JP3015871B2 - Silicon-containing (borylalkylidene) cycloalkane compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel 1- (1-borylalkylidene) -2- () which is a cyclic compound containing two different typical metal atoms in one molecule, which is useful as an intermediate for the production of medicinal and agricultural chemicals. 1-silylalkylidene) cycloalkane compounds, novel 1- (1-borylalkylidene) -2-
The present invention relates to (1-silylalkyl) cycloalkane compounds and methods for producing them.

[0002]

2. Description of the Related Art Hitherto, as a method for constructing a 1,2-dialkylidenecycloalkane structure or a 1-alkylidene-2-alkylcycloalkane structure, hydrogenation accompanied by cyclization of diyne or eneyne using a transition metal catalyst has been proposed. And a method utilizing the formation and isomerization of a carbon-carbon bond are known. In recent years, there has been reported an example in which a typical metal such as silicon or germanium is introduced simultaneously with cyclization by applying hydrosilylation, cyanosilylation, cyanogermylation, or the like to the reaction of diyne or enein (for example, , Chem. Rev., Vol. 88, No. 1081-1
119, 1988, Chem. Rev., 96, 635-662,
1996).

[0003] In any case, however, the number of typical metals introduced at the same time as ring formation was limited to one or less. In order to effectively use such a cyclized product as an organic synthesis reagent, it has been desired to establish a cyclic compound containing more typical metals and to establish an efficient synthesis method thereof.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a novel 1- (1) compound having two different typical metal elements in one molecule, which is a very useful reagent in organic synthesis of medicines, agricultural chemicals and the like.
-Borylalkylidene) -2- (1-silylalkylidene) cycloalkane compounds and novel 1- (1-borylalkylidene) -2- (1-silylalkyl) cycloalkane compounds, and methods for efficiently producing them. Aim.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a silylborane compound acts on a diyne compound or an eneyne compound in the presence of a Group 10 transition metal catalyst. With 1- (1) having two types of typical metal elements of boron and silicon in one molecule
-Borylalkylidene) -2- (1-silylalkylidene) cycloalkane compound or 1- (1-borylalkylidene) -2- (1-silylalkyl) cycloalkane compound can be obtained regioselectively and stereoselectively, The present invention has been completed.

That is, according to the present invention, the following general formula (1)

Embedded image(Where R¹, R^TwoAnd R^ThreeIs an aliphatic group or an aromatic group
R represents a group^FourAnd R ^FiveIs a halogen atom, alkoxy
Group, an aryloxy group or an amino group;^FourAnd
And R^FiveIs an alkoxy group, an aryloxy group or an amino
When representing a group, R^FourAnd R^FiveIs bonded to form a ring
May be, R⁶And R⁷Represents a hydrogen atom, an aliphatic group or
Represents an aromatic group;⁸May contain hetero elements
Represents a well-substituted or unsubstituted alkylene group. )
1- (1-borylalkylidene) -2- (1-silyl
(Alkylidene) cycloalkane compounds are provided.
Further, according to the present invention, the following general formula (2)

Embedded image (Wherein, R ^1, R ² and R ³ represents an aliphatic group or an aromatic group, R ⁴ and R ⁵ represents a halogen atom, an alkoxy group, an aryloxy group or an amino group, R ⁴ and R ^{When 5} represents an alkoxy group, an aryloxy group or an amino group, R ⁴ and R ⁵ may combine to form a ring, and R ⁶ and R ⁷ represent a hydrogen atom, an aliphatic group or an aromatic group. And R ⁸ represents a substituted or unsubstituted alkylene group which may contain a hetero element.) 1- (1-borylalkylidene) -2- (1-silylalkyl) cycloalkane compound Is provided. Further, according to the present invention, the following general formula (3)

Embedded image R¹R^TwoR^ThreeSi-BR^FourR^Five(3) (where R¹, R^TwoAnd R^ThreeIs an aliphatic group or an aromatic group
R represents a group^FourAnd R^FiveIs a halogen atom, alkoxy
Group, an aryloxy group or an amino group;^FourAnd
And R^FiveIs an alkoxy group, an aryloxy group or an amino
When representing a group, R ^FourAnd R^FiveIs bonded to form a ring
May be. ) And a silylborane compound represented by the following:
General formula (4)

Embedded image R ⁶ —C≡C—R ⁸ —C≡C—R ⁷ (4) (wherein R ⁶ and R ⁷ represent a hydrogen atom, an aliphatic group or an aromatic group, and R ⁸ represents Represents a substituted or unsubstituted alkylene group which may contain a hetero element.) In the presence of a catalyst comprising a Group 10 metal, a metal complex or a metal salt thereof; The obtained general formula (1)

Embedded image (Wherein, R ^1, R ² and R ³ represents an aliphatic group or an aromatic group, R ⁴ and R ⁵ represents a halogen atom, an alkoxy group, an aryloxy group or an amino group, R ⁴ and R ^{When 5} represents an alkoxy group, an aryloxy group or an amino group, R ⁴ and R ⁵ may combine to form a ring, and R ⁶ and R ⁷ represent a hydrogen atom, an aliphatic group or an aromatic group. And R ⁸ represents a substituted or unsubstituted alkylene group which may contain a hetero element.) 1- (1-borylalkylidene) -2- (1-silylalkylidene) cycloalkane compound Wherein the 1- (1-borylalkylidene) -2- is
A method for producing a (1-silylalkylidene) cycloalkane compound is provided. Still further, according to the present invention,
The following general formula (3)

Embedded image R ¹ R ² R ³ Si—BR ⁴ R ⁵ (3) wherein R ¹ , R ² and R ³ represent an aliphatic group or an aromatic group, and R ⁴ and R ⁵ are When R ⁴ and R ⁵ represent a halogen atom, an alkoxy group, an aryloxy group or an amino group and R ⁴ and R ⁵ represent an alkoxy group, an aryloxy group or an amino group, R ⁴ and R ⁵ are bonded to form a ring And a silylborane compound represented by the following general formula (5):

