CN106117257B - A method of synthesis α-boryl silane compound - Google Patents
A method of synthesis α-boryl silane compound Download PDFInfo
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- CN106117257B CN106117257B CN201610428311.7A CN201610428311A CN106117257B CN 106117257 B CN106117257 B CN 106117257B CN 201610428311 A CN201610428311 A CN 201610428311A CN 106117257 B CN106117257 B CN 106117257B
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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 speed synthesis α-boryl silane compound method.Using alkynes as raw material, using silane as silicon source, using borine as boron source, with CoX2- OIP complex compound is catalyst, in the presence of sodium triethylborohydride, at a temperature of -30 DEG C~80 DEG C, reacts 30 minutes~4 hours obtained alkenyl silanes, the alkynes, silane, borine, CoCl2- OIP complex compound, sodium triethylborohydride molar ratio be 1:1:1.2:0.0005-0.05:0.0015-0.15；Compared with the conventional method, this method is suitable for a variety of different types of alkynes, and reaction condition is mild, easy to operate, Atom economy 100%.In addition, reaction is not necessarily to the addition of other any toxic transition metal (such as ruthenium, rhodium, palladium) salts, there is biggish practical application value on pharmaceutical synthesis.And functional group's tolerance of reaction is good, regioselectivity is also higher, generally > 20:1.
Description
Technical field
This method is related to a kind of compound synthesis method, specifically, being a kind of high regioselectivity rapid synthesis α-boron
The method of base silane class compound.
Background technique
The α of quaternary structure-boryl silane compound is a kind of important synthesis unit, he not only can be with nucleopilic reagent
It acts on to construct the level Four allyl silicane class compound [a) Org.Lett.2011,13,1490.] with very big challenge, also
It can be constructed by Suzuki coupling reaction level Four silane compound [a) Chem.Eur.J.2011,17,13124.], and
And by aoxidizing available level Four alcohol [a) J.Org.Chem.1997,621112.] further across Fleming-Kumada.
The α of quaternary structure-boryl silane compound is by a series of available many carbon center's compounds replaced entirely of conversion.
However, building is more challenging with carbon boryl silane compound.The hydroboration that H.C.Brown is led is not
It can be well using same carbon level Four boryl silane compound be constructed, because boron ester is more when boron ester is to double bond addition
Tendency add to the small 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.].Silicon hydrogenation/the hydroboration for being catalyzed one kettle way alkynes by cheap metal is same come framework
Carbon boryl silane is significantly.
The present invention is catalyzed one kettle way alkynes silicon hydrogenation/hydroboration by cheap metal cobalt and is successfully realized same carbon boryl silane
The building of class compound.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of effective synthesis α-boryl silane compound method, be by
CoX2- OIP complex catalysis alkynes Shuan Mashi silicon hydrogen/Boron 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 synthesis α-boryl silane compound methods, using alkynes as raw material, using silane as silicon
Source, using borine as boron source, with CoX2- OIP complex compound is catalyst, in the presence of sodium triethylborohydride, -30 DEG C~80 DEG C temperature
Under degree, 30 minutes~4 hours obtained alkenyl silanes, the alkynes, silane, borine, CoCl are reacted2- OIP complex compound, three second
The molar ratio of base sodium borohydride is 1:1:1.2:0.0005-0.05:0.0015-0.15；
As a further improvement, the structural formula of alkynes of the present invention isR1, R2It can be optional
From aryl, heteroaryl, alkyl, hydrogen, aryl is optionally from the aryl replacedSubstituted 1- naphthalene2- naphthaleneHeterocyclic 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 F, Cl, Br, I, OAc, CF3SO3In any one.
As a further improvement, its structural formula of silane of the present invention isWherein R30, R31, R32It can be with
Optionally hydrogen, alkyl, alkoxy, substituted aryl, substituted heteroaryl.
As a further improvement, its structural formula of borine of the present invention isWherein R33, R34, R35,
R36It may optionally be hydrogen, alkyl, alkoxy, substituted aryl, substituted heteroaryl.
As a further improvement, CoX of the present invention2The structural formula of-OIP complex compound is optically pure following chemical combination
Object or its enantiomer or raceme, R25, R26, R27, R28, R29Optionally from C1-C16Alkyl, naphthalene, substituted aryl, benzyl:
X is F, Cl, Br, I, OAc, CF3SO3In any one.
