JP2863838B2 - (4-stannyl-2-alkene-1-yl) borane compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to (4-stannyl-
2-alkene-1-yl) borane compound and a method for producing the same. This (4-stannyl-2-alkene-1-yl) borane compound has a tin carbon and boron carbon bond having completely different reactivities in the molecule, and is a very useful compound as an organic synthesis reagent. A specific example of the use of the compound having an allyl-position carbon-tin bond obtained by this reaction is as follows.When a palladium complex is used as a catalyst, the aryl halide, allyl acetate, vinyl triflate, etc. The efficient progress of the ring reaction (eg, Synthesis, 803-81)
5 pages, 1992, Angew.Chem., Int.Ed.Engl., 25
Vol., Pp. 508-524, 1986), and the use of a rhodium complex as a catalyst to react with acid chloride to produce allyl nyl ketone in good yield (for example, J. Organomet. Ch.
em. Journal, Vol. 129, C36, 1997), and that the allylation of carbonyl compounds proceeds diastereoselectively by using a Lewis acid catalyst (for example, Acc. Che.
m.Res. Journal, Vol. 20, p. 243, 1987, “Organic Chemistry of Hetero Elements-How to Use Their Properties (Chemical Special Issue 11)
5) "Chemistry Dojin, p. 137, 1988). On the other hand, a boryl group can be easily converted to a hydroxyl group by oxidative hydrolysis (for example, Tetrahed
ron, Vol. 37, p. 3547, 1981), and further reports that compounds having an allylborane structure react in a highly stereoselective manner with aldehydes and ketones in the absence of a catalyst to produce alkoxyboranes in high yields. Allyl alcohol can be easily synthesized by hydrolyzing this product (for example, Angew. Chem., Int. Ed. Engl., Vol. 21,
555, 1982, Heterocycle, 18, 357, 1982, Synthesis, 973, 1982).

[0002]

2. Description of the Related Art Conventionally, (4-stannyl-2-alkene-1)
-Yl) silane compound (J. Am. Chem. Soc., 113, 93
68-9369, 1991), (4-silyl-2-alkene-1-yl) silane compounds (Organometallics, 11
Vol. 2353-2355, 1992), etc.
All have only the same group 14 silicon and tin atoms (allyl silane structure, allyl stannane structure),
In order to increase the difference in reactivity, it has been desired to provide a compound having atoms belonging to different groups in its structure.

[0003]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention provides a group 14 tin atom having completely different reactivity.
An object is to provide an (4-stannyl-2-alkene-1-yl) borane compound having an allylstannane structure or a borylstannane structure in which a boron atom of Group 13 is bonded to an allylic carbon, and an advantageous production method thereof.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have found that a 1,3-diene compound reacts with a stannyl borane compound in the presence of a Group 10 transition metal catalyst. (4-stanyl-2
-Alken-1-yl) borane compound was found to be efficiently obtained, and the present invention was completed. That is,
According to the present invention, the following general formula (1)

[0005]

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Wherein R ¹ , R ² , R ³ and R ⁴ are
A hydrogen atom, an aliphatic group, an aromatic group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic oxy group, an aromatic oxy group, a silyloxy group or a silyl group,
When R ¹ , R ² , R ³ and R ⁴ represent a group other than a hydrogen atom, ^{two of} R ¹ , R ² , R ³ and R ⁴ may be bonded to form a ring; ⁵ , R ⁶ and R ⁷ are
An aliphatic group or an aromatic group; R ⁸ and R ⁹ represent a halogen atom or an amino group; and when R ⁸ and R ⁹ represent an amino group, R ⁸ and R ⁹ are combined to form a ring (4-stannyl-2-alkene-1-yl) borane compound represented by the formula: further,
According to the present invention, in order to produce the (4-stannyl-2-alkene-1-yl) borane compound represented by the general formula (1), the following general formula (2)

[0007]