Embedded image R ⁶ —CH ＝ CH—R ⁸ —C≡C—R ⁷ (5) (wherein, R ⁶ and R ⁷ represent a hydrogen atom, an aliphatic group or an aromatic group, and R ⁸ represents Represents a substituted or unsubstituted alkylene group optionally containing a hetero element.) In the presence of a catalyst comprising a Group 10 metal, a metal complex or a metal salt thereof; The obtained general formula (2)

Embedded image (Wherein, R ^1, R ² and R ³ represents an aliphatic group or an aromatic group, R ⁴ and R ⁵ represents a halogen atom, an alkoxy group, an aryloxy group or an amino group, R ⁴ and R ^{When 5} represents an alkoxy group, an aryloxy group or an amino group, R ⁴ and R ⁵ may combine to form a ring, and R ⁶ and R ⁷ represent a hydrogen atom, an aliphatic group or an aromatic group. And R ⁸ represents a substituted or unsubstituted alkylene group which may contain a hetero element.) 1- (1-borylalkylidene) -2- (1-silylalkyl) cycloalkane compound Wherein the 1- (1-borylalkylidene) -2- (1
-Silylalkylidene) cycloalkane compounds are provided.

The 1- (1-borylalkylidene) of the present invention
The -2- (1-silylalkylidene) cycloalkane compound is a cyclic compound having a carbon-boron bond and a carbon-silicon bond having completely different reactivities in the molecule, and is a very useful compound as an organic synthesis reagent. 1 of the present invention
The-(1-borylalkylidene) -2- (1-silylalkylidene) cycloalkane compound has a vinyl borane structure and a vinyl silane structure, and the compound having a vinyl borane structure is, for example, when a palladium complex is used as a catalyst.
Capable of causing a regioselective and stereoselective coupling reaction with vinyl halide, allyl halide, etc. (for example, Chem. Rev., Vol. 95, No. 2457-2483)
Pp. 1995) and that aldehydes or ketones can be efficiently obtained by oxidation with aqueous hydrogen peroxide under basic conditions (for example, J. Am. Chem. Soc., Vol. 83, No. 3,
834, 1961). On the other hand, when a compound having a vinylsilane structure is reacted with an acid chloride or an alkoxymethyl chloride in the presence of aluminum chloride, a substitution product at a position having a silyl group can be obtained (for example, J. Chem. Soc., Perkin Trans. 1
Pp. 2485, 1980) that a coupling product with vinyl halide, allyl halide, etc. can be obtained by using a palladium complex as a catalyst in the presence of tetrabutylammonium fluoride (for example, Synlett).
Journal, pp. 845-853, 1991).

On the other hand, the 1- (1-borylalkylidene) -2- (1-silylalkyl) cycloalkane compound of the present invention has a vinylborane structure and a silyl group, and the silyl group is a hydrogen peroxide solution under basic conditions. It is easily oxidized with m-chloroperbenzoic acid or the like and is equivalent to a hydroxy group, so that it is useful as a 2-substituted hydroxymethylcycloalkane precursor, and has a reaction activity derived from the vinylborane structure. Therefore, the (1-borylalkylidene) -2- (1-silylalkylidene) cycloalkane compound and the (1-borylalkylidene)-of the present invention.
The 2- (1-silylalkyl) cycloalkane compound is
It is a novel and useful compound having both a reaction activity based on a vinyl borane structure and a reaction activity based on a vinyl silane structure or a silyl group.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The silylborane compound used as a reaction raw material in the present invention is represented by the above general formula (3). In the general formula (3), R ¹ , R ² and R ³
Represents an aliphatic group or an aromatic group. The aliphatic group includes a chain or cyclic alkyl group or alkenyl group. The carbon number of the aliphatic group is 1 to 18, preferably 1 to
8 Specific examples of the aliphatic group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a cyclohexyl group, a vinyl group, an allyl group, and the like.

The aromatic group includes both an aromatic group consisting of a carbocyclic ring and an aromatic group consisting of a heterocyclic ring. Specific examples of the aromatic group include a phenyl group, a tolyl group, a naphthyl group, a pyridyl group, a thienyl group, a furyl group and the like.

R ⁴ and R ⁵ represent a halogen atom, an alkoxy group, an aryloxy group or an amino group.
Examples of the halogen atom include chlorine, bromine and iodine. Specific examples of the alkoxy group and the aryloxy group include a methoxy group, an ethoxy group, a t-butoxy group, a phenoxy group, a benzyloxy group and the like. Also,
Specific examples of the amino group include an unsubstituted amino group, a dimethylamino group, a diethylamino group, a diphenylamino group, a dibenzylamino group, and the like. When R ⁴ and R ⁵ represent an alkoxy group, an aryloxy group or an amino group, R ⁴ and R ⁵ can combine to form a ring. The ring in this case is a ring containing boron and oxygen or nitrogen. The alkoxy group, aryloxy group or amino group forming such a ring includes aliphatic and aromatic divalent groups. Specific examples thereof include dimethylene dioxy, trimethylene dioxy, tetramethyl dimethylene dioxy, phenylenedioxy, N,
In addition to an alkylenediamino group such as an N-dimethyldimethylenediamino group, an N, N-dimethyltrimethylenediamino group and a cyclohexylenediamino group, an N, N-dimethylphenylenediamino group can be mentioned.

