CN106083908B - A method of synthesis α-alkenyl silanes class compound - Google Patents
A method of synthesis α-alkenyl silanes class compound Download PDFInfo
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Abstract
The invention discloses a kind of synthesis α-alkenyl silanes class compound methods, using alkynes as raw material, using silane as silicon 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 5 seconds~30 minutes obtained alkenyl silanes, alkynes, silane, CoCl2- OIP complex compound, sodium triethylborohydride molar ratio be 1:1:0.0005-0.02:0.0015-0.06；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 90:10- > 99:1.
Description
Technical field
This method is related to chemical synthesis process, specifically, being a kind of high chemo-selective, regioselectivity and three-dimensional choosing
Selecting property synthesizes α-alkenyl silanes class compound method.
Background technique
Organosilan is a kind of very important synthesis unit [a) In Chemistry in organic synthesis and Material Field
ofOrganic Silicon Compounds；Rappoport,Z.,Apeloig,Y.,Eds.；Wiley:Chichester,
1998,p 1687].Wherein, alkenyl silanes are a kind of highly useful intermediates, potentially act as stable alkenyl anion or
Alkenyl cation synthon [a) Chem.Rev.1986,86,857.].The hydrogenation of alkynes silicon is a kind of to meet the straight of atom economy
It is bonded into the method [a) Angew.Chem., Int.Ed.2004,43,2749.] of alkenyl silanes.However, highly selective synthesis
α-alkenyl silanes only have several seldom reports, and catalyst used in it is noble metal complexes (Ru, Rh, Pd etc.)
[a)J.Am.Chem.Soc.2001,123,12726.b)Org.Lett.2000,2,1887.c)Org.Lett.2002,4,
2825.d)J.Org.Chem.2005,70,10717.].Up to the present, the highly selective α silicon of the alkynes of cheap metal catalysis
The method of hydrogenation is not yet reported that.
Therefore, develop the silicon hydrogenation of the alkynes of the highly selective cheap metal catalysis of high efficiency to synthesize α-alkenyl silicon
Alkane has great meaning.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of effective method of synthesis alkenyl silanes class compound, be by
CoX2- OIP complex catalysis alkynes geneva silicon hydrogenation, high chemo-selective, high regioselectivity, highly-solid selectively close
At the method for alkenyl silanes class compound.
The present invention is achieved through the following technical solutions:
The invention discloses a kind of methods for synthesizing alkenyl silanes class compound, using alkynes as raw material, using silane as silicon source,
With CoX2- OIP complex compound is catalyst, in the presence of sodium triethylborohydride, at a temperature of -30 DEG C~80 DEG C, and reaction 5 seconds~30
Minute obtained alkenyl silanes, alkynes, silane, CoCl2- OIP complex compound, sodium triethylborohydride molar ratio be 1:1:
0.0005-0.02:0.0015-0.06；
The structural formula of alkynes isR1, R2Optionally aryl, heteroaryl, alkyl, hydrogen, aryl optionally replace
ArylSubstituted 1- naphthalene2- naphthalene
Heterocyclic arylY is any one in N, O, S, 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, hydrocarbon sulphur
Base, amino, amido, thiophene, any one in pyrroles, 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, R32Optionally
For 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, CoX2- OIP complex compound, sodium triethylborohydride
Molar ratio be 1:1:0.004-0.02:0.012-0.06.
As a further improvement, reaction temperature is -10 DEG C~40 DEG C in synthetic method of the present invention.
As a further improvement, reaction temperature is 20 DEG C in synthetic method of the present invention, the reaction time is 5 minutes
Or 20 minutes.
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 to synthesize
The method of alkenyl silanes class compound.Compared with the conventional method, this method is suitable for a variety of different types of alkynes, reaction condition
Mildly, easy to operate, Atom economy 100%.In addition, reaction is not necessarily to other any toxic transition metal (such as ruthenium, rhodium, palladiums
Deng) addition of salt, there is biggish practical application value on pharmaceutical synthesis.And functional group's tolerance of reaction is good, region
Also higher, the generally 90:10- > 99:1 of selectivity.
Specific embodiment
Method of the invention is a kind of method for effectively synthesizing alkenyl silanes class compound by alkynes.This method is to use
CoX2The synthesis alkenyl silanes of-OIP complex compound as the high regioselectivity of catalyst.
The general molecular formula of alkenyl silanes class compound synthesized by the method for the present invention is:R1, R2It can be with
Optionally from aryl, heteroaryl, alkyl, hydrogen, aryl is optionally from the aryl replacedSubstituted 1- naphthalene2- naphthaleneHeterocyclic aryl(in Y 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, R24Optionally from H, halogen, C1-C16Alkyl, C1-C16Oxyl, sulfenyl, amino, amido, thiophene, Bi Kazhong
Any one, X F, Cl, Br, I, OAc, CF3SO3In any one.Above-mentioned alkyl can be alkyl, naphthenic base, benzyl
Base.