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Wherein R ¹ , R ² , R ³ and R ⁴ are
A hydrogen atom, an aliphatic group, an aromatic group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic oxy group, an aromatic oxy group, a silyloxy group or a silyl group,
When R ¹ , R ² , R ³ and R ⁴ represent a group other than a hydrogen atom, ^{two of} R ¹ , R ² , R ³ and R ⁴ may combine to form a ring) A 1,3-diene compound represented by the following general formula (3)

[0009]

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(Wherein R ⁵ , R ⁶ and R ⁷ represent an aliphatic group or an aromatic group, R ⁸ and R ⁹ represent a halogen atom or an amino group, and R ⁸ and R ⁹ represent an amino group Wherein R ⁸ and R ⁹ may combine to form a ring) in the presence of a catalyst comprising a Group 10 metal, a metal complex or a metal salt thereof. Provided.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by the general formula (1) is obtained by reacting the compound represented by the general formula (2) with the compound represented by the general formula (3). In the 1,3-diene compound represented by the general formula (2), R
¹ , R ² , R ³ and R ⁴ are a hydrogen atom, an aliphatic group, an aromatic group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic oxy group, an aromatic oxy group, a silyloxy group or a silyl group. Is shown. The aliphatic group is a chain or cyclic alkyl group or alkenyl group having 1 carbon atom.
-18, preferably 1-12, more preferably 1-5 lower alkyl or alkenyl groups. The aliphatic group may have various substituents. As such a substituent, in addition to a hydrocarbon group such as an aryl group, various groups containing a hetero atom to an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, etc., for example, an aliphatic oxy group, an aromatic Examples include an oxy group, a silyloxy group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, a dialkylamino group, an alkylthio group, a silyl group, and a halogen atom. Specific examples of the aliphatic group include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group,
Octyl, cyclohexyl, 3-butenyl, 2-
Pentenyl group, benzyl group, 3- (benzyloxy) propyl group, 4- (phenoxy) cyclohexyl group, trimethylsiloxyhexyl group, 2-chloroethyl group, dimethylaminomethyl group, 3- (dimethylphenylsilyl)
Butyl group and the like.

The aromatic group includes both an aryl group composed of a carbocyclic ring and an aromatic group composed of a heterocyclic ring. In this case, the carbon ring preferably has 6 to 18, more preferably 6 to 12, and particularly preferably 6 to 12 carbon atoms.
And condensed rings such as a naphthalene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring and an azulene ring in addition to a benzene ring and a biphenyl ring. On the other hand, such a heterocyclic ring is preferably a 5- or 6-membered ring, and a furan ring, a pyrrole ring, a thiophene ring,
5-membered ring such as pyrazole ring, imidazole ring, oxazole ring, thiazole ring; 6-membered ring such as pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring; benzofuran ring, indole ring, benzothiazole ring, purine ring, Examples thereof include condensed rings such as a quinoline ring, an isoquinoline ring, a quinoxaline ring, a dibenzofuran ring, a carbazole ring and an acridine ring. The aromatic group may have various substituents. Such substituents include
In addition to the hydrocarbon group, various substituents described for the aliphatic group are exemplified. Specific examples of the aromatic group include a phenyl group, a tolyl group, a naphthyl group, a dimethylaminophenyl group, a pyridyl group, and a quinoxalinyl group.

The aliphatic oxycarbonyl group preferably has 2 to 18, more preferably 2 to 12, carbon atoms.
Particularly preferred are those having 2 to 6, and the aromatic oxycarbonyl group preferably has 7 to 18, more preferably 7 to 12, and particularly preferably 7 to 8 carbon atoms. Examples thereof include an alkoxycarbonyl or aryloxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a phenoxycarbonyl group, a benzyloxycarbonyl group, and a butyroxycarbonyl group. These aliphatic oxycarbonyl group and aromatic oxycarbonyl group can have various substituents described for the aliphatic group and the aromatic group.