Specific examples of the silylborane compound represented by the general formula (3) are as follows. Chloro (dimethylamino) (trimethylsilyl) borane, bromo (dimethylamino) (trimethylsilyl) borane, iodo (dimethylamino) (trimethylsilyl) borane,
Bis (dimethylamino) (tributylsilyl) borane,
Bis (diethylamino) (trimethylsilyl) borane,
Di-t-butoxy (dimethylphenylsilyl) borane,
4,4,5,5-tetramethyl-2- (dimethylphenylsilyl) -1,3-dioxa-2-boracyclopentane, 4,4,5,5-tetramethyl-2- (triphenylsilyl) ) -1,3-Dioxa-2-boracyclopentane, 2- (triethylsilyl) -1,3-dioxa-
2-boracyclopentane, 2- (dimethylphenylsilyl) -1,3-dioxa-2-boracyclopentane, B
-(Dimethylphenylsilyl) catecholborane, 1,
3-dimethyl-2- (trimethylsilyl) -1,3-diaza-2-boracyclopentane, 1,3-dimethyl-2
-(T-butyldimethylsilyl) -1,3-diaza-2
-Boracyclopentane, 1,3-dimethyl-2- (triphenylsilyl) -1,3-diaza-2-boracyclopentane, 1,3-dimethyl-2- (dimethylphenylsilyl) -1,3-diaza -2-boracyclopentane,
1,3-dimethyl-2- (triphenylsilyl) -1,
3-diaza-2-boracyclohexane and the like. Further, the silylborane compound used in the present invention can be used as it is without purification after synthesis.

The diyne compound used as a reaction raw material in the present invention is represented by the general formula (4). In the general formula (4), R ⁶ and R ⁷ represent a hydrogen atom, an aliphatic group or an aromatic group.

The aliphatic group includes a chain or cyclic alkyl group or alkenyl group. The aliphatic group has 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms. The aliphatic group may have various substituents. Examples of such a substituent include various types containing a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom, for example, an aliphatic oxy group, an aromatic oxy group, a siloxy group, an aliphatic oxycarbonyl group, and an aromatic oxy group. Group oxycarbonyl group, acyl group, amino group, nitro group, cyano group, thionyl group, silyl group, halogen and the like. Specific examples of the aliphatic group include, for example, methyl, ethyl, propyl, butyl, hexyl, octyl, cyclohexylmethyl, trimethylsiloxyhexyl, 2-chloroethyl, dimethylaminomethyl, 5- Hexenyl group, 2,
2-di (ethoxycarbonyl) -4-pentenyl group and the like.

The aromatic group includes both an aromatic group consisting of a carbocyclic ring and an aromatic group consisting of a heterocyclic ring. In this case, examples of the carbon ring include condensed rings such as a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring, in addition to a benzene ring, a biphenyl ring, and a bis (phenyl) alkane. On the other hand, as the heterocycle, a five-membered ring such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazyl; a six-membered ring such as pyran, pyrone, pyridine, pyridazine, pyrimidine, pyrazine; indole, carbazole, coumarin, benzopyrone, And condensed rings such as quinoline, isoquinoline, acridine, phthalazine, quinazirine, and quinolixane.

Specific examples of the aromatic group include a phenyl group, a tolyl group, a naphthyl group, a pyridyl group, a thienyl group, and a furyl group. Also, this aromatic ring is
It may have various substituents. Examples of such a substituent include hydrocarbon groups such as an alkyl group and an alkenyl group, and the various substituents described above for the substituent of the aliphatic group.

In formula (4), R ⁸ represents a substituted or unsubstituted alkylene group which may contain a hetero atom. The alkylene group includes a chain divalent group and a cyclic divalent group, and the hetero atom includes an oxygen atom,
Examples include a nitrogen atom and a sulfur atom.

Further, as a substituent of the alkylene chain,
Aliphatic group, aromatic group, aliphatic oxy group, aromatic oxy group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, acyl group, acyloxy group, amino group, carbamoyl group, nitro group, cyano group, sulfonyl group And a halogen group. Examples of the aliphatic group and the aromatic group in this case include those described above for R ⁶ and R ⁷ .

Examples of the aliphatic oxycarbonyl group and the aromatic oxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a ^t- butyloxycarbonyl group, a benzyloxycarbonyl group and a phenoxycarbonyl group. These aliphatic oxycarbonyl group and aromatic oxycarbonyl group can have various substituents described for the aliphatic group.

Examples of the aliphatic oxy group and the aromatic oxy group include a methoxy group, an ethoxy group, a propoxy group, a benzyloxy group and a phenoxy group. These aliphatic oxy groups and aromatic oxy groups can have various substituents described for the aliphatic groups.

Examples of the acyl group and acyloxy group include an acetyl group, a propionyl group, a benzoyl group, a furoyl group, a nicotinoyl group, an acetyloxy group and a benzoyloxy group. These acyl groups and acyloxy groups can have various substituents described for the aliphatic groups.

Examples of the amino group, carbamoyl group and sulfonyl group include dimethylamino group, dibenzylamino group, dimethylaminocarbonyl group, diphenylaminocarbonyl group, tosyl group and mesyl group.

Further specific examples of the alkylene group include:
Examples having no substituent include a propylene group, a butylene group, a 2-oxapropylene group, a 2-thiapropylene group, an o-dimethylenephenylene group, a 2,3-dimethylenethienylene group, and a 2,3-dimethylene. Furanylene group, 2,3
-Dimethylenepyridylene group, methylenethienylene group, methylenefuranylene group, 1,8-naphthalene group, and the like, and those having a substituent include a 2,2-dimethylpropylene group, a 1-phenylpropylene group, 2,2-di (benzyloxymethyl) propylene group, 2,2-dicyanopropylene group, 2,2-dinitropropylene group, 2,2
-Di (ethoxycarbonyl) propylene group, 2,2-di (butoxycarbonyl) propylene group, 2-tosyl-2
-Azapropylene groups and the like.