Alkenyl silanes class compound of the invention is using alkynes as raw material, and diphenyl silane is silicon source, in boron triethyl hydrogen
It is solvent in tetrahydrofuran, with CoX in the presence of changing sodium2- 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 alkenyl silicon.
Technical solution of the present invention is further illustrated below by specific embodiment:
Embodiment 1:CoX2The silicon hydrogenation of the terminal alkyne of-OIP complex catalysis
20 DEG C, under condition of nitrogen gas, CoX is sequentially added in a dry reaction tube2- OIP complex compound (0.02mmol),
Tetrahydrofuran (2ml), diphenyl silicon hydrogen (1.0mmol) are injected into sodium triethylborohydride (0.06mmol), alkynes
(1.0mmol) then stirs column chromatography for separation after five minutes and obtains product.P1:Diphenyl (1-phenylvinyl) silane
White solid, 86% yield.M.P.:59~60 DEG C .IR (cm-1):3063,2127,1491,1429,1113.1H
NMR(CDCl3,400MHz):δ7.51-7.61(m,4H),7.30-7.45(m,8H),7.17-7.29(m,3H),6.25-6.32
(m,1H),5.66-5.72(m,1H),5.37-5.42(m,1H)；13C NMR:(CDCl3,100MHz):δ145.9,142.9,
135.8,133.0,132.1,129.8,128.4,128.0,127.1,126.7.HRMS(EI)calculated for
[C20H18Si]+requires m/z 286.1178,found m/z 286.1181.
P2:Diphenyl (1- (p-tolyl) vinyl) silane
White solid, 96% yield.M.P.:64~65 DEG C .IR (cm-1):2919,2126,1565,1428,803.1H
NMR(CDCl3, 400MHz): δ 7.53-7.59 (m, 4H), 7.32-7.45 (m, 6H), 7.22-7.25 (m, 2H), 7.06 (d, J=
8.0Hz, 2H), 6.26 (d, J=2.4Hz, 1H), 5.63 (d, J=2.4Hz, 1H), 5.38 (s, 1H), 2.30 (s, 3H)；13C
NMR:(CDCl3,100MHz):δ145.4,139.9,136.8,135.8,133.2,131.3,129.7,129.1,128.0,
126.6,21.1.HRMS(EI)calculated for[C21H20Si]+requires m/z 300.1334,found m/z
300.1333.
P3:(1- (4-Bromophenyl) vinyl) diphenylsilane
White solid, 96% yield.M.P.:84~85 DEG C .IR (cm-1):3066,2129,1484,1429,1114.1H
NMR(CDCl3, 400MHz): δ 7.51-7.61 (m, 4H), 7.32=7.45 (m, 8H), 7.15-7.22 (m, 2H), 6.25 (d, J
=2.2Hz, 1H), 5.70 (d, J=2.2Hz, 1H), 5.36 (s, 1H)；13C NMR:(CDCl3,100MHz):δ145.0,
141.8,135.7,132.6,132.5,131.5,129.9,128.3,128.1,121.1.HRMS(EI)calculated for
[C20H17BrSi]+requires m/z 364.0283,found m/z 364.0286.
P4:(4- (1- (Diphenylsilyl) vinyl) phenyl) methanol
Colourless liquid, 65% yield.IR(cm-1):3322,3017,2126,1428,1113.1H NMR(CDCl3,
400MHz): δ 7.56 (d, J=7.2Hz, 4H), 7.30-7.43 (m, 8H), 7.23 (d, J=7.2Hz, 2H), 6.28 (d, J=
2.0Hz, 1H), 5.68 (d, J=2.0Hz, 1H), 5.39 (s, 1H), 4.60 (s, 2H), 1.74 (brs, 1H)；13C NMR:
(CDCl3,100MHz):δ145.5,139.6,135.7,132.9,132.2,129.8,128.0,127.1,126.9,
65.0.HRMS(EI)calculated for[C21H20OSi]+requires m/z 316.1283,found m/z
316.1287.
P4:1- (4- (1- (Diphenylsilyl) vinyl) phenyl) ethanone
White solid, 85% yield.M.P.:73~74 DEG C .IR (cm-1):3066,2128,1681,1601,1114.1H
NMR(CDCl3, 400MHz): δ 7.90 (d, J=8.4Hz, 2H), 7.53-7.58 (m, 4H), 7.32-7.43 (m, 8H), 6.33
(d, J=2.4Hz, 1H), 5.79 (d, J=2.4Hz, 1H), 5.40 (s, 1H), 2.55 (s, 3H)；13C NMR:(CDCl3,
100MHz):δ197.6,147.9,145.5,135.7,133.8,132.4,130.0,128.5,128.1,126.9,
26.5.HRMS(EI)calculated for[C22H20OSi]+requires m/z 328.1283,found m/z
328.1282.
P5:Diphenyl (1- (thiophen-2-yl) vinyl) silane
- 30 DEG C, under condition of nitrogen gas, CoX is sequentially added in a dry reaction tube2- OIP complex compound
(0.02mmol), tetrahydrofuran (2ml), diphenyl silicon hydrogen (1.0mmol) are injected into sodium triethylborohydride (0.06mmol),
Alkynes (1.0mmol) then stirs column chromatography for separation after five minutes and obtains product.White solid, 85% yield.M.P.:54~55
℃.IR(cm-1):3067,2130,1484,1231,1114.1H NMR(CDCl3, 400MHz): δ 7.59 (d, J=7.2Hz,
4H), 7.33-7.45 (m, 6H), 7.12 (d, J=5.2Hz, 1H), 6.91 (d, J=3.6Hz, 1H), 6.86 (t, J=4.4Hz,
1H), 6.33 (s, 1H), 5.50 (d, J=1.6Hz, 1H), 5.41 (s, 1H)；13C NMR:(CDCl3,100MHz):δ146.3,
137.9,135.8,132.4,130.0,129.6,128.1,127.5,125.9,124.1.HRMS(EI)calculated for
[C18H16SSi]+requires m/z 292.0742,found m/z 292.0739.
Embodiment 2:CoX2The silicon hydrogenation of the non-end alkynes of-OIP complex catalysis
20 DEG C, under condition of nitrogen gas, CoX is sequentially added in a dry reaction tube2- OIP complex compound (0.02mmol),
Tetrahydrofuran (2ml), diphenyl silicon hydrogen (1.0mmol) are injected into sodium triethylborohydride (0.06mmol), alkynes
(1.0mmol) then stirs column chromatography for separation after five minutes and obtains product.
P6:(E)-dec-5-en-5-yldiphenylsilane
Colourless liquid, 97% yield.IR(cm-1):3002,2957,2116,11429,1111.1H NMR(CDCl3,
400MHz):δ7.52-7.59(m,4H),7.31-7.42(m,6H),5.86-5.93(m,1H),5.07(s,1H),2.13-2.26
(m,4H),1.18-1.42(m,8H),0.86-0.94(m,3H),0.76-0.83(m,3H).HRMS(EI)calculated for
[C22H30Si]+requires m/z 322.2117,found m/z 322.2119.
P7:(E)-diphenyl (1-phenylbut-1-en-1-yl) silane
White solid, 88% yield.M.P.:47~48 DEG C .IR (cm-1):2965,2123,1600,1429,1070.1H
NMR(CDCl3,400MHz):δ7.48-7.55(m,3H),7.30-7.42(m,6H),7.18-7.24(m,2H),7.10-7.17
(m, 1H), 6.95-7.01 (m, 2H), 6.19 (t, J=7.4Hz, 2H), 5.18 (s, 1H), 2.05-2.15 (m, 2H), 0.95 (t,
J=7.4Hz, 3H)；13C NMR:(CDCl3,100MHz):δ149.4,141.3,137.2,135.7,133.6,129.6,
128.3,128.0,127.9,125.8,23.6,14.0.HRMS(EI)calculated for[C22H22Si]+requires m/z
314.1491,found m/z 314.1495.
P8:(E)-(4,4-dimethylpent-2-en-2-yl) diphenylsilane
Colourless liquid, 89% yield.IR(cm-1): 3067,2956,2117,1428,1112.1H NMR(CDCl3,
400MHz): δ 7.52-7.57 (m, 4H), 7.32-7.41 (m, 6H), 6.01 (q, J=1.8Hz, 1H), 4.98 (s, 1H), 1.90
(d, J=1.8Hz, 3H), 1.16 (s, 9H)；13C NMR:(CDCl3,100MHz):δ155.4,135.6,134.0,129.5,
128.9,127.9,35.1,30.6,16.3HRMS(EI)calculated for[C19H24Si]+requires m/z
280.1647,found m/z 280.1645.
P9:(E)-diphenyl (2-phenyl-1- (thiophen-2-yl) vinyl) silane
Colourless liquid, 68% yield.1H NMR(CDCl3, 400MHz): δ 7.59 (dd, J=8.0,1.6Hz, 4H), 7.30-
7.39 (m, 6H), 7.15 (s, 5H), 7.04-7.09 (m, 2H), 6.79-6.85 (m, 1H), 6.66 (dd, J=3.6,1.2Hz,
1H),5.35(s,1H).Anal.Calcd for C24H20SSi:C,78.21；H,5.47.Found:C,77.75；H,5.63.