The aliphatic oxy group preferably has 1 to 18, more preferably 1 to 12, particularly preferably 1 to 6, and the aromatic oxy group preferably has 1 to 6 carbon atoms. 7 to 18, more preferably 7 to 12,
Particularly preferred are those having 7 to 9, and specific examples thereof include alkoxy or aryloxy groups such as methoxy group, ethoxy group, butyloxy group, phenoxy group, naphthyloxy group and benzyloxy group. These aliphatic oxy groups and aromatic oxy groups can have various substituents described for the aliphatic groups and aromatic groups. Silyloxy groups include aliphatic groups, aromatic groups,
A silyloxy group substituted by an aliphatic oxy group or an aromatic oxy group is included. In this case, examples of the aliphatic group and the aromatic group include those described above. Specific examples of the silyloxy group include a trimethylsilyloxy group,
Examples include a triphenylsilyloxy group and a t-butyldimethylsilyloxy group.

The silyl group includes an aliphatic group, an aromatic group, a silyl group substituted with an aliphatic oxy group or an aromatic oxy group. In this case, as the aliphatic group or the aromatic group,
The various things mentioned above are mentioned. Specific examples of the substituted silyl group include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a phenyldimethylsilyl group, a butyldimethylsilyl group, a trimethoxysilyl group,
Examples include a triethoxysilyl group, a triphenoxysilyl group, a phenoxysimethoxysilyl group, and a butoxydimethoxysilyl group.

When R ¹ , R ² , R ³ and R ⁴ represent a group other than a hydrogen atom, ^{two of} R ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. it can. Such a ring is an aliphatic 5-18 membered ring, more preferably a 5 to 18 membered ring.
A ring having 10 to 10 members and further substituted by itself, and a ring containing a hetero element such as nitrogen, oxygen, silicon, phosphorus, and sulfur are included. Specific examples thereof include a dimethylene group, a trimethylene group, a tetramethylene group, a dimethylsilylene group, and a malonyl group.

Specific examples of the 1,3-diene compound represented by the general formula (2) are as follows.
Butadiene, isoprene, 1,3-pentadiene, 2-
Phenylbutadiene, 2,3-dimethylbutadiene,
3,5-decadiene, 1,3,7-octatriene, 2
-Trimethylsiloxy-1,3-butadiene, dimethyl muconate, cyclopentadiene, 1,3-cyclohexadiene, 1-methylidene-2-cyclohexene, 1-vinyl-1-cyclohexene, 1,2-dimethylidenecyclopentane, furan , N-trimethylsilylpyrrole,
Thiophene, 1,1-dimethylsila-2,4-cyclopentadiene, 1,4-dioxo-5-oxa-2,3-
Dimethylidenecyclopentane and the like.

In the general formula (3), which represents a stannylborane compound used as a reaction raw material in the present invention, R ⁵ , R ^5
6 and R ⁷ represents an aliphatic group or an aromatic group, R ⁸
And R ⁹ represent a halogen atom or an amino group. The stannyl borane compound shown here is a compound which can be easily obtained by reacting a stannyl lithium compound with a haloborane compound (for example, J. Org. Chem., 52
Vol. 297-306, 1973, Chem. Ber.
3056-3062, 1981). In this case, the aliphatic group has preferably 1 to 18, more preferably 1 to 1 carbon atoms.
2, particularly preferably 1 to 6, and the aromatic group preferably has 6 to 18 carbon atoms, more preferably 6 to 1 carbon atom.
2, particularly preferably 6 to 8, for example, an alkyl group or an aryl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a phenyl group. Examples of the halogen atom include chlorine, bromine and iodine. Amino groups include substituted and unsubstituted amino groups. The substituted amino group includes an amino group substituted with an aliphatic group or an aromatic group. In this case, examples of the aliphatic group and the aromatic group include those described above. Specific examples of the amino group include a dimethylamino group, a diethylamino group, a diphenylamino group, a dibenzylamino group and the like. When R ⁸ and R ⁹ represent an amino group, R ⁸ and R ⁹ can combine to form a ring with a boron atom. The ring thus formed is a ring having a boron atom and at least two nitrogen atoms, preferably a 5- to 7-membered ring. The amino group forming such a ring includes aliphatic and aromatic divalent amino groups. As a specific example, N, N '
A phenylenediamino group and a xylylenediamino group in addition to alkylenediamino groups such as -dimethyldimethylenediamino group, N, N'-dimethyltrimethylenediamino group and cyclohexylenediamino group.