Specific examples of the diyne compound represented by the general formula (4) are as follows. 1,6-heptadiyne, 1,7-octadiyne, dipropargyl ether, 1,2-dipropargylbenzene, 2,3-dipropargylthiophene, 1,8-diethynylnaphthalene,
4,4-dimethyl-1,6-heptadiyne, 3-phenyl-1,6-heptadiyne, 4,4-di (benzyloxymethyl) -1,6-heptadiyne, 4,4-dicyano-1,6-heptadiyne , 4,4-dinitro-1,6-
Heptadiyne, 4,4-di (ethoxycarbonyl)-
1,6-heptadiyne, 4,4-di (butoxycarbonyl) -1,6-heptadiyne, dipropargyltosylamide, dimethyldipropargylsilane, 4,4,9,9
-Tetra (ethoxycarbonyl) -1-dodeken-6,
11-diyne and the like.

The eneyne compound used as a reaction raw material in the present invention is represented by the above general formula (5). In the general formula (5), R ⁶ and R ⁷ represent hydrogen, an aliphatic group and an aromatic group, and R ⁸ represents a substituted or unsubstituted alkylene group which may contain a hetero atom. As the aliphatic group, aromatic group and alkylene group in this case, those described for the general formula (4) can be mentioned.

Specific examples of the enyne compound represented by the general formula (5) are as follows. 1-heptene-
6-yne, 1-octen-7-yne, allylpropargyl ether, 1-allyl-2-propargylbenzene,
2-allyl-3-propargylfuran, 3-allyl-2
-Propargylpyridine, 2-vinyl-3-propargylthiophene, 1-vinyl-8-ethynylnaphthalene,
4,4-dimethyl-1-hepten-6-yne, 3-phenyl-1-hepten-6-yne, 4,4-di (benzyloxymethyl) -1-hepten-6-yne, 4,4-dicyano -1-hepten-6-yne, 4,4-dinitro-
1-heptene-6-yne, 4,4-di (ethoxycarbonyl) -1-hepten-6-yne, 4,4-di (butoxycarbonyl) -1-hepten-6-yne, allylpropargyltosylamide, allyl Dimethylpropargylsilane, 4,4-di (ethoxycarbonyl) -1-nonen-6-yne and the like.

The Group 10 metal catalyst used in the present invention includes nickel, palladium, platinum metals, metal complexes or metal salts. Specific examples of these complexes and salts are as follows.

Tetracarbonyl nickel, dicarbonyl bis (triphenylphosphine) nickel, bis (1,
5-cyclooctadiene) nickel, (η ² -ethylene) bis (triethylphosphine) nickel, tetrakis (tricyclohexylphosphine) nickel, dimethylbis (trimethylphosphine) nickel, chloro (η
-Cyclopentadienyl) (triphenylphosphine)
nickel.

Palladium acetate, tetrakis (triphenylphosphine) palladium, tetrakis (trimethylphosphine) palladium, tris (triethylphosphine) palladium, bis (tricyclohexylphosphine) palladium, tetrakis (triethylphosphite)
Palladium, tetrakis (tri phenylene Racing) palladium, (triphenylphosphine) palladium, (Myu2- ethylene) bis (triphenylphosphine) palladium, (mu ² - maleic anhydride) [1,2
-Bis (diphenylphosphino) ethane] palladium, bis (cycloocta-1,5-diene) palladium, tris (dibenzylideneacetone) dipalladium,
Bis (dibenzylideneacetone) palladium, chloro (methyl) (1,5-cyclooctadiene) palladium, diethylbis (triphenylphosphite) palladium, diethylbis (trimethylphosphite) palladium, diethylbis (tri-i-propylphosphite) Palladium, dimethyl [1,2-bis (dimethylphosphino) ethane] palladium, dimethyl [1,3-bis (dimethylphosphino) propane] palladium, dimethyl [1,2-bis (dimethylamino) ethane] palladium, dimethyl Bis (4-ethyl-1-phospha-2,
6,7-trioxabicyclo [2,2,2] octane)
Palladium, bis (t-butylisocyanide) dimethylpalladium bis (1,1,3,3-tetramethylbutylisocyanide) dimethylpalladium diphenylbis (methyldiphenylphosphinite) palladium, dibenzylbis (trimethylphosphine) palladium, diethynylbis (triethylphosphine) Palladium, dineopentyl (2,2′-bipyridyl) palladium, bromo (methyl) bis (triethylphosphine) palladium, benzoyl (chloro) bis (trimethylphosphine) palladium, cyclopentadienyl (phenyl) (triethylphosphine) palladium, η- Allyl (pentamethylcyclopentadienyl) palladium, η-allyl (cyclopentadienyl) palladium, η-allyl (1,5-cyclooctadiene) palladium Supported palladium metals such as radium tetrafluoroborate, bis (η-allyl) palladium, bis (acetylacetonato) palladium, dichloroethylenediaminepalladium, palladium chloride, and palladium carbon.

Metal platinum catalysts such as tetrakis (triphenylphosphine) platinum, tris (triethylphosphine) platinum, bis (1,5-cyclooctadiene) platinum, bis (dibenzylideneacetone) platinum and platinum black.

These Group 10 metal catalysts also include complexes solvated with general-purpose solvents such as tetrahydrofuran and benzene. These catalysts may be used as they are without being purified from those synthesized in the reaction system, or may be used as a mixed catalyst of two or more kinds of catalysts. Further, the above-mentioned complex and various ligands may be mixed in the system and used as they are. For example, tris (dibenzylideneacetone) dipalladium and 4-ethyl-1-phospha-2,6,7-trioxabicyclo [2 , 2,2] octane, tris (dibenzylideneacetone) dipalladium and trimethylphosphine, palladium acetate and 1,1,3,3-tetramethylbutyl isocyanide, μ-allyl (cyclopentane A mixed system of dienyl) palladium and 4-ethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane, μ-allyl (cyclopentadienyl) palladium and 1,1,3 It can also be used as a mixed system of 1,3-tetramethylbutyl iliocyanide. When a catalyst having a phosphorus ligand is used in the catalyst system of this reaction, the equivalent ratio of the catalyst metal atom in the system to the phosphorus atom in the ligand is one metal atom.
On the other hand, the phosphorus atom is preferably 4 or less, more preferably 0.5 to 2.0. As the phosphorus ligand, a sterically small phosphine or phosphite ligand is desirable.

