxane solvent. The yield was measured. The yield of 3-phenylcyclohexanone with respect to the charged 2-cyclohexen-1-one was 98%.

<Example 4>
(Synthesis of 3-phenylcyclohexanone by carbon-carbon bond formation reaction by 1,4-addition of phenylboronic acid to 2-cyclohexen-1-one)
In Example 2, 3-phenylcyclohexanone was obtained in the same manner as in Example 2 except that dimethyl ether containing 0.07% by weight of 1,5-cyclooctadiene was used instead of the mixed 1,4-dioxane solvent. The yield was measured. The yield of 3-phenylcyclohexanone with respect to the charged 2-cyclohexen-1-one was 97%.

<Example 5>
(Synthesis of 3-phenylcyclopentanone by carbon-carbon bond formation reaction by 1,4-addition of phenylboronic acid to 2-cyclopenten-1-one)
1.5 mmol of phenylboronic acid and 1 mmol of 2-cyclopenten-1-one were dissolved in 2 ml of mixed 1,4-dioxane solvent under an argon stream to obtain a solution. To the obtained solution, 60 mg of the rhodium-supported hydrotalcite catalyst prepared in Example 1 was added, and the reaction was performed by stirring at 150 ° C. for 5 hours in an argon atmosphere. After completion of the reaction, the reaction mixture was cooled and the catalyst was separated by filtration. The solvent of the obtained filtrate was removed by evaporation to obtain a residue. The obtained residue was dissolved in a normal hexane / ethyl acetate mixed solvent (volume ratio: 9/1) and silica gel column chromatography at room temperature. (Eluent: normal hexane / ethyl acetate = 9/1 (volume ratio)) and dried to obtain 3-phenylcyclopentanone. When the weight of the obtained 3-phenylcyclopentanone was measured and the isolated yield was calculated, it was 75% with respect to the charged 2-cyclopenten-1-one.

<Example 6>
(Synthesis of 4-phenylbutan-2-one by carbon-carbon bond formation reaction by 1,4-addition of phenylboronic acid to 3-buten-2-one)
In Example 5, except that the amount of phenylboronic acid was 1 mmol, 3-buten-2-one was used instead of 2-cyclopenten-1-one, the reaction temperature was 100 ° C., and the stirring time was 4 hours. In the same manner as in Example 5, 4-phenylbutan-2-one was obtained and the isolated yield was measured. The isolated yield of 4-phenylbutan-2-one relative to the charged 3-buten-2-one was 92%.

<Example 7>
(Synthesis of 3-phenylnonan-2-one by carbon-carbon bond formation reaction by 1,4-addition of phenylboronic acid to 3-nonen-2-one)
In Example 5, 3-phenylnonan-2-one was used in the same manner as in Example 5 except that 3-nonen-2-one was used instead of 2-cyclopenten-1-one and the stirring time was changed to 8 hours. And the isolated yield was measured. The isolated yield of 3-phenylnonan-2-one relative to the charged 3-nonen-2-one was 76%.

<Example 8>
(Synthesis of 1,3,3-triphenyl-1-propanone by carbon-carbon bond formation reaction by 1,4-addition of phenylboronic acid to 1,3-diphenyl-2-propen-1-one)
In Example 5, 1,3-diphenyl-2-propen-1-one was used instead of 2-cyclopenten-1-one, and the stirring time was 24 hours. 3,3-triphenyl-1-propanone was obtained and the isolation yield was measured. The isolated yield of 1,3,3-triphenyl-1-propanone with respect to 1,3-diphenyl-2-propen-1-one charged was 99%.

<Example 9>
(Synthesis of 3,3-diphenylpropanal by carbon-carbon bond formation reaction by 1,4-addition of phenylboronic acid to 3-phenyl-2-propenal)
In Example 2, 3,3-diphenylpropanal was used in the same manner as in Example 2 except that 3-phenyl-2-propenal was used instead of 2-cyclohexen-1-one and the reaction temperature was 150 ° C. And the yield was measured. The yield of 3,3-diphenylpropanal with respect to the charged 3-phenyl-2-propenal was 74%.