P10:(E)-(1,2-diphenylvinyl) diphenylsilane
80 DEG C, under condition of nitrogen gas, CoX is sequentially added in a dry reaction tube2- OIP complex compound (0.02mmol),
Tetrahydrofuran (2ml), diphenyl silicon hydrogen (1.0mmol) are injected into sodium triethylborohydride (0.06mmol), alkynes
(1.0mmol) then stirs column chromatography for separation after five minutes and obtains product.Colourless liquid, 33% yield.IR(cm-1):3062,
1595,1489,1429,1110.1H NMR(CDCl3,400MHz):δ7.51-7.60(m,4H),7.21-7.40(m,6H),
6.93-7.20(m,11H),5.28(s,1H)；13C NMR:(CDCl3,100MHz):δ142.9,141.6,140.2,136.9,
135.8,133.0,129.8,129.6,128.6,128.02,128.98,127.9,127.5,126.1.HRMS(EI)
calculated for[C26H22Si]+requires m/z 362.1491,found m/z 362.1489.
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 (8)
1. a kind of method for synthesizing alkenyl silanes class compound, characterized in that using alkynes as raw material, using silane as silicon 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 5 seconds~30 points
Alkenyl silanes, the alkynes, silane, CoX is made in clock2- OIP complex compound, sodium triethylborohydride molar ratio be 1:1:
0.0005-0.02:0.0015-0.06；
The structural formula of the alkynes isR1, R2Optionally aryl, heteroaryl, alkyl, hydrogen, aryl optionally replace
ArylSubstituted 1- naphthalene2- naphthalene
Heterocyclic arylY is any one in N, O, S, R1,R2,R3, R4, R5, R6, R7, R8, R9, R10, R11, R12,
R13, R14, R15, R16, R17, R18, R19, R20, R21, R22Optionally from H, halogen, C1-C16Alkyl, C1-C16Oxyl, hydrocarbon sulphur
Base, amino, amido, thiophene, any one in pyrroles, the CoX2The structural formula of-OIP complex compound is optically pure as follows
Compound or its enantiomer or raceme, R23, R24, R25, R26, R27Optionally from C1-C16Alkyl, naphthalene, substituted aryl, benzyl
Base:
X is F, Cl, Br, I, OAc, CF3SO3In any one.
2. the method for synthesis alkenyl silanes class compound according to claim 1, characterized in that its structure of the silane
Formula isWherein Ar2、Ar3Aryl, the substituted heteroaryl optionally replaced.
3. the method for synthesis alkenyl silanes class compound according to claim 1, characterized in that have in the synthetic method
The participation of organic solvent, 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.
4. the method for synthesis alkenyl silanes class compound according to claim 1, characterized in that in the synthetic method not
Add any solvent.
5. the method for synthesis alkenyl silanes class compound according to claim 1 or 2 or 3 or 4, characterized in that described
Alkynes, silane, CoX2- OIP complex compound, sodium triethylborohydride molar ratio be 1:1:0.004-0.02:0.012-0.06.
6. the method for synthesis alkenyl silanes class compound according to claim 1 or 2 or 3 or 4, characterized in that the conjunction
At in method, reaction temperature is -10 DEG C~40 DEG C.
7. the method for synthesis alkenyl silanes class compound according to claim 6, characterized in that in the synthetic method,
Reaction temperature is 20 DEG C, and the reaction time is 5 minutes or 20 minutes.
8. synthesizing the method for alkenyl silanes class compound described according to claim 1 or 2 or 3 or 4 or 7, characterized in that gained
Product be by recrystallization, thin-layer chromatography, column chromatography or vacuum distillation separated.
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| Aryl–aryl interactions as directing motifs in the stereodivergent iron-catalyzed hydrosilylation of internal alkynes;Christian Belger等，;《Chem. Commun.》;20120417;第48卷;第5419–5421页 |
| Bis(acetylacetonato)Ni(II)/NaBHEt3-catalyzed hydrosilylation of 1,3-dienes, alkenes and alkynes;Venu Srinivas等，;《Journal of Organometallic Chemistry》;20160223;第809卷;第57-62页，尤其是第61页表3 |
| Hydrosilylation of Internal Alkynes Catalyzed by TrisImidazolium Salt-Stabilized Palladium Nanoparticles;Marc Planellas等，;《Adv. Synth. Catal.》;20140113;第356卷;全文 |
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