According to the method of the present invention, a 1- (1-borylalkylidene) -2- (1-silylalkylidene) cycloalkane compound represented by the general formula (1) or 1- (1-
To produce a (borylalkylidene) -2- (1-silylalkyl) cycloalkane compound, the compound represented by the general formula (3)
Is reacted with a diyne compound represented by the general formula (4) or an eneyne compound represented by the general formula (5) in the presence of the catalyst. The reaction temperature is 0 to 250 ° C, preferably 50 to 150 ° C.
° C. The ratio of the silyl borane compound to the diyne compound or the enyne compound is not particularly limited, but the silyl borane compound is used in an amount of 0.3 to 3.0 mol, preferably 0.5 to 3.0 mol per mol of the diyne compound or the enyne compound.
The ratio is preferably 2.0 mol. Furthermore, the amount of the catalyst used is 0.000 per mole of the silylborane compound.
The ratio is preferably from 0.1 to 0.1 mol, more preferably from 0.001 to 0.05 mol.

When the above reaction is carried out, a reaction solvent is not necessarily required, but when a solvent is used, aromatic hydrocarbons such as toluene and benzene, ethers such as diethyl ether, dibutyl ether and tetrahydrofuran, acetonitrile, Examples thereof include nitriles such as propionnitrile, and aliphatic saturated hydrocarbons such as pentane, hexane, and decane. Separation of the product after the reaction is easily carried out by ordinary purification and isolation methods such as distillation and recrystallization.

In the present invention, the above-mentioned general formulas (1) and (2)
1- (1-borylalkylidene) -2- represented by
The (1-silylalkylidene) cycloalkane compound and the 1- (1-borylalkylidene) -2- (1-silylalkyl) cycloalkane compound are both novel compounds. 1- (1-borylalkylidene) -2- (1-silylalkylidene) represented by the general formula (1)
Specific examples of the cycloalkane compound are as follows. 1-[(1,3-dimethyl-1,3-diaza-
2-bora-2-cyclopentanyl) methylidene] -2-
[(Dimethylphenylsilyl) methylidene] cyclopentane, 1-[(1,3-dimethyl-1,3-diaza-2)
-Bora-2-cyclopentanyl) methylidene] -2-
[(Triphenylsilyl) methylidene] cyclopentane, 1-[(1,3-dimethyl-1,3-diaza-2-
Bora-2-cyclopentanyl) methylidene] -2-
[(Dimethylphenylsilyl) methylidene] cyclohexane, 4,4-di (ethoxycarbonyl) -1-
[(1,3-dimethyl-1,3-diaza-2-bora-2
-Cyclopentanyl) methylidene] -2-[(trimethylsilyl) methylidene] cyclopentane, 4,4-di (butoxycarbonyl) -1-[(1,3-dimethyl-
1,3-diaza-2-bora-2-cyclopentanyl) methylidene] -2-[(trimethylsilyl) methylidene]
Cyclopentane, 1-[(1,3-dimethyl-1,3-
Diaza-2-bora-2-cyclopentanyl) methylidene] -4-tosyl-2-[(dimethylphenylsilyl)
Methylidene] -4-azacyclopentane, 1-[(1,
3-dimethyl-1,3-diaza-2-bora-2-cyclopentanyl) methylidene] -4-tosyl-2-[(t-
Butyldimethylsilyl) methylidene] -4-azacyclopentane, 1-[(1,3-dimethyl-1,3-diaza-2-bora-2-cyclopentanyl) methylidene] -2
-[(Dimethylphenylsilyl) methylidene] -4-oxacyclopentane, 4,4-di (ethoxycarbonyl) -1-[(1,3-dimethyl-1,3-diaza-2
-Bora-2-cyclopentanyl) methylidene] -2-
[1- (Trimethylsilyl) propylidene] cyclopentane, 4,4-di (ethoxycarbonyl) -1-
[(1,3-dimethyl-1,3-diaza-2-bora-2
-Cyclopentanyl) methylidene] -2- [1- (dimethylphenylsilyl) -3,3-di (ethoxycarbonyl) -5-hexenylidene] cyclopentane, 4,4-
Dimethyl-1- [bromo (dimethylamino) borylmethylidene] -2-[(trimethylsilyl) methylidene] cyclopentane, 4,4-dibenzyloxymethyl-1-
[Iodo (dimethylamino) borylmethylidene] -2-
[(Trimethylsilyl) methylidene] cyclopentane,
4,4-dicyano-1- [bis (dimethylamino) borylmethylidene] -2-[(tributylsilyl) methylidene] cyclopentane, 4,4-dinitro-1- [bis (diethylamino) borylmethylidene] -2-[(trimethylsilyl ) Methylidene] cyclopentane, 1- [bis (dimethylamino) borylmethylidene] -2-[(tributylsilyl) methylidene] acenaphthene, 1- [bis (dimethylamino) borylmethylidene] -2-[(tributylsilyl) methylidene] -1 , 2,3,4-tetrahydronaphthalene, 1-[(1,3-dioxa-2-
Bora-2-cyclopentanyl) methylidene] -2-
[(Triethylsilyl) methylidene] -4-oxacyclopentane, 1-[(4,4,5,5-tetramethyl-
1,3-dioxa-2-bora-2-cyclopentanyl)
Methylidene] -2-[(dimethylphenylsilyl) methylidene] cyclopentane,