<Example 10>
(Synthesis of 3- (p-tolyl) cyclohexanone by carbon-carbon bond formation reaction by 1,4-addition of p-tolylboronic acid to 2-cyclohexen-1-one)
In Example 5, 3- (p-tolyl) was used in the same manner as in Example 5 except that 1 mmol of p-tolylboronic acid was used instead of 1.5 mmol of phenylboronic acid, the reaction temperature was 100 ° C., and the stirring time was 4 hours. ) Cyclohexanone was obtained and the isolated yield was measured. The isolated yield of 3- (p-tolyl) cyclohexanone relative to the charged 2-cyclohexen-1-one was 99%.

<Example 11>
(Synthesis of 3- (4-methoxyphenyl) cyclohexanone by carbon-carbon bond formation reaction by 1,4-addition of p-anisboronic acid to 2-cyclohexen-1-one)
In Example 5, 3- (4-methoxy) was used in the same manner as in Example 5 except that 1 mmol of p-anisboronic acid was used instead of 1.5 mmol of phenylboronic acid, the reaction temperature was 100 ° C., and the stirring time was 4 hours. Phenyl) cyclohexanone was obtained and the isolated yield was measured. The isolated yield of 3- (4-methoxyphenyl) cyclohexanone relative to the charged 2-cyclohexen-1-one was 75%.

<Comparative Example 1>
(Synthesis of 3-phenylcyclohexanone by carbon-carbon bond formation reaction by 1,4-addition of phenylboronic acid to 2-cyclohexen-1-one using hydrotalcite as a catalyst)
In Example 2, an experiment was conducted in the same manner as in Example 2 except that hydrotalcite (HT5-4 manufactured by Tomita Pharmaceutical Co., Ltd.) was used as a catalyst instead of the rhodium-supported hydrotalcite catalyst prepared in Example 1. The operation was performed and the yield of 3-phenylcyclohexanone was measured. The yield of 3-phenylcyclohexanone relative to the charged 2-cyclohexen-1-one was 0%.

<Comparative example 2>
(Synthesis of 3-phenylcyclohexanone by carbon-carbon bond formation reaction by 1,4-addition of phenylboronic acid to 2-cyclohexen-1-one using rhodium chloride as a catalyst)
1 mmol of phenylboronic acid and 1 mmol of 2-cyclohexen-1-one were dissolved in 2 ml of mixed 1,4-dioxane solvent under an argon stream to obtain a solution. To the resulting solution, 0.012 mmol of rhodium chloride hydrate (manufactured by N.E. Chemcat Co., Ltd.) was added as a catalyst in terms of rhodium, and the reaction was performed by stirring at 100 ° C. for 4 hours in an argon atmosphere. . After completion of the reaction, the reaction mixture was cooled and filtered, but rhodium used as a catalyst could not be separated by filtration. The obtained filtrate was diluted with a mixed 1,4-dioxane solvent and subjected to GC, and the yield of 3-phenylcyclohexanone was measured. The yield of 3-phenylcyclohexanone relative to the charged 2-cyclohexen-1-one was 0%.

<Comparative Example 3>
(Synthesis of 3-phenylcyclohexanone by carbon-carbon bond formation reaction by 1,4-addition of phenylboronic acid to 2-cyclohexen-1-one using 2,4-pentanedionatodicarbonylrhodium as a catalyst: Non-patent document 2)
2 mmol of phenylboronic acid and 0.03 mmol of 2,4-pentanedionatodicarbonylrhodium (manufactured by N.E. Chemcat Co., Ltd.) and 0.03 mmol of 1,4-bis (diphenylphosphino) butane were placed in 6 ml of cyclohexane under an argon stream. In addition, the mixture was stirred at room temperature for 15 minutes. 1 ml of water and 1 mmol of 2-cyclohexen-1-one were added to the resulting solution, and the mixture was stirred at 50 ° C. for 6 hours. After cooling, the product was extracted with benzene, washed with brine, and then dried over magnesium sulfate to obtain 3-phenylcyclohexanone dissolved in benzene. The obtained 3-phenylcyclohexanone was diluted with benzene and subjected to GC, and the yield of 3-phenylcyclohexanone was measured. The yield of 3-phenylcyclohexanone with respect to the charged 2-cyclohexen-1-one was 52%.