As a further improvement, have the participation of organic solvent in synthetic method of the present invention, the organic solvent
Be benzene, carbon tetrachloride, toluene, tetrahydrofuran, ether, methylene chloride, acetonitrile, dioxane, petroleum ether, hexamethylene, n-hexane,
Ethyl acetate, chloroform, N, any one in N- diformamide.
As a further improvement, any solvent is not added in synthetic method of the present invention.
As a further improvement, alkynes of the present invention, silane, borine, CoX2- OIP complex compound, boron triethyl hydrogen
The molar ratio for changing sodium is 1:1:1.2:0.01-0.05:0.03-0.15.
As a further improvement, reaction temperature of the present invention is -10 DEG C~40 DEG C.
As a further improvement, reaction temperature of the present invention is 25 DEG C, the reaction time is 4 hours.
As a further improvement, the resulting product of the present invention is steamed by recrystallization, thin-layer chromatography, column chromatography or decompression
It evaporates and is separated.
Beneficial effects of the present invention are as follows:
Present approach provides one kind effectively by CoX2- OIP complex compound is catalyst, is hydrogenated by alkynes silicon Qing/Boron
To synthesize α-boryl silane compound method.Compared with the conventional method, this method is suitable for a variety of different types of alkynes,
Reaction condition is mild, easy to operate, Atom economy 100%.In addition, reaction is not necessarily to other any toxic transition metal (such as
Ruthenium, rhodium, palladium etc.) salt addition, on pharmaceutical synthesis have biggish practical application value.And functional group's tolerance of reaction
Good, regioselectivity is also higher, generally > 20:1.
Specific embodiment
Method of the invention is that one kind effectively synthesizes α-boryl silane compound method by alkynes.This method is to use
CoX2Synthesis α-boryl silane compound of-OIP the complex compound as the high regioselectivity of catalyst.
α synthesized by the method for the present invention-boryl silane compound general molecular formula is:R1, R2It can
With optionally from aryl, heteroaryl, alkyl, hydrogen, aryl is optionally from the aryl replacedSubstituted 1- naphthalene2- naphthaleneHeterocyclic aryl(Y 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 F, Cl, Br, I, OAc, CF3SO3In any one.Above-mentioned alkyl can be alkyl, naphthenic base,
Benzyl.
The compound of the present invention is using alkynes as raw material, and diphenyl silane is silicon source, that alcohol borine of piece is boron source, in three second
It is solvent in toluene, with CoX in the presence of base sodium borohydride2- OIP complex compound can use following formula table as made from catalyst reaction
Show:
The structural formula of alkynes are as follows:Wherein, R1, R2As previously described；The general structure of catalyst is (to appoint
Optically pure structure of anticipating or its enantiomer or raceme are not limited by diagram)
R25, R26, R27, R28, R29Optionally from C1-C16Alkyl, naphthalene, substituted aryl, benzyl.
The alkynes, diphenyl silane, CoX2- OIP complex compound, sodium triethylborohydride molar ratio be 1:1:
0.0005-0.05:0.0015-0.15；Further 1:1:0.004-0.0:2:0.012-0.06.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.Reaction time is recommended as -48 hours 3 minutes, further pushes away
Recommend is -20 minutes 5 seconds, 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 described.
The group that alkyl mentioned in the present invention, recommendation carbon number are 1~16, it is further recommended that carbon number is 1~10, especially
Recommending carbon number is 1~6.The group that the naphthenic base that the present invention mentions, recommendation carbon number are 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, naphthalene and containing N, the heteroaryl of O, S.
The reaction of the method for the present invention can also carried out in solvent-free lower progress in polarity or nonpolar solvent,
As benzene, carbon tetrachloride, toluene, tetrahydrofuran, ether, methylene chloride, acetonitrile, dioxane, petroleum ether, hexamethylene, n-hexane,
Ethyl acetate, chloroform, N, N- diformamide etc..
The method of the present invention can be chromatographed by recrystallization, thin-layer chromatography, column or vacuum distillation is separated.The method of the present invention
Provide the synthetic method of some new α-boryl silane compounds.
Technical solution of the present invention is further illustrated below by specific embodiment:
Embodiment 1:CoX2Silicon hydrogen/hydroboration of the alkynes of-OIP complex catalysis
25 DEG C, under condition of nitrogen gas, CoX is added in a dry reaction tube2- OIP complex compound (0.02mmol), tetrahydro
Furans (2ml), diphenyl silane (1.0mmol) are injected into sodium triethylborohydride (0.06mmol), alkynes (1.0mmol), so
It stirs 5 minutes afterwards, is then injected into that alcohol borine (1.2mol) of piece, obtains product by column chromatography for separation after reaction 4 hours.