Further, 1- represented by the general formula (2)
Specific examples of the (1-borylalkylidene) -2- (1-silylalkyl) cycloalkane compound are as follows. 1-[(1,3-dimethyl-1,3-diaza-2-bora-2-cyclopentanyl) methylidene]-
2-[(dimethylphenylsilyl) methyl] cyclopentane, 1-[(1,3-dimethyl-1,3-diaza-2)
-Bora-2-cyclopentanyl) methylidene] -2-
[(Trimethylsilyl) methyl] cyclohexane, 4,
4-di (ethoxycarbonyl) -1-[(1,3-dimethyl-1,3-diaza-2-bora-2-cyclopentanyl) methylidene] -2-[(dimethylphenylsilyl)
Methyl] cyclopentane, 4,4-di (ethoxycarbonyl) -1-[(1,3-dimethyl-1,3-diaza-
2-bora-2-cyclopentanyl) methylidene] -2-
[(Triphenylsilyl) methyl] cyclopentane,
4,4-di (butoxycarbonyl) -1-[(1,3-
Dimethyl-1,3-diaza-2-bora-2-cyclopentanyl) methylidene] -2-[(trimethylsilyl) methyl] cyclopentane, 1-[(1,3-dimethyl-
1,3-diaza-2-bora-2-cyclopentanyl) methylidene] -4-tosyl-2-[(trimethylsilyl)
Methyl] -4-azacyclopentane, 1-[(1,3-
Dimethyl-1,3-diaza-2-bora-2-cyclopentanyl) methylidene] -4-tosyl-2-[(t-butyldimethylsilyl) methyl] -4-azacyclopentane, 1-[(1, 3-dimethyl-1,3-diaza-2-
Bora-2-cyclopentanyl) methylidene] -2-
[(Trimethylsilyl) methyl-4-oxacyclopentane, 4,4-di (ethoxycarbonyl) -1-
[(1,3-dimethyl-1,3-diaza-2-bora-2
-Cyclopentanyl) methylidene] -2- [1- (trimethylsilyl) propyl] cyclopentane, 4,4-dimethyl-1- [bromo (dimethylamino) borylmethylidene] -2-[(trimethylsilyl) methyl] cyclopentane, , 4-Dibenzyloxymethyl-1- [iodo (dimethylamino) borylmethylidene] -2-[(trimethylsilyl) methyl] cyclopentane, 4,4-dicyano-1- [bis (dimethylamino) borylmethylidene] -2- [ (Tributylsilyl) methyl] cyclopentane, 4,4-dinitro-1- [bis (diethylamino) borylmethylidene] -2-[(trimethylsilyl)
Methyl] cyclopentane, 1- [bis (dimethylamino) borylmethylidene] -2-[(tributylsilyl)
Methyl] acenaphthene, 2- [bis (dimethylamino)
Borylmethylidene] -3-[(tributylsilyl) methyl] -1,2,3,4-tetrahydronaphthalene, 5-
[Bis (dimethylamino) borylmethylidene] -6-
[(Tributylsilyl) methyl] -4,5,6,7-tetrahydrobenzofuran, 7- [bis (dimethylamino) borylmethylidene] -6-[(tributylsilyl)
Methyl] -5,6,7,8-tetrahydroquinone, 4,
4-di (ethoxycarbonyl) -1-[(4,4,5,
5-tetramethyl-1,3-dioxa-2-bora-2-
Cyclopentanyl) methylidene] -2-[(dimethylphenylsilyl) methyl] cyclopentane, 4,4-di (ethoxycarbonyl) -1-[(4,4,5,5-tetramethyl-1,3-dioxa -2-bora-2-cyclopentanyl) methylidene] -2-[(triethylsilyl) methyl] cyclopentane.

[0036]

Next, the present invention will be described more specifically with reference to examples.

Example 1 Tris (dibenzylideneacetone) dipalladium (0.00
5 mmol) and 4-ethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane (0.01 mmol
A solution of l) in benzene (0.2 ml) is heated at 80 degrees for 5 minutes. Then, under a nitrogen atmosphere, 1,6-heptadiyne (0.
3 mmol) and 1,3-dimethyl-2- (dimethylphenylsilyl) -1,3-diaza-2-boracyclopentane (0.2 mmol) and reacting at 110 ° C. for 2 hours. 1-[(1,3-dimethyl-1,
3-Diaza-2-bora-2-cyclopentanyl) methylidene] -2-[(dimethylphenylsilyl) methylidene] cyclopentane (Compound A) was obtained in 84% yield.

Embedded image (In the formula, Me; methyl group, Ph; phenyl group)

Next, the spectrum of Compound A is shown. ^{. bp128-132 ℃ / 2.8x10 -3 mmHg 1} H-NMR (C 6 D 6): δ0.38 (s,
6H, SiCH ₃ ), 1.46-1.68 (m, 2H), 2.31-2.41 (m, 4H),
2.46 (s, 6H, NCH ₃ ), 2.83 (s, 4H, NCH ₂ ), 5.40 (s, 1
H, = CH), 5.62 (s, 1H, = CH), 7.12-7.31 (m, 3H, arom
atic), 7.42-7.60 (m, 2H, aromatic). ¹³ C-NMR (C ₆ D ₆ )
-1.9, 21.3, 34.7, 36.6, 37.7, 51.6,119.4 (broad),
121.9, 127.8, 128.6, 133.8, 141.2, 156.4, 160.7.
²⁹ Si-NMR (C ₆ D ₆ ) -14.1.

Example 2 Tris (dibenzylideneacetone) dipalladium (0.00
5 mmol) and 4-ethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane (0.01 mmol
A solution of l) in benzene (0.2 ml) is heated at 80 degrees for 5 minutes. Thereafter, under a nitrogen atmosphere, 1,7-octadiyne (0.
3 mmol) and 1,3-dimethyl-2- (dimethylphenylsilyl) -1,3-diaza-2-boracyclopentane (0.2 mmol) and reacting at 110 ° C. for 2 hours. 1-[(1,3-dimethyl-1,
3-diaza-2-bora-2-cyclopentanyl) methylidene] -2-[(dimethylphenylsilyl) methylidene] cyclohexane (Compound B) was obtained in 18% yield.

Embedded image (In the formula, Me; methyl group, Ph; phenyl group)

Next, the spectrum of Compound B is shown. ¹ H-NMR (C ₆ D ₆ ): 0.40 and 0.43 (both s, 6H, SiCH ₃ ),
1.45-1.73 (m, 4H), 2.20-2.40 (m, 4H), 2.55 (s, 6
H, NCH ₃ ), 2.83-.297 (m, 4H, NCH ₂ ), 5.30 (s, 1H, = C
H), 5.47 (s, 1H, = CH), 7.05-7.26 (m, 3H, aromati
c), 7.54-7.63 (m, 2H, aromatic). ¹³ C-NMR (C ₆ D ₆ )-
2.2, -1.9, 29.3, 30.0, 34.8, 43.3, 44.6, 51.8, 11
7.6 (broad), 121.3, 127.8, 128.7, 134.0, 141.3, 15
^{7.3, 162.0. 29 Si-NMR} (C 6 D 6) -14.0.

Example 3 Instead of 0.01 mmol of the phosphorus ligand of Example 1, 0.02 mmo
When the reaction is carried out in the same manner using l, 1-[(1,3-dimethyl-1,3-diaza-2-bora-2-cyclopentanyl) methylidene] -2-[(dimethylphenylsilyl) methylidene] Cyclopentane was obtained in 79% yield. The spectrum of the compound obtained was consistent with that obtained in Example 1.

Example 4 The 4-ethyl-1-phospho-2,6,7-trioxabicyclo [2,2,2] octane of Example 1 (0.01 mmo
When the same reaction is carried out using trimethylphosphine (0.02 mmol) instead of l), 1-[(1,3-dimethyl-1,3-diaza-2-bora-2-cyclopentanyl) methylidene] -2-[(dimethylphenylsilyl)
[Methylidene] cyclopentane was obtained in a 25% yield.
The spectrum of the compound obtained was consistent with that obtained in Example 1.

Example 5 Tris (dibenzylideneacetone) dipalladium (0.00
5 mmol) and 4-ethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane (0.02 mmol
A solution of l) in benzene (0.2 ml) is heated at 80 degrees for 5 minutes. Thereafter, under a nitrogen atmosphere, 4,4-di (ethoxycarbonyl) -1-hepten-6-yne (0.22 mmol) and 1,3-dimethyl-2- (dimethylphenylsilyl) -1,3-diaza- 2-boracyclopentane (0.2
mmol) and reacted at 110 ° C. for 2 hours to give 1-[(1,3-dimethyl-1,3-diaza-2-bora-2-cyclopentanyl) methylidene]-represented by the following formula:
2-[(Dimethylphenylsilyl) methyl] cyclopentane (Compound C) was obtained in 84% yield.

Embedded image (In the formula, Me; methyl group, Et; ethyl group, Ph; phenyl group)

Next, the spectrum of compound C is shown. ¹ H-NMR (C ₆ D ₆ ): 0.24 and 0.26 (both s, 6H, SiCH ₃ ),
0.82 (dd, J = 11.9 and 14.6, 1H, SiCH ₂ ), 0.90 and
0.91 (both t, J = 7.1 and 6H, OCH ₂ CH ₃ ), 1.32 (dd, J
= 2.0 and 14.6, 1H, SiCH ₂ ), 1.80-1.93 (m, 1H, C
H ₂ ), 2.50 (s, 6H, NCH ₃ ), 2.74-3.07 (m, 7H, NCH ₂ , CH
₂ , and CH), 3.14 (d, J = 17.5, 1H, CH ₂ ), 3.32 (d, J = 1
7.5, 1H, CH ₂ ), 3.85-4.03 (m, 4H, OCH ₂ CH ₃ ), 5.43
(s, 1H, = CBH), 7.13-7.27 (m, 3H, aromatic), 7.45-
7.53 (m, 2H, aromatic) . 13 C-NMR (C 6 D 6) -2.3, -2.1,
14.0, 23.8, 34.2, 38.7, 42.8, 43.9, 51.7, 59.6, 6
1.1, 115.0 (broad), 128.0, 129.0, 133.8, 139.6, 16
^{0.4, 171.5, 171.6. 29 Si} -NMR (C 6 D 6) -3.5.

Example 6 η-allyl (cyclopentadienyl) palladium (0.01
mmol) and 1,1,3,3-tetramethylbutyl isocyanide (0.02 mmol) in benzene (0.2 ml) under a nitrogen atmosphere under a nitrogen atmosphere.
3-dimethyl-2- (dimethylphenylsilyl) -1,
When 3-diaza-2-boracyclopentane (0.2 mmol) was added and the reaction was carried out at 110 ° C. for 2 hours, 1-[(1,3
-Dimethyl-1,3-diaza-2-bora-2-cyclopentanyl) methylidene] -2-[(dimethylphenylsilyl) methylidene] cyclopentane was obtained in 80% yield. The spectrum of the compound obtained was consistent with that obtained in Example 1.

Example 7 Dipalladium acetate (0.01 mmol) and 1,1,3,3-tetramethylbutyl isocyanide (0.02 mmol) in benzene
(0.2 ml) solution, under a nitrogen atmosphere, 4,4-di (ethoxycarbonyl) -1-hepten-6-yne (0.3 mmol) and 1,3-dimethyl-2- (dimethylphenylsilyl) -1,3. -Diaza-2-boracyclopentane (0.2
mmol) and reacted at 110 ° C. for 2 hours.
[(1,3-dimethyl-1,3-diaza-2-bora-2
-Cyclopentanyl) methylidene] -2-[(dimethylphenylsilyl) methyl] cyclopentane was obtained in 83% yield. The spectrum of the obtained compound was consistent with that obtained in Example 5.

[0047]

According to the present invention, the compound represented by the general formula (1)
-(1-borylalkylidene) -2- (1-silylalkylidene) cycloalkane compound and 1- (1-borylalkylidene) -2 represented by the general formula (2)
The-(1-silylalkyl) cycloalkane compound is a novel compound having a vinylborane structure and a vinylsilane structure or a silyl group, and having a very different reaction activity and being extremely useful as an intermediate in the organic synthesis of drugs and agricultural chemicals. According to the method of the present invention, a silylborane compound is allowed to act on a diyne compound or an eneyne compound in the presence of a catalyst comprising a Group 10 metal, a metal complex or a metal salt thereof, so that silicon and boron can be contained in one molecule. The above (1-borylalkylidene)-having two kinds of metal elements-
2- (1-silylalkylidene) cycloalkane compound or 1- (1-borylalkylidene) -2- (1
(-Silylalkyl) cycloalkane compounds can be advantageously prepared.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI // C07B 61/00 300 C07B 61/00 300 (56) References JP-A-10-114780 (JP, A) JP-A-11-12285 ( JP, A) Organometal. Chem., 15 [26] (1996), 5450-5452. Commun. (13) (1997), 1229-1230. (58) Fields investigated (Int. Cl. ⁷ , DB name) C07F 7/02 C07F 7/08 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (4)

(57) [Claims] [Claim 1] The following general formula (1) (Wherein, R ^1, R ² and R ³ represents an aliphatic group or an aromatic group, R ⁴ and R ⁵ represents a halogen atom, an alkoxy group, an aryloxy group or an amino group, R ⁴ and R ^{When 5} represents an alkoxy group, an aryloxy group or an amino group, R ⁴ and R ⁵ may combine to form a ring, and R ⁶ and R ⁷ represent a hydrogen atom, an aliphatic group or an aromatic group. And R ⁸ represents a substituted or unsubstituted alkylene group which may contain a hetero element.) 1- (1-borylalkylidene) -2- (1-silylalkylidene) cycloalkane compound . 2. The following general formula (2): (Wherein, R ^1, R ² and R ³ represents an aliphatic group or an aromatic group, R ⁴ and R ⁵ represents a halogen atom, an alkoxy group, an aryloxy group or an amino group, R ⁴ and R ^{When 5} represents an alkoxy group, an aryloxy group or an amino group, R ⁴ and R ⁵ may combine to form a ring, and R ⁶ and R ⁷ represent a hydrogen atom, an aliphatic group or an aromatic group. And R ⁸ represents a substituted or unsubstituted alkylene group which may contain a hetero element.) 1- (1-borylalkylidene) -2- (1-silylalkyl) cycloalkane compound . 3. The following general formula (3):¹R^TwoR^ThreeSi-BR^FourR^Five(3) (where R¹, R^TwoAnd R^ThreeIs an aliphatic group or an aromatic group
R represents a group^FourAnd R^FiveIs a halogen atom, alkoxy
Group, an aryloxy group or an amino group;^FourAnd
And R^FiveIs an alkoxy group, an aryloxy group or an amino
When representing a group, R^FourAnd R^FiveIs bonded to form a ring
May be. ) And a silylborane compound represented by the following:
General formula (4)⁶-C≡CR⁸-C≡CR⁷(4) (where R⁶And R⁷Represents a hydrogen atom, an aliphatic group or
Represents an aromatic group;⁸May contain a hetero element
Represents a substituted or unsubstituted alkylene group. )
The diyne compound may be a Group 10 metal, its metal complex or gold.
Reaction in the presence of a catalyst consisting of
The following general formula (1)(Where R¹, R^TwoAnd R^ThreeIs an aliphatic group or an aromatic group
R represents a group^FourAnd R ^FiveIs a halogen atom, alkoxy
Group, an aryloxy group or an amino group;^FourAnd
And R^FiveRepresents an alkoxy group or an amino group,^FourYou
And R^FiveMay be bonded to form a ring;⁶And
And R⁷Represents a hydrogen atom, an aliphatic group or an aromatic group,
R⁸Is substituted or unsubstituted which may contain a hetero element
Represents a substituted alkylene group. 1)-(1-Bol
Rualkylidene) -2- (1-silylalkylidene) si
Isolating a chloroalkane compound;
(1-borylalkylidene) -2- (1-silylalkyl
Riden) A method for producing a cycloalkane compound. 4. A compound represented by the following general formula (3): R ¹ R ² R ³ Si—BR ⁴ R ⁵ (3) wherein R ¹ , R ² and R ³ are an aliphatic group or an aromatic group. R ⁴ and R ⁵ represent a halogen atom, an alkoxy group, an aryloxy group or an amino group; and when R ⁴ and R ⁵ represent an alkoxy group, an aryloxy group or an amino group, R ⁴ and R ⁵ May be bonded to form a ring.) And a silylborane compound represented by the following general formula (5): R ⁶ —CH ＝ CH—R ⁸ —C≡C—R ⁷ ( 5) (wherein, R ⁶ and R ⁷ represent a hydrogen atom, an aliphatic group or an aromatic group, and R ⁸ represents a substituted or unsubstituted alkylene group which may contain a hetero element). The enyne compound represented is reacted in the presence of a catalyst comprising a Group 10 metal, a metal complex or a metal salt thereof, And then the resulting general formula (2): (Wherein, R ^1, R ² and R ³ represents an aliphatic group or an aromatic group, R ⁴ and R ⁵ represents a halogen atom, an alkoxy group, an aryloxy group or an amino group, R ⁴ and R ^{When 5} represents an alkoxy group, an aryloxy group or an amino group, R ⁴ and R ⁵ may combine to form a ring, and R ⁶ and R ⁷ represent a hydrogen atom, an aliphatic group or an aromatic group. And R ⁸ represents a substituted or unsubstituted alkylene group which may contain a hetero element.) 1- (1-borylalkylidene) -2- (1-silylalkyl) cycloalkane compound Wherein the 1- (1-borylalkylidene) -2- (1
-Silylalkylidene) a process for producing a cycloalkane compound.