CN106117257A - A kind of method synthesizing α boryl silane compound - Google Patents

A kind of method synthesizing α boryl silane compound Download PDF

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CN106117257A
CN106117257A CN201610428311.7A CN201610428311A CN106117257A CN 106117257 A CN106117257 A CN 106117257A CN 201610428311 A CN201610428311 A CN 201610428311A CN 106117257 A CN106117257 A CN 106117257A
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boryl
synthesis
silane
silane compound
alkynes
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CN106117257B (en
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陆展
郭军
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages

Abstract

This method discloses a kind of method of speed synthesis α boryl silane compound.With alkynes as raw material, with silane for silicon source, with borine as boron source, with CoX2OIP complex is catalyst, in the presence of sodium triethylborohydride, at a temperature of 30 DEG C～80 DEG C, reacts 30 minutes～4 hours prepared alkenyl silanes, described alkynes, silane, borine, CoCl2OIP complex, the mol ratio of sodium triethylborohydride are 1:1:1.2:0.0005 0.05:0.0015 0.15；Compared with the conventional method, the method is applicable to the alkynes of number of different types, and reaction condition is gentle, easy and simple to handle, Atom economy 100%.It addition, reaction is without the addition of other any poisonous transition metal (such as ruthenium, rhodium, palladium etc.) salts, pharmaceutical synthesis has bigger actual application value.And functional group's tolerance of reaction is good, regioselectivity is the highest, generally > 20:1.

Description

A kind of method synthesizing α-boryl silane compound
Technical field
This method relates to a kind of compou nd synthesis method, specifically, is a kind of high regioselectivity Fast back-projection algorithm α-boron The method of base silane compounds.
Background technology
The α of quarternary structure-boryl silane compound is the synthesis unit that a class is important, and he is possible not only to and nucleopilic reagent Effect builds has the biggest challenging level Four allyl silicane compounds [a) Org.Lett.2011,13,1490.], also Level Four silane compound [a) Chem.Eur.J.2011,17,13124.] can be built by Suzuki coupling reaction, and And through level Four alcohol [a) J.Org.Chem.1997,621112.] can be obtained further across Fleming-Kumada oxidation. The α of quarternary structure-boryl silane compound can obtain many complete substituted carbon center compound through a series of conversion. But, building with carbon boryl silane compound is that comparison is challenging.The hydroboration that H.C.Brown leads is not Can well should be used for build same carbon level Four boryl silane compound because when boron ester to double bond addition when, boron ester is more Tendency add to the little one end of steric hindrance generate anti-geneva product [a) J.Am.Chem.Soc.1964,86,393.b) J.Am.Chem.Soc.1964,86,397.].Framework is carried out same by the silicon hydrogenation/hydroboration of cheap metal catalysis one kettle way alkynes Carbon boryl silane is significantly.
The present invention is successfully realized same carbon boryl silane by cheap metal cobalt catalysis one kettle way alkynes silicon hydrogenation/hydroboration The structure of compounds.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of method of effective synthesis α-boryl silane compound, be by CoX2-OIP complex catalysis alkynes Shuan Mashi silicon hydrogen/hydrogenation, high chemo-selective, the same carbon of high regio-selective synthesis The method of boryl silane compound.
The present invention is achieved through the following technical solutions:
The invention discloses a kind of method synthesizing α-boryl silane compound, with alkynes as raw material, with silane as silicon Source, with borine as boron source, with CoX2-OIP complex is catalyst, in the presence of sodium triethylborohydride, and-30 DEG C～80 DEG C of temperature Under degree, react 30 minutes～4 hours prepared alkenyl silanes, described alkynes, silane, borine, CoCl2-OIP complex, three second The mol ratio of base sodium borohydride is 1:1:1.2:0.0005-0.05:0.0015-0.15；
As improving further, the structural formula of alkynes of the present invention isR1, R2Can optionally certainly Aryl, heteroaryl, alkyl, hydrogen, aryl is optionally from substituted arylSubstituted 1-naphthyl2-naphthylHeterocyclic arylY is in N, O, S Any one；Wherein, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24Selected from H, halogen, C1-C16Alkyl, C1-C16Oxyl, sulfenyl, amino, amido, thiophene, in pyrroles Any one, X is F, Cl, Br, I, OAc, CF3SO3In any one.
As improving further, its structural formula of silane of the present invention isWherein R30, R31, R32Permissible It is optionally hydrogen, alkyl, alkoxyl, substituted aryl, substituted heteroaryl.
As improving further, its structural formula of borine of the present invention isWherein R33, R34, R35, R36May optionally be hydrogen, alkyl, alkoxyl, substituted aryl, substituted heteroaryl.
As improving further, CoX of the present invention2The structural formula of-OIP complex is optically pure following chemical combination Thing or its enantiomer or raceme, R25, R26, R27, R28, R29Optionally from C1-C16Alkyl, naphthyl, substituted aryl, benzyl:
X is F, Cl, Br, I, OAc, CF3SO3In any one.
As improving further, synthetic method of the present invention has the participation of organic solvent, described organic solvent Be benzene, carbon tetrachloride, toluene, oxolane, ether, dichloromethane, acetonitrile, dioxane, petroleum ether, hexamethylene, normal hexane, Ethyl acetate, chloroform, N, any one in N-diformamide.
As improving further, synthetic method of the present invention is not added with any solvent.
As improving further, alkynes of the present invention, silane, borine, CoX2-OIP complex, boron triethyl hydrogen The mol ratio changing sodium is 1:1:1.2:0.01-0.05:0.03-0.15.
As improving further, reaction temperature of the present invention is-10 DEG C～40 DEG C.
As improving further, reaction temperature of the present invention is 25 DEG C, and the response time is 4 hours.
As improving further, the product of gained of the present invention is to steam through recrystallization, thin layer chromatography, column chromatography or decompression Evaporate to be separated and form.
Beneficial effects of the present invention is as follows:
Present approach provides a kind of effective by CoX2-OIP complex is catalyst, by alkynes silicon hydrogen/hydrogenation The method synthesizing α-boryl silane compound.Compared with the conventional method, the method is applicable to the alkynes of number of different types, Reaction condition is gentle, easy and simple to handle, Atom economy 100%.It addition, reaction without other any poisonous transition metal (as Ruthenium, rhodium, palladium etc.) addition of salt, pharmaceutical synthesis has bigger actual application value.And functional group's tolerance of reaction Good, regioselectivity is the highest, generally > 20:1.
Detailed description of the invention
The method of the present invention is a kind of method effectively being synthesized α-boryl silane compound by alkynes.The method is to use CoX2-OIP complex is as the synthesis α-boryl silane compound of catalyst high regioselectivity.
The general molecular formula of the α synthesized by the inventive method-boryl silane compound is:R1, R2Can With optionally from aryl, heteroaryl, alkyl, hydrogen, aryl is optionally from substituted arylSubstituted 1-naphthyl2-naphthylHeterocyclic aryl(Y is N, O, S In any one)；Wherein, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24Optionally from H, halogen, C1-C16Alkyl, C1-C16Oxyl, sulfenyl, amino, amido, thiophene, pyrroles In any one, X is F, Cl, Br, I, OAc, CF3SO3In any one.Above-mentioned alkyl can be alkyl, cycloalkyl, Benzyl.
The compound of the present invention is with alkynes as raw material, and diphenyl silane is silicon source, and that alcohol borine of sheet is boron source, in three second In the presence of base sodium borohydride, it is solvent at toluene, with CoX2-OIP complex prepares as catalyst reaction, available following formula table Show:
The structural formula of alkynes is:Wherein, R1, R2As previously mentioned；The general structure of catalyst is (for appointing Optically pure structure of anticipating or its enantiomer or raceme, do not limited by diagram)
R25, R26, R27, R28, R29Optionally from C1-C16Alkyl, naphthyl, substituted aryl, benzyl.
Described alkynes, diphenyl silane, CoX2-OIP complex, the mol ratio of sodium triethylborohydride are 1:1: 0.0005-0.05:0.0015-0.15；1:1:0.004-0.0:2:0.012-0.06 further.Reaction temperature is recommended as-30 DEG C ～80 DEG C, it is further recommended that-10 DEG C～40 DEG C, it is particularly recommended that 20 DEG C.Response time is recommended as 3 minutes-48 hours, pushes away further Recommend is 5 seconds-20 minutes, it is particularly recommended that 5 minutes.Wherein, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29As previously mentioned.
The alkyl mentioned in the present invention, the group all recommending carbon number to be 1～16, it is further recommended that carbon number is 1～10, especially Recommending carbon number is 1～6.The cycloalkyl that the present invention mentions, the group all recommending carbon number to be 3～16, it is further recommended that carbon number is 3 ～10, it is particularly recommended that carbon number is 3～6.The aryl that the present invention mentions, refers both to phenyl, naphthyl and contains N, the heteroaryl of O, S.
The reaction of the inventive method can be carried out under solvent-free, it is also possible to is carrying out in polarity or non-polar solven, As benzene, carbon tetrachloride, toluene, oxolane, ether, dichloromethane, acetonitrile, dioxane, petroleum ether, hexamethylene, normal hexane, Ethyl acetate, chloroform, N, N-diformamide etc..
The inventive method can be passed through recrystallization, thin layer chromatography, column chromatography or decompression distillation and be separated.The inventive method Provide the synthetic method of some new α-boryl silane compounds.
Below by specific embodiment, technical scheme is illustrated further:
Embodiment 1:CoX2Silicon hydrogen/the hydroboration of the alkynes of-OIP complex catalysis
25 DEG C, under condition of nitrogen gas, in a reaction tube being dried, add CoX2-OIP complex (0.02mmol), tetrahydrochysene Furan (2ml), diphenyl silane (1.0mmol), it is injected into sodium triethylborohydride (0.06mmol), alkynes (1.0mmol), so Rear stirring 5 minutes, is then injected into that alcohol borine (1.2mol) of sheet, obtains product through column chromatography for separation after reacting 4 hours.
P1:Diphenyl (1-phenyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) ethyl)silane
Colourless liquid, 60% productivity.IR(cm-1):2979,2141,1595,1309,1144.1HNMR(CDCl3, 400MHz): δ 7.61 (d, J=7.6Hz, 2H), 7.37-7.42 (m, 1H), 7.27-7.36 (m, 7H), 7.19-7.26 (m, 4H), 7.08-7.14(m,1H),4.99(s,1H),1.60(s,3H),1.14(s,6H),1.10(s,6H)；13C NMR:(CDCl3, 100MHz):δ143.3,136.3,136.0,133.6,133.1,129.5,129.3,127.7,127.6,127.5,127.3, 124.1,83.4,24.8,24.5,16.6.HRMS(EI)calculated for[C26H31BO2Si]+requires m/z 414.2186,found m/z 414.2185.
P2:(1-([1,1'-Biphenyl]-4-yl)-1-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)ethyl)diphenylsilane
Colourless liquid, 64% productivity.IR(cm-1):2978,2139,1605,1307,1143.1H NMR(CDCl3, 400MHz): δ 7.61 (d, J=7.6Hz, 4H), 7.47 (d, J=8.0Hz, 2H), 7.41 (t, J=7.6Hz, 2H), 7.26- 7.38(m,9H),7.17-7.23(m,2H),4.99(s,1H),1.61(s,3H),1.12(s,6H),1.08(s,6H)；13C NMR:(CDCl3,100MHz):δ142.6,141.2,136.7,136.3,136.1,133.5,133.0,129.6,129.3, 128.6,128.0,127.5,127.3,126.8,126.7,126.3,83.5,24.8,24.6,16.7.HRMS(EI) calculated for[C32H35BO2Si]+requires m/z 490.2499,found m/z490.2507.
P3:(1-(Naphthalen-2-yl)-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)ethyl)diphenylsilane
Colourless liquid, 64% productivity.IR(cm-1):2978,2140,1596,1308,1143.1H NMR(CDCl3, 400MHz):δ7.74-7.78(m,1H),7.65-7.70(m,2H),7.60(d,2H),7.53-7.58(m,2H),7.24-7.43 (m, 8H), 7.15 (t, J=7.6Hz, 2H), 5.05 (s, 1H), 1.68 (s, 3H), 1.12 (s, 6H), 1.07 (s, 6H)；13C NMR:(CDCl3,100MHz):δ141.2,136.4,136.0,133.7,133.5,133.1,131.1,129.6,129.3, 127.7,127.6,127.34,127.29,126.7,125.4,124.8,124.6,83.5,24.8,24.5,16.8.HRMS (EI)calculated for[C30H33BO2Si]+requires m/z464.2343,found m/z 464.2345.
Embodiment 2:CoX2Silicon hydrogen/the hydroboration of the alkynes of-OIP complex catalysis
40 DEG C, under condition of nitrogen gas, in a reaction tube being dried, add CoX2-OIP complex (0.02mmol), tetrahydrochysene Furan (2ml), diphenyl silane (1.0mmol), it is injected into sodium triethylborohydride (0.06mmol), alkynes (1.0mmol), so Rear stirring 5 minutes, is then injected into that alcohol borine (1.2mol) of sheet, obtains product through column chromatography for separation after reacting 4 hours.
P4:4-(1-(Diphenylsilyl)-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)ethyl)-N,N-diethylbenzam ide
Colourless liquid, 78% productivity.IR(cm-1):2977,2138,1628,1311,803.1H NMR(CDCl3, 400MHz): δ 7.61 (d, J=8.0,1.6Hz, 2H), 7.15-7.40 (m, 12H), 4.97 (s, 1H), 3.52 (s, 2H), 3.27 (s,2H),1.58(s,3H),1.03-1.28(m,18H)；13C NMR:(CDCl3,100MHz):δ171.7,144.8,136.2, 135.9,135.0,133.1,132.7,132.7,129.6,129.3,128.0,127.5,127.3,127.2,125.8,83.5, 43.3,39.1,24.7,24.4,16.3,14.1,12.8.HRMS(EI)calculated for[C31H40BNO3Si]+ requires m/z 513.2871,found m/z 513.2867.
P5:Methyl4-(1-(diphenylsilyl)-1-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)ethyl)benzoate
Colourless liquid, 39% productivity.IR(cm-1):2926,2140,1721,1605,1280.1HNMR(CDCl3, 400MHz): δ 7.88 (d, J=8.4Hz, 2H), 7.58 (d, J=7.2Hz, 2H), 7.27-7.41 (m, 8H), 7.17-7.23 (m, 2H),4.97(s,1H),3.89(s,3H),1.59(s,3H),1.11(s,6H),1.06(s,6H)；13C NMR:(CDCl3, 100MHz):δ167.6,149.8,136.3,136.0,133.0,132.6,129.8,129.6,129.1,127.7,127.54, 127.51,125.9,83.7,51.9,24.8,24.5,16.5.HRMS(EI)calculated for[C28H33BO4Si]+ requires m/z 472.2241,found m/z 472.2251.
Embodiment 3:CoX2Silicon hydrogen/the hydroboration of the alkynes of-OIP complex catalysis
-10 DEG C, under condition of nitrogen gas, in a reaction tube being dried, add CoX2-OIP complex (0.02mmol), four Hydrogen furan (2ml), diphenyl silane (1.0mmol), it is injected into sodium triethylborohydride (0.06mmol), alkynes (1.0mmol), Then stirring 5 minutes, are then injected into that alcohol borine (1.2mol) of sheet, obtain product through column chromatography for separation after reacting 4 hours.
P6:Diphenyl (1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1- (thiophen-2-yl)ethyl)silane
Colourless liquid, 56% productivity.IR(cm-1):2935,2144,1315,1143,803.1H NMR(CDCl3, 400MHz): δ 7.64 (dd, J=8.0,1.6Hz, 2H), 7.29-7.41 (m, 6H), 7.21-7.27 (m, 2H), 7.02 (dd, J= 5.2,1.2Hz, 1H), 6.88-6.92 (m, 1H), 6.80 (dd, J=3.6,1.2Hz, 1H), 4.98 (s, 1H), 1.64 (s, 3H), 1.12(s,6H),1.06(s,6H)；13C NMR:(CDCl3,100MHz):δ149.0,136.2,136.0,133.2,132.6, 129.7,129.5,127.6,127.4,126.5,123.1,121.5,83.7,24.9,24.5,19.1.HRMS(EI) calculated for[C24H29BO2SSi]+requires m/z420.1751,found m/z 420.1755.
Finally, in addition it is also necessary to be only several specific embodiments of the present invention it is noted that listed above.Obviously, this Bright it is not limited to above example, it is also possible to have many deformation.Those of ordinary skill in the art can be from present disclosure The all deformation directly derived or associate, are all considered as protection scope of the present invention.

Claims (10)

1. the method synthesizing α-boryl silane compound, is characterized in that with alkynes as raw material, with silane for silicon source, with boron Alkane is boron source, with CoX2-OIP complex is catalyst, in the presence of sodium triethylborohydride, at a temperature of-30 DEG C～80 DEG C, instead Answer 30 minutes～4 hours prepared alkenyl silanes, described alkynes, silane, borine, CoCl2-OIP complex, boron triethyl hydrogenate The mol ratio of sodium is 1:1:1.2:0.0005-0.05:0.0015-0.15；
The structural formula of described alkynes isR1, R2Can be optionally from aryl, heteroaryl, alkyl, hydrogen, aryl is appointed Selected from substituted arylSubstituted 1-naphthyl2-naphthylHeterocyclic arylY is any one in N, O, S；Wherein, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24Selected from H, halogen, C1-C16 Alkyl, C1-C16Oxyl, sulfenyl, amino, amido, thiophene, any one in pyrroles, X is F, Cl, Br, I, OAc, CF3SO3In any one.
The method of synthesis α-boryl silane compound the most according to claim 1, is characterized in that, its knot of described silane Structure formula isWherein R30, R31, R32May optionally be hydrogen, alkyl, alkoxyl, substituted aryl, substituted heteroaryl.
The method of synthesis α-boryl silane compound the most according to claim 1, is characterized in that, its knot of described borine Structure formula isWherein R33, R34, R35, R36May optionally be hydrogen, alkyl, alkoxyl, substituted aryl, substituted Heteroaryl.
4., according to the method for the synthesis alkenyl silanes compounds described in claim 1 or 2 or 3, it is characterized in that, described CoX2- The structural formula of OIP complex is optically pure following compound or its enantiomer or raceme, R25, R26, R27, R28, R29Optionally From C1-C16Alkyl, naphthyl, substituted aryl, benzyl:
X is F, Cl, Br, I, OAc, CF3SO3In any one.
The method of synthesis α-boryl silane compound the most according to claim 1, is characterized in that, in described synthetic method Having the participation of organic solvent, described organic solvent is benzene, carbon tetrachloride, toluene, oxolane, ether, dichloromethane, second Nitrile, dioxane, petroleum ether, hexamethylene, normal hexane, ethyl acetate, chloroform, N, any one in N-diformamide.
The method of synthesis α-boryl silane compound the most according to claim 1, is characterized in that, in described synthetic method It is not added with any solvent.
7., according to the method for the synthesis α-boryl silane compound described in claim 1 or 2 or 3 or 5 or 6, it is characterized in that, institute The alkynes stated, silane, borine, CoX2-OIP complex, the mol ratio of sodium triethylborohydride are 1:1:1.2:0.01-0.05: 0.03-0.15。
8., according to the method for the synthesis α-boryl silane compound described in claim 1 or 2 or 3 or 5 or 6, it is characterized in that, described Reaction temperature be-10 DEG C～40 DEG C.
The method of synthesis α-boryl silane compound the most according to claim 8, is characterized in that, described reaction temperature Being 25 DEG C, the response time is 4 hours.
10. according to the method for the synthesis α-boryl silane compound described in claim 1 or 2 or 3 or 5 or 6 or 9, its feature It is that the product of gained is to be separated form through recrystallization, thin layer chromatography, column chromatography or decompression distillation.
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