P1:Diphenyl (1-phenyl-1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)
ethyl)silane
Colourless liquid, 60% yield.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% yield.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% yield.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/hydroboration of the alkynes of-OIP complex catalysis
40 DEG C, under condition of nitrogen gas, CoX is added in a dry reaction tube2- OIP complex compound (0.02mmol), tetrahydro
Furans (2ml), diphenyl silane (1.0mmol) are injected into sodium triethylborohydride (0.06mmol), alkynes (1.0mmol), so
It stirs 5 minutes afterwards, is then injected into that alcohol borine (1.2mol) of piece, obtains product by column chromatography for separation after reaction 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% yield.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% yield.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/hydroboration of the alkynes of-OIP complex catalysis
- 10 DEG C, under condition of nitrogen gas, CoX is added in a dry reaction tube2- OIP complex compound (0.02mmol), four
Hydrogen furans (2ml), diphenyl silane (1.0mmol) are injected into sodium triethylborohydride (0.06mmol), alkynes (1.0mmol),
Then it stirs 5 minutes, is then injected into that alcohol borine (1.2mol) of piece, obtains product by column chromatography for separation after reaction 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% yield.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.
The above list is only a few specific embodiments of the present invention for finally, it should also be noted that.Obviously, this hair
Bright to be not limited to above embodiments, acceptable there are many deformations.Those skilled in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (9)
1. a kind of synthesis α-boryl silane compound method, it is characterized in that using alkynes as raw material, using silane as silicon source, with boron
Alkane is boron source, with CoX2- OIP complex compound is catalyst, in the presence of sodium triethylborohydride, at a temperature of -30 DEG C~80 DEG C, instead
Answer 30 minutes~4 hours obtained alkenyl silanes, the alkynes, silane, borine, CoX2- OIP complex compound, boron triethyl hydrogenation
The molar ratio of sodium is 1:1:1.2:0.0005-0.05:0.0015-0.15；
The structural formula of the alkynes isR1, R2Can be optionally from aryl, heteroaryl, alkyl, hydrogen, aryl is optionally certainly
Substituted arylSubstituted 1- naphthalene2- naphthalene
Heterocyclic 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-C16Alkyl, C1-C16Oxyl,
Sulfenyl, amino, amido, thiophene, any one in pyrroles, the CoX2The structural formula of-OIP complex compound is optically pure
Following compound or its enantiomer or raceme, R25, R26, R27, R28, R29Optionally from C1-C16Alkyl, naphthalene, substituted virtue
Base, benzyl:
X is F, Cl, Br, I, OAc, CF3SO3In any one.
2. synthesis α-boryl silane compound method according to claim 1, characterized in that its knot of the silane
Structure formula isWherein R30, R31, R32It may optionally be hydrogen, alkyl, alkoxy, substituted aryl, substituted heteroaryl
Base.
3. synthesis α-boryl silane compound method according to claim 1, characterized in that its knot of the borine
Structure formula isWherein R33, R34, R35, R36May optionally be hydrogen, alkyl, alkoxy, substituted aryl, replace
Heteroaryl.
4. synthesis α-boryl silane compound method according to claim 1, characterized in that in the synthetic method
There is the participation of organic solvent, the organic solvent is benzene, carbon tetrachloride, toluene, tetrahydrofuran, ether, methylene chloride, second
Nitrile, dioxane, petroleum ether, hexamethylene, n-hexane, ethyl acetate, chloroform, N, any one in N- diformamide.
5. synthesis α-boryl silane compound method according to claim 1, characterized in that in the synthetic method
Any solvent is not added.
6. synthesizing α-boryl silane compound method described according to claim 1 or 2 or 3 or 4 or 5, characterized in that institute
Alkynes, silane, borine, the CoX stated2- OIP complex compound, sodium triethylborohydride molar ratio be 1:1:1.2:0.01-0.05:
0.03-0.15。
7. synthesizing α-boryl silane compound method described according to claim 1 or 2 or 3 or 4 or 5, characterized in that described
Reaction temperature be -10 DEG C~40 DEG C.
8. synthesis α-boryl silane compound method according to claim 7, characterized in that the reaction temperature
It is 25 DEG C, the reaction time is 4 hours.
9. synthesizing α-boryl silane compound method, feature described according to claim 1 or 2 or 3 or 4 or 5 or 7
It is that resulting product is separated by recrystallization, thin-layer chromatography, column chromatography or vacuum distillation.
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