Specific examples of the stannyl borane compound represented by the general formula (3) are as follows. Chloro (dimethylamino) (trimethylstannyl) borane, bromo (dimethylamino) (trimethylstannyl) borane, iodo (dimethylamino) (trimethylstannyl)
Borane, bis (dimethylamino) (tributylstannyl) borane, bis (diethylamino) (trimethylstannyl) borane, 1,3-dimethyl-2- (trimethylstannyl) -1,3-diaza-2-boracyclopentane ,
1,3-dimethyl-2- (triphenylstannyl)-
1,3-diaza-2-boracyclohexane and the like. The reaction between the compound of the general formula (2) and the compound of the general formula (3) is represented by R ^{1 to} R ⁴ ,
When R ^{5 to} R ⁷ are a group containing an aliphatic group or an aromatic group, the desired compound represented by the general formula (1) can be obtained irrespective of its carbon number. In addition, the stannyl borane compound used in the present invention can be used without purification after synthesis.

In the present invention, a catalyst comprising a Group 10 metal, a metal complex thereof or a metal salt thereof is used. Group 10 metals used for this catalyst are, for example, palladium and platinum, and specific examples of this catalyst are as follows. Supported palladium metal such as palladium carbon, palladium acetate dichlorobis (benzonitrile) palladium,
Dichlorobis [4-ethyl-2,6,7-trioxa-
1-phosphabicyclo (2.2.2) octane] palladium, dichloro (1,5-cyclooctadiene) palladium, dibromobis (dimethylphenylphosphine)
Palladium, dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium, diiodo [1,4
-Bis (dimethylphosphino) butane], di-μ-chloro-dichlorobis (isocyanide) dipalladium, di-
μ-chloro-dichlorobis (triphenylphosphine)) palladium, dichloro-μ-bis [bis (diphenylphosphino) methane] dipalladium, bis (tricyclohexylphosphine) palladium, carbonyltris (triphenylphosphine) palladium, (η ² −
Ethylene) bis (triphenylphosphine) palladium, bis (cycloocta-1,5-diene) palladium, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, chloro (methyl) (1,5-cyclooctane) Diene) palladium, dimethyl [1,2-bis (dimethylphosphino) ethane] palladium, dimethyl [1,3-bis (dimethylphosphino) propane] palladium, dimethyl [1,2
-Bis (dimethylamino) ethane] palladium, dimethylbis (1-phospha-2,6,7-oxobicyclo [2.2.2] octane) palladium, diphenylbis (methyldiphenylphosphinito) 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, eta ³ - allyl (pentamethylcyclopentadienyl) palladium, eta ³ - allyl (1,5-cyclooctadiene Palladium tetrafluoroborate, bis (η ³ -allyl) palladium, bis (acetylacetonato) palladium, dichloroethylenediaminepalladium, palladium chloride. Dichlorobis (acetonitrile) platinum, bis (1,5-cyclooctadiene) platinum, bis (dibenzylideneacetone) platinum and the like.

These Group 10 metal catalysts also include complexes solvated with general-purpose solvents such as tetrahydrofuran and benzene. These catalysts may be used directly without purification in a reaction system. Further, these catalysts can be used as a mixed catalyst of two or more kinds, or as a mixed catalyst with the ligand used in the complex. When a phosphorus ligand is used in the reaction catalyst system, the equivalent ratio of the metal atom to the phosphorus atom is preferably 0 to 3 phosphorus atoms, preferably 0.5 to 2.5, relative to 1 metal atom.

In order to produce the (4-stannyl-2-alkene-1-yl) borane compound of the general formula (1) according to the present invention, the 1,3-diene compound of the general formula (2) and the general formula The stannylborane compound of (3) is reacted in the presence of the catalyst. The reaction temperature is from 20 to 250C, preferably from 60 to 150C. The reaction time is 1 to 50 hours. The amount ratio of the 1,3-diene compound to the stannyl borane compound is not particularly limited, but the ratio of the 1,3-diene compound is preferably 1 to 10 mol, preferably 2 to 6 mol per mol of the stannyl borane compound. The amount of the catalyst used is 0.0000 per mole of the stannyl borane compound.
The ratio is preferably 1 to 0.3 mol, more preferably 0.001 to 0.1 mol. When carrying out the reaction, 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 and propionitrile And the like. Separation of the product after the reaction is easily carried out by ordinary purification and isolation methods such as distillation and recrystallization.

According to the method of the present invention, the general formula (1)
(4-stannyl-2-alkene-1-yl) borane compound is obtained. In the general formula (1), R ^{1 to} R ⁴ are preferably an alkyl group, a phenyl group or a hydrogen atom, and more preferably R ^{1 to} R ^4.
One of R ¹ and R ⁴ is a hydrogen atom. R ^{5 to} R ⁷ are
It is an alkyl group or a phenyl group. R ^8, R ⁹ is an amino group or a halogen atom, 5 attached R ⁸ and R ⁹
It forms a 7-membered nitrogen-containing heterocycle. Specific examples of the (4-stannyl-2-alkene-1-yl) borane compound represented by the general formula (1) are as follows.
1,3-dimethyl-2- [4- (trimethylstannyl)
-2-buten-1-yl] -1,3-diaza-2-boracyclopentane, 1,3-dimethyl-2- [4- (trimethylstannyl) -3- (trimethylsilyloxy)-
2-buten-1-yl] -1,3-diaza-2-boracyclopentane, 1,3-dimethyl-2- [3-methyl-
4- (trimethylstannyl) -2-buten-1-yl]
-1,3-diaza-2-boracyclopentane, 1,3-
Dimethyl-2- [4- (trimethylstannyl) -2-penten-1-yl] -1,3-diaza-2-boracyclopentane, 1,3-dimethyl-2- [3-phenyl-4
-(Triphenylstannyl) -2-buten-1-yl]
-1,3-diaza-2-boracyclohexane, 1,3-
Dimethyl-2- [2,3-dimethyl-4- (trimethylstannyl) -2-buten-1-yl] -1,3-diaza-2-boracyclopentane, [1-butyl-4- (trimethylstannyl) Nyl) -2-hexen-1-yl] (dimethylamino) chloroborane, dimethyl 2- [bromo (dimethylamino) boryl] -5-trimethylstannyl-3
-Hexendioate 1- [iodo (dimethylamino)
Boryl] -4-trimethylstannyl-2-cyclopentene, 1,3-dimethyl-2- [4- (trimethylstannyl) -2-cyclohexen-1-yl] -1,3-diaza-2-boracyclopentane , 1- [bis (dimethylamino) borylmethyl] -3- (tributylstannyl)-
1-cyclohexene, 1- [2-bis (dimethylamino) borylethylidene] -2- (tributylstannyl)
Cyclohexane, 1- [bis (diethylamino) borylmethyl] -2-trimethylstannylmethyl-1-cyclopentene, 1,3-dimethyl-2- [4- (trimethylstannyl) -2-oxa-4-cyclopentene-1- Yl] -1,3-diaza-2-boracyclopentane, 2-
[Bis (diethylamino) boryl] -5-trimethylstannyl-1-trimethylsilyl-1-aza-3-cyclopentene, 2- [bis (diethylamino) boryl] -5
-Trimethylstannyl-1-thia-3-cyclopentene, 2- [bis (diethylamino) boryl] -5-trimethylstannyl-1,1-dimethyl-1-sila-3-cyclopentene, 2- [bis (diethylamino) Borylmethyl] -3- (trimethylstannylmethyl) maleic anhydride and the like.

[0024]

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

Example 1 Dichlorobis (benzonitrile) palladium (0.01 mmo
l) and 4-ethyl-2,6,7-trioxa-1-phosphabicyclo (2.2.2) octane (0.02 mmol)
Of tetrahydrofuran (0.5 ml) in a nitrogen atmosphere
Stir at 0 ° for 5 minutes, at room temperature isoprene (1 mmol) and 1,3-dimethyl-2- (trimethylstannyl)-
1,3-diaza-2-boracyclopentane (0.2 mmol)
Was added and the reaction was carried out at 80 ° C. for 1 hour, to give 1,3-dimethyl-2- [3-methyl-4- (trimethylstannyl) -2-buten-1-yl] -1, represented by the following formula: 3-
Diaza-2-boracyclopentane (Compound A) yield 8
Obtained at 1%.

[0026]

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Next, the spectrum of Compound A is shown. ¹ H-NMR (C ₆ D ₆ ): δ 0.14 (s, J _HSn = 52.2 Hz, 9H, SnM
e ₃ ), 1.60 (d, J = 7.7 Hz, 2H, BCH ₂ ), 1.68 (d, J =
1.2 Hz, J _HSn = 12.0 Hz, 3H, CCH ₂ ), 1.83 (s, J _HSn =
67.8 Hz, 2H, SnCH ₂ ), 2.62 (s, 6H, NMe), 2.97 (s,
4H, NCH ₂ ), 5.20 (t, J = 7.7 Hz, 1H, CH); ¹³ C-NMR (C
₆ D ₆ ): δ-9.33, 11.8, 17.6, 26.0, 34.0, 51.6, 117.
2, 132.8

Example 2 When the reaction was carried out using benzene in place of tetrahydrofuran in Example 1, 1,3-dimethyl-2-
[3-Methyl-4- (trimethylstannyl) -2-buten-1-yl] -1,3-diaza-2-boracyclopentane (Compound A) was obtained in a yield of 37%. The spectrum of the compound obtained was consistent with that obtained in Example 1.

Example 3 The reaction was carried out in the same manner as in Example 1 except that tris (dibenzylideneacetone) dipalladium (0.005 mmol) was used instead of dichlorobis (benzonitrile) palladium (0.01 mmol). Dimethyl-2- [3-methyl-
4- (trimethylstannyl) -2-buten-1-yl]
-1,3-Diaza-2-boracyclopentane (Compound A) was obtained in a yield of 83%. The spectrum of the compound obtained was consistent with that obtained in Example 1.

Example 4 Tris (dibenzylideneacetone) dipalladium (0.00
5 mmol) and 4-ethyl-2,6,7-trioxa-1-
Phosphabicyclo (2, 2, 2) octane (0.02 mmo
l) in tetrahydrofuran (0.5 ml) is stirred at 80 ° C for 5 minutes under a nitrogen atmosphere, and at room temperature 2,3-dimethylbutadiene (1 mmol) and 1,3-dimethyl-2- (trimethylstannyl) -1, By adding 3-diaza-2-boracyclopentane (0.2 mmol) and performing a reaction at 80 ° C. for 3 hours, 1,3-dimethyl-2- [4
-(Trimethylstannyl) -2,3-dimethyl-2-buten-1-yl] -1,3-diaza-2-boracyclopentane (Compound B) was obtained in high yield.

[0031]

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Next, the spectrum of Compound B is shown. ¹ HNMR (C ₆ D ₆ ) 0.15 (S, J _HSn = 51.6 Hz, 9H, SnCH ₃ ), 1.66 (s, 3H,
CCH ₃ ), 1.72 (s, 2H, BCH ₂ ), 1.78 (s, 3H, CCH ₃ ), 1.88
(s, 2H, SnCH ₂ ), 2.62 (s, 6H, NCH ₃ ), 2.99 (s, 4H, NC
H ₂ ), ¹³ C NMR (C ₆ D ₆ ) -9.2 (J _CSn = 308 Hz, SnCH ₃ ), 19.3 (broad, BCH ₂ ), 20.7
(J _CSn = 320Hz, SnCH ₂ ), 20.9 (CCH ₃ ), 33.8 (NCH ₃ ), 51.7
(NCH ₂ ), 122.0 (C = C), 124.9 (C = C).

Example 5 When butadiene was used in place of 2,3-dimethylbutadiene in Example 4 to carry out the same reaction, 1,3-dimethyl-2- [4- (trimethylsta Nyl) -2-buten-1-yl] -1,3-diaza-2-
Boracyclopentane (Compound C) was obtained with a yield of 87%.

[0034]

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Next, the boiling point and spectrum of Compound C are shown. Bp.85 ° C / 1.5 × 10 ^-3 mmHg; ¹ HNMR (C ₆ D ₆ ) 0.13 (S, J _HSn = 52.6 Hz, 9H, SnCH ₃ ), 1.70 (d, J =
7.5Hz, 2H, BCH ₂ ), 1.84 (d, J = 8.7Hz, 2H, SnCH ₂ ),
2.62 (s, 6H, NCH ₃ ), 2.96 (s, 4H, NCH ₂ ), 5.47 (td, J =
7.5, 10.4Hz, C = CH) , 5.59 (td, J = 8.7, 10.4Hz, C = CH), 13 CNMR (C 6 D 6) -9.9 (J CSn = 318Hz, SnCH 3), 10.9 (broad, BCH ₂ ), 12.4
(J _CSn = 312Hz, SnCH ₂ ), 34.0 (NCH ₃ ), 51.6 (NCH ₂ ), 126.
0 (C = C), 128.2 (C = C).

[0036]

According to the method of the present invention, a Group 10 metal,
In the presence of a catalyst comprising the metal complex or the metal salt,
A (4-stannyl-2-alkene-1-yl) borane compound useful as an organic synthesis reagent having an allylstannane structure and an allylborane structure in a molecule is easily produced from a 1,3-diene compound and a stannylborane compound under mild conditions. can do.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Masato Tanaka 1-1-1, Higashi, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (56) References JP-A-9-241272 (JP, A) ONAZAWA, S . , Et. a l. , Organometallics, Vol. 15, No. 26, 1996, p5450-5452 (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 7/22 CAPLUS (STN) REGISTRY (STN) WPI (DIALOG)

Claims (2)

(57) [Claims] [Claim 1] The following general formula (1) (Wherein R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, an aliphatic group, an aromatic group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic oxy group, an aromatic oxy group, shows the silyloxy group or a silyl group, R ^1, R
^{When 2} , R ³ and R ⁴ represent a group other than a hydrogen atom, R ¹
, Two of R ^2, R ³ and R ⁴ may form a ring, R ^5, R ⁶ and R ⁷ represents an aliphatic group or an aromatic group, R ⁸ and R ⁹ represents a halogen atom or an amino group, and when R ⁸ and R ⁹ represent an amino group, R ⁸ and R ⁹ may combine to form a ring) (4-stannyl-2) -Alkene-1
-Yl) borane compounds. 2. The following general formula (1): (Wherein R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, an aliphatic group, an aromatic group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic oxy group, an aromatic oxy group, shows the silyloxy group or a silyl group, R ^1, R
^{When 2} , R ³ and R ⁴ represent a group other than a hydrogen atom, R ¹
, Two of R ^2, R ³ and R ⁴ may form a ring, R ^5, R ⁶ and R ⁷ represents an aliphatic group or an aromatic group, R ⁸ and R ⁹ represents a halogen atom or an amino group, and when R ⁸ and R ⁹ represent an amino group, R ⁸ and R ⁹ may combine to form a ring) (4-stannyl-2) -Alkene-1
-Yl) borane compound in a method for producing the same, which is represented by the following general formula (2): (Wherein R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, an aliphatic group, an aromatic group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic oxy group, an aromatic oxy group, shows the silyloxy group or a silyl group, R ^1, R
^{When 2} , R ³ and R ⁴ represent a group other than a hydrogen atom, R ¹
, R ² , R ³ and R ⁴ may be bonded to form a ring), and a 1,3-diene compound represented by the following general formula (3): (Wherein R ⁵ , R ⁶ and R ⁷ represent an aliphatic group or an aromatic group, R ⁸ and R ⁹ represent a halogen atom or an amino group, and R ⁸ and R ⁹ represent an amino group ,
R ⁸ and R ⁹ may combine to form a ring) in the presence of a catalyst comprising a Group 10 metal, a metal complex thereof or a metal salt thereof. The method.