<Comparative example 4>
(Preparation of rhodium supported alumina catalyst)
A solution was obtained by dissolving 0.2 mmol of rhodium chloride hydrate (manufactured by NE Chemcat Co., Ltd.) in 200 ml of water. To this solution, 1.0 g of activated alumina (manufactured by Wako Pure Chemical Industries, Ltd., 75 μm column chromatograph) was added and stirred at room temperature for 9 hours to obtain a reaction mixture. This reaction mixture was filtered and dried to obtain 1.0 g of a rhodium-supported alumina catalyst.

<Comparative Example 5>
(Synthesis of 3-phenylcyclohexanone by carbon-carbon bond formation reaction by 1,4-addition of phenylboronic acid to 2-cyclohexen-1-one using rhodium supported alumina catalyst)
1 mmol of phenylboronic acid and 1 mmol of 2-cyclohexen-1-one were dissolved in 2 ml of mixed 1,4-dioxane solvent under an argon stream to obtain a solution. To the obtained solution, 60 mg of the rhodium-supported alumina catalyst prepared in Comparative Example 4 was added, and the reaction was performed by stirring at 100 ° C. for 4 hours in an argon atmosphere. After completion of the reaction, the reaction mixture was cooled and the catalyst was separated by filtration. The obtained filtrate was diluted with a mixed 1,4-dioxane solvent and subjected to GC, and the yield of 3-phenylcyclohexanone was measured. The yield of 3-phenylcyclohexanone relative to the charged 2-cyclohexen-1-one was 0%.

Claims (5)

  A catalyst for carbon-carbon bond generation reaction by 1,4-addition of an aromatic boronic acid compound to a conjugated enone compound, comprising a hydrotalcite carrier and rhodium supported on the hydrotalcite carrier. The hydrotalcite carrier has the following general formula (I):
[Mg _8-z Al _z (OH) ₁₆ ] ^{z +} [X ^n- _{z / n} ] ・ mH ₂ O (I)
(In the formula, Z is a real number of 0 ≦ Z ≦ 4, X ⁿ⁻ represents an anion having an n-valent charge, n is a natural number of 1 ≦ n ≦ 3, and m is 0 ≦ m ≦ 12. Real number.)
The catalyst for carbon-carbon bond production | generation reaction which concerns on the hydrotalcite represented by these. The aromatic boronic acid compound is represented by the following general formula (II):

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group or a halogen atom, provided that R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , or R ⁴ and R ⁵ may combine to form an alkylene group, an alkenylene group or a benzoalkenylene group.)
The conjugated enone compound is represented by the following general formula (III):

(In the formula, R ⁶ and R ⁷ independently represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, provided that R ⁶ and R ⁷ are bonded to form an alkylene group, an alkenylene group or a benzoalkenylene group. A bond represented by a wavy line that directly bonds R ⁷ to a carbon atom may form a hydrogen atom bonded to carbon atoms at both ends of a carbon-carbon double bond, when R ⁷ is not a hydrogen atom; (This means that the configuration of the group represented by -COR ⁶ and the group represented by R ⁷ may be either E configuration or Z configuration.)
The catalyst for carbon-carbon bond production | generation reaction based on Claim 1 or 2 characterized by the above-mentioned.   Carbon in which an aromatic boronic acid compound is 1,4-added to a conjugated enone compound in a wet manner in the presence of the carbon-carbon bond generation reaction catalyst according to any one of claims 1 to 3. -Method for generating carbon bonds. The aromatic boronic acid compound is a compound represented by the general formula (II), the conjugated enone compound is a compound represented by the general formula (III), and the 1,4-addition product is The following general formula (IV):

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as described above.)
The method for producing a carbon-carbon bond according to claim 4, wherein the compound is represented by the formula: