CN109503645A - It is a kind of containing there are four si-h bond chirality together with two silicon substrate alkane compounds and its synthetic method and application - Google Patents
It is a kind of containing there are four si-h bond chirality together with two silicon substrate alkane compounds and its synthetic method and application Download PDFInfo
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- CN109503645A CN109503645A CN201811375242.3A CN201811375242A CN109503645A CN 109503645 A CN109503645 A CN 109503645A CN 201811375242 A CN201811375242 A CN 201811375242A CN 109503645 A CN109503645 A CN 109503645A
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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
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
- C07F7/0829—Hydrosilylation reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
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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
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
Abstract
The invention discloses a kind of chiralitys containing there are four si-h bond together with two silicon substrate alkane compounds, as shown in Formula IV, and two kinds of chiralitys are disclosed together with the synthetic method of two silicon substrate alkane compounds: under (one) inert gas, using three hydrogen silanes shown in alkenyl silanes class compound shown in Formula V and formula IV as raw material, with chiral CoX2- IIP complex compound is catalyst, in the presence of a reducing agent, reacts and Formula IV is made；(2) under inert gas, using three hydrogen silanes shown in three hydrogen silanes, formula IV shown in alkynes shown in Formulas I and Formula II as raw material, with CoY2, bis- (2- diphenylphosphine phenyl) ethers and chirality CoX2- IIP complex compound is catalyst, in the presence of a reducing agent, reacts and Formula IV is made.The method of the present invention reaction condition is mild, easy to operate, and Atom economy is high, has outstanding yield (57%~84%), high regioselectivity (> 19:1), high enantioselectivity (91.6-98.8%ee).
Description
Technical field
This method is related to a kind of containing there are four the chiral of si-h bond together with two silicon substrate alkane compounds and its synthetic method and to answer
With.
Background technique
Chiral organosilan is in organic synthesis [(a) Masse, C.E.；Panek,J.S.Chem.Rev.1995,95,1293.
(b)Fleming,I.；Barbero,A.；Walter,D.Chem.Rev.1997,97,2063.(c)Brook,M.A.Silicon
in Organic,Organometallic and Polymer Chemistry,Wiley,New York,2000.(d)Zhang,
H.-J.；Priebbenow,D.L.；Bolm, C.Chem.Soc.Rev.2013,42,8540.] and functional material [(a) Ojima,
I.In The Chemistry of Organic Silicon Compounds；Patai,S.,Rappoport,Z.,Eds.；
Wiley:Chichester,1989；Vol.1,Chapter 25.(b)Silicon in Organic,Organometallic,
and Polymer Chemistry；Brook,M.A.,Ed.；Wiley:New York,1999.(c)Ponomarenko,S.A.；
Kirchmeyer, S.Adv Polym Sci.2011,235,33.] etc. fields have important application.Together with two silicon substrate alkane, i.e.,
Two silicon substrate groups are connected in the compound on the same carbon of alkyl, on the one hand modifiable there are two due to such compound
Silicon substrate, compared to single silicon compound, conversion has more diversity；On the other hand, together with the special steric effect of two silicon substrates and electronics
The chemo-selective of the changeable tradition reaction of effect, regioselectivity, stereoselectivity, therefore have extensively in organic synthesis
Application [(a) Gao, L.；Zhang,Y.-B.；Song,Z.-L.Synlett 2013,24,139.(b)Wu,Y.；Li,L.；Li,
H.；Gao,L.；Xie,H.；Zhang,Z.；Su,S.；Hu,C.；Song,Z.Org.Lett.2014,16,1880-1883.(c)
Gao,L.；Lu,J.；Song,Z.L.；Lin,X.L.；Xu,Y.J.；Yin,Z.P.Chem.Commun.2013,49(79),8961-
8963.(d)Liu,Z.J.；Lin,X.L.；Yang,N.；Su,Z.S.；Hu,C.W.；Xiao,P.H.；He,Y.Y.；Song,
Z.L.J.Am.Chem.Soc.2016,138(6),1877-1883.(e)Chu,Z.W.；Wang,K.；Gao,L.；Song,
Z.L.Chem.Commun.2017,53(21),3078-3081.(f)Chu,Y.；Pu,Q.；Tang,Z.X.；Gao,L.；Song,
Z.L.Tetrahedron 2017,73(26),3707-3713.].However, due to lacking effective method at present to efficiently just
Prompt ground synthesis of chiral is more widely applied exploration and is greatly limited together with two silicon substrate alkane, such chiral organosilan.
The chirality containing multiple si-h bonds is especially prepared together with two silicon substrate alkane, there is meaning of the utmost importance.The chirality of more si-h bonds is together with two
Silicon substrate alkane contains multiple modifiable si-h bonds, and si-h bond can be converted into silicon-carbon bonds, silicon halogen key, and silicon oxygen bond etc. has
Subsequent modification and conversion abundant, there is great application value [Cheng, B.；Lu,P.；Zhang,H；Cheng,X.；Lu,
Z.J.Am.Chem.Soc.2017,139,9439-9442]。
The series connection silicon hydrogenation of alkynes, has many advantages, such as that reaction raw materials are easy to get, and reaction of atomic economy is high, is efficiently to make
The ideal method of standby more silicon compounds.In 2002, professor Hayashi etc. reported the company of Pd Yu the syncatalytic aryl alkynes of Pt
Continuous silicon hydrogenation comes synthesis of chiral 1,2- bis- silicon compound [Shimada, T.；Mukaide,K.；Shinohara,A.；Han,
J.W.；Hayashi,T.J.Am.Chem.Soc.2002,124,1584].However the series connection could not be prepared together with two silicon compounds,
The compound of silicon-hydrogen bond containing could not be prepared, and aliphatic alkynes is not reported.
Compared to platinum-group noble metals, the earth get bumper crops transition metal (Fe, Co, Ni etc.) there is big (the wherein metallic cobalt of reserves
Shell content is up to 7,160,000 tons, a total of about 7.1 ten thousand tons of platinum group metal allowable exploitation), low toxicity, the features such as cheap, bio-compatibility is good.
From angle of sustainable development, earth high yield transition metal is the ideal substitute of platinum-group noble metals, is with a wide range of applications.
[(a)Pellissier,H.Coord.Chem.Rev.2018,360,122.(b)Moselage,M.；Li,J.；Ackermann,
L.ACS Catal.2016,6,498.(c)Gao,K.；Yoshikai,N.Acc.Chem.Res.2014,47,1208.(d)
Pellissier,H.；Clavier,H.Chem.Rev.2014,114,2775.(e)Cahiez,G.；Moyeux,
A.Chem.Rev.2010,110,1435.].Therefore, develop the end rouge of the highly selective earth high yield metal catalytic of high efficiency
The series connection silicon hydrogenation of fat race alkynes has great meaning together with two silicon substrate alkane compounds synthesize more si-h bonds.
Three hydrogen silanes contain a changeable alkyl group and three si-h bonds, be it is simple and easy to get, be easy to modify it is more
Hydrogen silane.If the silicon hydrogenation that anti-geneva selection occurs for three hydrogen silane of a molecule and a molecular end alkynes generates alkenyl silication and closes
Then object passes through Asymmetric hydrosilylation by alkenyl silicon compound again, then can prepare containing the chirality there are four si-h bond together with two
Silicon compound.But there are reactive chemistry selectivity, regioselectivity, enantioselectivities the difficulties such as to be difficult to for the reaction, it is real
Such existing conversion is extremely challenging.Especially since two parts of silane used is all three hydrogen silanes, difference only has the upper of silane
The regulation of one substituent group difference, mapping selection is particularly difficult.In addition, in tandem reaction there are 1,1- addition, 1,2- addition,
The regulation of 2,1- additions, 2,2- addition, four kinds of regional choices, regional choice equally has very big challenge.Finally, how to adjust
Control generate four silicon hydrogen chiralitys together with two silicon compounds not with alkynes further occurrence it is excessive react and a big difficulty.
Therefore, it is made by the alkynes series connection silicon hydrogenation of cheap metal catalysis or alkenyl silicon Asymmetric hydrosilylation
The standby chirality containing there are four si-h bond has great challenge together with two silicon substrate alkane compounds.Containing there are four the chiralitys of si-h bond
Efficient preparation together with two silicon substrate alkane compounds has not been achievable before this, and the preparation of such compound is to organic synthesis
, the development of material, medicine and other fields have great importance.
Summary of the invention
The problem to be solved in the present invention is to provide it is a kind of containing there are four si-h bond it is chiral together with two silicon substrate alkane compounds and
Its synthetic method.
The technical solution adopted by the present invention is that: it is a kind of containing there are four the chiral together with two silicon substrate alkane compounds of si-h bond, by
CoX2The synthesis of-IIP complex catalysis is made.
It is a kind of containing there are four si-h bond chirality together with two silicon substrate alkane compounds, as shown in Formula IV:
In Formula IV, R2,R3For different group.
In Formula IV, * represents asymmetric carbon atom.
In Formula IV, R1Optionally from the silylation of the naphthenic base or C1~C16 of the alkyl of H, C1-C16 or C3-C16；The alkane
H on base, naphthenic base or silylation is not substituted or is replaced by 1 or more substituent A, and the substituent A includes C1-C10
Alkenyl, nitro, halogen, aryl A, heterocyclic aryl A, phthalimide-based, methoxycarbonyl group, trifluoromethyl, hydroxyl, C1~
The aldehyde radical of C3, the carboxyl of C1~C3, amino, the ester group of C1~C16, the silylation of C1-C16, the siloxy of C1-C16, C1-C16
Alkoxy, the sulfonyl of C1~C16, benzyloxy or C1-C10 amide groups；The aryl A includes phenyl or naphthyl；It is described
Heterocyclic aryl A includes indyl, thienyl, pyridyl group, piperidyl, quinolyl, group shown in carbazyl or Formula VII；It is described
Alkenyl, aryl A, the H on heterocyclic aryl A are not substituted or are replaced by 1 or more substituent B, the substituent B include C1~
The alkyl of C6, the alkoxy of C1~C3, halogen, trifluoromethyl, hydroxyl, the aldehyde radical of C1~C3, the carboxyl of C1~C3, amino, C1
Ester group, phenyl or the amide groups of~C3；
In Formula VII, right end horizontal line "-" indicates the connecting key of group and carbon atom, without indicating methyl
R2,R3Optionally from benzyl, phenylethyl, the alkyl of C1-C16, aryl B or heterocyclic aryl B, the aryl B such as formula
Shown in X or Formula XI:
In Formula X, R4、R5、R6、R7、R8Optionally from H, halogen, the alkyl of C1-C16, the alkoxy of C1-C16, C1-C16 alkane
Sulfenyl, phenyl, trifluoromethyl, methoxycarbonyl group, nitro, hydroxyl, the aldehyde radical of C1~C3, the carboxyl of C1~C3, amino, C1~C16
Ester group, the silylation of C1-C16, the siloxy of C1-C16, benzyloxy, amide groups, acetyl-o-methyl, 2- methyl-1,3-dioxy
Any one in cyclopenta；R4、R5、R6、R7、R8When being all H, group shown in Formula X is phenyl；
In Formula XI, R9、R10、R11、R12、R13、R14、R15Optionally from H, halogen, the alkyl of C1-C16, C1-C16 alcoxyl
Base, the alkylthio group of C1-C16, phenyl, trifluoromethyl, methoxycarbonyl group, nitro, hydroxyl, the aldehyde radical of C1~C3, C1~C3 carboxyl,
Amino, the ester group of C1~C16, the silylation of C1-C16, the siloxy of C1-C16, benzyloxy, amide groups, acetyl-o-methyl, 2-
Any one in methyl-1,3-dioxy cyclopenta；R9、R10、R11、R12、R13、R14、R15When being all H, group shown in Formula XI
As naphthalene；
The heterocyclic aryl B is indyl, thienyl, pyridyl group, piperidyl, carbazyl or quinolyl.
Further, the preferably described R1For the silylation of the alkyl of H, C1-C16, the naphthenic base of C3-C16 or C1~C16；Institute
It states the H on alkyl not to be substituted or replaced by 1 or more substituent A, the substituent A includes alkenyl, halogen, phenyl, naphthalene
Base, thienyl, indyl, pyridyl group, quinolyl, piperidyl, carbazyl, methoxycarbonyl group, trifluoromethyl, hydroxyl, amino, C1~
Ester group, tertiary butyl dimethyl Si base, benzyloxy, amide groups, tolysulfonyl amido, the mesyl, N of C10, N- diethyl
Group shown in amine carbonyl or Formula VII；H on the phenyl, naphthalene is not substituted or is replaced by 1 or more substituent B, institute
Stating substituent B includes the alkyl of C1~C3, the alkoxy of C1~C3, halogen, trifluoromethyl, hydroxyl, the carboxyl of C1~C3, ammonia
Base, the ester group of C1~C3, phenyl or amide groups；
Preferably, R2、R3For benzyl, phenylethyl or aryl B, wherein aryl B is as shown in Formula X or Formula XI:
Group shown in Formula X is preferably phenyl or the substituted-phenyl containing 1~2 or less substituent group: the alkyl of C1~C4,
Phenyl, the alkoxy of C1~C4, methyl mercapto, F, Cl, Br, trifluoromethyl, methoxycarbonyl group, acetyl-o-methyl.
Group shown in Formula XI is preferably naphthalene or the substituted naphthyl containing 1~2 or less substituent group: the alkane of C1~C4
Base, phenyl, the alkoxy of C1~C4, methyl mercapto, F, Cl, Br, trifluoromethyl, methoxycarbonyl group, acetyl-o-methyl.
Further, in the Formula IV, R1The preferably alkyl of H, C1-C10, the naphthenic base of C3-C10 or trimethyl silicane
Base, the alkyl can be indicated by following formula: CnH2n+1Or RA—(CH2)n-, the integer that n is 1~10, CnH2n+1It indicates
H on alkyl is not substituted, RA—(CH2)n- in RAFor the substituent group in carbochain, RAIncluding ethylenyl, halogen, phenyl,
Naphthalene, thienyl, piperidyl, indyl, carbazyl, hydroxyl, methoxycarbonyl group, tertiary butyl dimethyl Si base, benzyloxy, amide
Base, ethyoxyl oxalic acid ester group, tosyl amido, mesyl, N, group shown in N- diethylamide carbonyl or Formula VII, institute
The H on phenyl is stated not to be substituted or replaced by 1~2 substituent B, the substituent B include the alkyl of C1~C3, halogen,
Trifluoromethyl or phenyl；Further, when the H on the phenyl is replaced by 1~2 substituent B, preferably substituted-phenyl is neighbour
Aminomethyl phenyl, aminomethyl phenyl, p-methylphenyl or xenyl.
Further, preferably R2, R3Optionally benzyl, phenylethyl, phenyl, naphthalene, rubigan or to methoxybenzene
Base；
It is described the present invention also provides the synthetic method containing there are four the chirality of si-h bond together with two silicon substrate alkane compounds
Method is one of the following: under method (one) inert gas, with three hydrogen shown in alkenyl silanes class compound shown in Formula V and formula IV
Silane is raw material, with chiral CoX2- IIP complex compound is catalyst, in the presence of a reducing agent, reacts to be made shown in Formula IV and contain
The chirality of four si-h bonds is together with two silicon substrate alkane compounds；
Shown in reaction equation such as following formula (1):
In Formula V, IV, R1、R2、R3It is defined as described above, R2,R3For different group.
Under method (two) inert gas, with three hydrogen shown in three hydrogen silanes, formula IV shown in alkynes shown in Formulas I and Formula II
Silane is raw material, with CoY2, bis- (2- diphenylphosphine phenyl) ethers (Dpephos) and chirality CoX2- IIP complex compound is catalyst,
In the presence of reducing agent, reacts and be made shown in Formula IV containing the chirality there are four si-h bond together with two silicon substrate alkane compounds；
Shown in reaction equation such as following formula (2):
Formulas I, Formula II, in IV, R1、R2、R3It is defined as described above, R2,R3For different group.
In the method (one), alkenyl silanes class compound shown in Formula V can refer to ACS Catal.2018, and 8,5896-
5900 or Chem.Commun., 2018,54,12322-12325 document are synthesized.
In the method (two), CoY2In Y be F, Cl, Br, I, OAc (acetate anion), Acac (acetylacetone,2,4-pentanedione yin from
Son) in any one, the preferred OAc of Y.
In the method (two), more specifically, preferably reacts and carry out by the following method: under inert gas, alkynes shown in Formulas I
Three hydrogen silanes, CoY shown in hydrocarbon and Formula II2, bis- (2- diphenylphosphine phenyl) ethers in the presence of a reducing agent, reaction 0.5~60 is small
When (preferably 0.5~10 hour, more preferable 3~4 hours) after, add chiral CoX2Shown in-IIP complex compound catalyst, formula IV
Three hydrogen silanes and reducing agent, react 0.5~60 hour (preferably 0.5~10 hour, more preferable 3~4 hours), be made Formula IV institute
The chirality of si-h bond containing there are four shown is together with two silicon substrate alkane compounds.
Catalyst used in the present invention is chirality CoX2- IIP complex compound (IIP: '-imine pyridinyl imidazoline ligand), wherein hand
Property CoX2The structural formula of-IIP complex compound is formula III compound represented or its enantiomer, and the enantiomer is the mirror of formula III
Picture.
In formula III, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25,R26,R27,R28Optionally from the alkane of H, C1-C16
Base, the alkoxy of C1-C16, phenyl, naphthalene or benzyl: H on the alkyl, alkoxy is not substituted or is taken by 1 or more
For base E replace, the substituent group E include nitro, halogen, phenyl, methoxycarbonyl group, trifluoromethyl, hydroxyl, C1~C3 aldehyde radical,
The carboxyl of C1~C3, amino, C1~C3 ester group or amide groups；
The phenyl, benzyl, the H on naphthalene are not substituted or are replaced by 1 or more substituent group D, the substituent group D packet
Include the alkyl of C1~C3, the alkoxy of C1~C3, nitro, halogen, phenyl, methoxycarbonyl group, trifluoromethyl, hydroxyl, C1~C3
Aldehyde radical, the carboxyl of C1~C3, amino, C1~C3 ester group or amide groups；
X is F, Cl, Br, I, OAc, CF3SO3In any one.
Further, the chirality CoX2The structural formula of-IIP complex compound is preferably formula III compound represented, in formula III,
It is preferred that R16、R17、R18、R26、R27It is H；R19For methyl；R20For C1-C4Alkyl, R21For H, R22For H, C1-C4Alkyl, C1-
C4Alkoxy or halogen；R23For H；R24For C1-C4Alkyl；R25For C1-C4Alkyl, benzyl or phenyl；R28For C1-C4's
Alkyl, benzyl or phenyl；X is Cl.
It is furthermore preferred that chiral CoX used2- IIP complex compound is as shown in formula III -1
In the method for the present invention, chiral CoX2The synthetic method of-IIP complex compound can refer to document
J.Am.Chem.Soc.2017,139,15316-15319
As a further improvement, two kinds of synthetic methods of the present invention can it is solvent-free or in organic solvent into
Row, when reacting in organic solvent, the organic solvent can be benzene, toluene, tetrahydrofuran, ether, dioxane, petroleum
Ether, hexamethylene, n-hexane, any one in ethyl acetate, preferably toluene.
The volumetric usage of the organic solvent is generally with alkynes shown in Formulas I or with the substance of alkenyl silicon shown in Formula V
Amount be calculated as 0.1~10mL/mmol.
Present invention reaction all carries out under an inert gas, and the inert gas can be nitrogen or argon gas.
In synthetic method (one) of the present invention, three hydrogen silicon shown in alkenyl silanes class compound, formula IV shown in Formula V
Alkane, chirality CoX2The ratio between amount of substance of-IIP complex compound, reducing agent is 1:0.1-10:0.0000005-0.1:0.000003-
0.33, preferably 1:0.1-3:0.005-0.1:0.015-0.33, more preferably 1:0.5-2.5:0.01-0.1:0.015-
0.33；More preferable 1:1.0-1.5:0.01-0..05:0.03-0.15；Most preferably 1:1.1:0.03:0.09.
In synthetic method (two) of the present invention, shown in three hydrogen silanes, formula IV shown in alkynes, Formula II shown in Formulas I
Three hydrogen silanes, CoY2, bis- (2- diphenylphosphine phenyl) ethers, chirality CoX2The ratio between amount of substance of-IIP complex compound, reducing agent is 1:
0.1-10:0.1-10:0.0000005-0.1:0.0000005-0.1:0.0000005-0.1: 0.000003-0.33, preferably
1:0.1-3:0.1-3:0.005-0.1:0.005-0.1:0.005-0.1:0.015-0.33 more preferably 1:0.5-2.5:0.5-
2.5:0.01-0.1:0.01-0.1:0.01-0.1:0.015-0.33；More preferably 1:1.0-1.5:1.0-1.5:0.01-0.1:
0.01-0.1:0.01-0.05:0.015-0.33 is most preferably 1:1:1:0.02:0.024:0.03:0.15.
In the method (two), reducing agent is divided into two parts addition, total dosage that the dosage of above-mentioned reducing agent refers to.
Further, in method (two), the amount of reducing agent is the total amount that two-step reaction is added, and first step reaction and second step are anti-
The ratio between amount of substance of reducing agent that should be separately added into is 2:3.
As a further improvement, reaction temperature is -30 DEG C~80 DEG C, excellent in two kinds of synthetic methods of the present invention
- 10 DEG C~50 DEG C of choosing, it is particularly recommended that 5~30 DEG C.
The reaction time of the method for the present invention (one) preferably -60 hours 0.5 hour, more preferably -10 hours 0.5 hour, especially
It is recommended 2~3 hours.
In the method for the present invention, the reducing agent is sodium triethylborohydride, three sec-butyl sodium borohydrides, boron triethyl hydrogenation
Lithium, sodium tert-butoxide, potassium tert-butoxide, tert-butyl alcohol lithium, sodium tert-amyl alcohol, sodium ethoxide, sodium methoxide, any one in potassium methoxide, preferably
Sodium triethylborohydride, sodium tert-butoxide, sodium ethoxide, sodium methoxide, more preferably sodium triethylborohydride.
As a further improvement, the method for the present invention (one) and method (two) are after reaction, gained crude product passes through
Post-process and chirality shown in Formula IV be made together with two silicon substrate alkane compounds, further, the post-processing approach be it is following a kind of or
Two or more: recrystallization, thin-layer chromatography, column chromatography or vacuum distillation, preferably column chromatograph.
The method of the present invention (one) provides one kind effectively by chiral CoX2- IIP is catalyst, by alkenyl silanes class chemical combination
Object and three hydrogen silanes be raw material high efficiency, high regioselectivity, high enantioselectivity synthesis of chiral together with two silicon substrate alkane chemical combination
The method of object.This method reaction condition is mild, easy to operate, and Atom economy is high, and reacts with medium to outstanding yield
(57%~85%), high regioselectivity (> 19:1), high enantioselectivity (91.6-98.8%ee).
The method of the present invention (two) provides one kind effectively by chiral CoX2- IIP is catalyst, by alkynes and two kinds of differences
Three hydrogen silanes be raw material, high efficiency, high regioselectivity, high enantioselectivity synthesis of chiral together with two silicon substrate alkane compounds
Method.This method reaction condition is mild, easy to operate, and Atom economy is high, is easy to get compared to method (one) with raw material, grasps
Make more convenient advantage, and reacts with outstanding yield (72%~84%), high regioselectivity (> 19:1), high mapping
Selectivity (97.6-98.8%ee)；
Chirality shown in Formula IV provided by the invention can be used for oxidative synthesis fat aldehydes together with two silicon substrate alkane compounds
Object is closed, chiral silicon alcohol compound, chiral polysubstituted silane compound, chiral fluoro are together with two silicon substrate alkane compounds etc..Often
Rule are outer disappear together with two silicon substrate alkane or the like compound for synthctic fat aldehyde compound, chiral silicon alcohol compound,
Chiral polysubstituted silane compound all belongs to known to method, and convert silanol for si-h bond and polysubstituted silane method is same
There are a large amount of documents can for reference, and the chirality that the present invention synthesizes is equally applicable together with disilane hydrocarbon compound.Its difference only exists, this
Invention can be that Material synthesis goes out corresponding chiral product, therefore the chirality of the application is together with disilane hydrocarbon together with disilane hydrocarbon by chirality
It can be further used for the synthesis of optically active organo-silicon compound, there is biggish application value.
Further, chirality shown in the Formula IV can be used for oxidative synthesis fat aldehydes chemical combination together with two silicon substrate alkane compounds
Object, the method are together with two silicon substrate alkane compounds by chirality shown in Formula IV through H2O2Oxidation, reaction are obtained as shown in formula A
Fatty aldehyde compound, reaction equation is shown below:
Further, the reaction condition of the oxidative synthesis fat aldehyde compound is general are as follows: chirality is together with two shown in Formula IV
After silicon substrate alkane compound and tetrafluoro boric acid-etherate catalyst are stirred to react, then with tetrabutyl ammonium fluoride, bicarbonate
Fatty aldehyde compound shown in formula A is made in potassium, hydrogen peroxide reaction；
Further, the reaction step of the preferably described oxidative synthesis fat aldehyde compound are as follows: chirality is together with two shown in Formula IV
Silicon substrate alkane compound and tetrafluoro boric acid-etherate catalyst are in chloroform solvent, and back flow reaction 10~30 hours,
Solvent is removed, tetrahydrofuran, methanol, tetrabutyl ammonium fluoride, saleratus, hydrogen peroxide is added, 1~10h of reaction is stirred at room temperature, adds
It is saturated NaHSO3Solution dilution is made shown in formula A after removing solvent through column chromatography for separation after ether extraction, washing, water removal are dry
Fatty aldehyde compound；Chirality shown in the Formula IV is together with two silicon substrate alkane compounds, tetrafluoro boric acid-etherate, four
Butyl ammonium fluoride, saleratus, H2O2The ratio between the amount of substance be 1:5~8:5~10:8~10:40~50.
Further, chirality shown in the Formula IV can be used for the polysubstituted silanes of synthesis of chiral together with two silicon substrate alkane compounds
Compound, the method are as follows: by chirality shown in Formula IV together with two silicon substrate alkane compounds and CH2I2Reaction, in Et2The work of Zn
Under, reaction is obtained such as the polysubstituted silane compound of chirality shown in formula B；Reaction equation is as follows:
Further, the reaction step of the polysubstituted silane compound of the synthesis of chiral are as follows: under the protection of argon gas, Formula IV
Shown in chirality together with two silicon substrate alkane compounds and CH2I2In 1,2- dichloroethanes (DCE) solvent, 5~10 are stirred at 0 DEG C
After minute, ZnEt is slowly added dropwise2, continue to stir 30~60 minutes at 0 DEG C, be then stirred to react 30~60 in room temperature condition
Hour, after completion of the reaction, NH is saturated in 0 DEG C of addition4Cl solution quenching reaction, is extracted with dichloromethane, dries, after removing solvent
It obtains through column chromatography for separation such as the polysubstituted silane compound of chirality shown in formula B.Chirality shown in the Formula VII is together with two silicon substrates
Alkane compound, CH2I2、ZnEt2The ratio between the amount of substance be 1:50:30.
Further, the polysubstituted silane compound of chirality shown in the formula B can be further converted to chirality shown in formula C
Together with two silicon substrate alkane compounds, chirality fluoro shown in the formula C can converted further fluoro together with two silicon substrate alkane compounds
For chirality silicon alcohol compound shown in formula D.
Further, chirality fluoro shown in the polysubstituted silane compound preparation formula C of the chirality as shown in formula B is together with two
The reaction step of silicon substrate alkane compound are as follows: the polysubstituted silane compound of chirality shown in formula B and boron trifluoride ether, acetic acid
In chloroform solvent, back flow reaction 16 hours at 65 DEG C.After completion of the reaction, methylene chloride dilution is added, uses saturated sodium carbonate
Solution washing, and it is dry with anhydrous sodium sulfate, the chirality fluoro as shown in formula C is obtained together with two through column chromatography for separation after removing solvent
Silicon substrate alkane compound.The substance of the polysubstituted silane compound of chirality, boron trifluoride ether shown in the formula B, acetic acid
The ratio between amount is 1:10:40.
Further, the chirality fluoro as shown in formula C is together with chirality silanol shown in two silicon substrate alkane compound preparation formula D
The reaction step of compound are as follows: chirality fluoro shown in formula C together with two silicon substrate alkane compounds and anhydrous potassium fluoride, m-CPBA (
Chloroperoxybenzoic acid) in anhydrous DMF (n,N-Dimethylformamide) solvent, 36 are stirred in dry reaction tube at room temperature
Hour.After completion of the reaction, methylene chloride dilution is added, with saturated sodium thiosulfate solution, saturated sodium carbonate solution, saturated common salt
Water washing, and it is dry with anhydrous sodium sulfate, the chirality silicon alcohol compound as shown in formula D is obtained through column chromatography for separation after removing solvent
Compound.Chirality fluoro shown in the formula C together with two silicon substrate alkane compounds, potassium fluoride, metachloroperbenzoic acid substance
The ratio between amount is 1:5:5.
The present invention provides a kind of effectively by alkenyl silicon and three hydrogen silane synthesis of chiral together with the side of disilane hydrocarbon compound
Method；And it is a kind of effectively by alkynes and two different three hydrogen silanes synthesis of chiral together with the method for disilane hydrocarbon compound.It should
Method is with chiral CoX2- IIP complex compound, can be by alkenyl silicon and three hydrogen silanes or by alkynes and different as catalyst
Selectively synthesizing optical is active containing there are four the chiral together with disilane hydrocarbonylation of si-h bond for three hydrogen silane high efficiency, high antimer
Close object.
It is that the present invention synthesizes for the first time containing there are four the chiralitys of si-h bond together with two silicon substrate alkane compounds, not only has optics living
Property, and so many si-h bond can bring a possibility that more for the modification in compound later period, have more diversity using upper,
Have great importance to the development of Synthetic Organic Chemistry, material, medicine and other fields.
Detailed description of the invention
Fig. 1 catalyst chirality CoX2The mono-crystalline structures figure of-IIP complex compound III-1.
Mono-crystalline structures figure of Fig. 2 chirality together with two silicon substrate alkane products VI-6.
Specific embodiment
Technical solution of the present invention is further illustrated below by specific embodiment, but protection of the invention
Range is without being limited thereto:
Alkenyl silanes class compound shown in starting materials of formulae V can refer to ACS Catal.2018,8,5896-5900 or
Chem.Commun., 2018,54,12322-12325 document is synthesized.
In embodiment, chiral CoX used2Shown in the following formula III -1 of the chemical formula of-IIP complex compound:
It is specific the preparation method is as follows:
Under nitrogen protection, palladium acetate (0.0576g, 0.26mmol) is added into dry Schlenk reaction tube, triphen
Base phosphorus (0.1336g, 0.51mmol), cuprous iodide (0.9677g, 5.1mmol), 11 carbon -7- alkene of 1,8- diazabicylo
(0.75mL, 1.018g/mL, 5.0mmol), (S) -4- isopropyl-N- phenyl -4,5- dihydro -1H- imidazoles (0.9517g,
5.1mmol), 6- (1- (N-2,6- diisopropyl phenyl) ethyleneimine base)) -2 bromopyridines (1.8164g, 5.1mmol), 15mL
DMF.Three times, reaction mixture stirs 22 hours the effective liquid nitrogen degassing of Schlenk in 110 DEG C of oil baths, is then cooled to room temperature,
The sand core suction filtration for being placed with silica gel is poured into, is diluted with 300mL ether, is successively washed with 10% ammonia spirit (2 × 250mL) and full
It is washed with NaCl solution, with Na2SO4Make desiccant dryness.After rotary evaporation removes solvent, with petroleum ether: ethyl acetate (2:1)
Mixed solvent carries out the isolated yellow solid XII-1 of column chromatography chromatogram as stationary phase as mobile phase, silica gel
(1.4648g, 3.1mmol, 61% yield).Optical Rotation:[α]20 D=-35.8 (c 0.93, CHCl3) .M.P.:
110-113oC.IR(cm-1):2960,1645,1592,1497,1389.1H NMR(400MHz,CDCl3): δ 8.29 (d, J=
7.6Hz, 1H), 8.08 (d, J=8.0Hz, 1H), 7.82 (dd, J=8.0,7.6Hz, 1H), 7.17-7.07 (m, 4H), 7.07-
7.01 (m, 1H), 6.93 (dd, J=7.6,7.2Hz, 1H), 6.82 (d, J=7.2Hz, 2H), 4.22-4.09 (m, 2H), 3.78-
3.65(m,1H),2.69-2.50(m,2H),2.06-1.91(m,1H),1.53(s,3H),1.16-0.97(m,18H)；13C NMR
(100MHz,CDCl3):δ167.0,159.9,154.8,148.6,146.2,143.7,136.9,135.7,135.6,128.2,
125.1,123.4,123.2,122.81,122.78,121.6,70.5,56.6,33.1,28.05,28.01,23.12,23.09,
22.8,19.0,18.0,16.4；HRMS(EI)calculated for[C31H38N4]+requires m/z 466.3096,
found m/z 466.3099.
In N2Under protection, XII-1 (0.4667g, 1.0mmol) is added into dry Schlenk pipe, THF (5mL),
CoCl2(0.1215g,0.94mmol).After reaction mixture stirs 3h at 25 DEG C, injection 20mL ether enters reaction mixing
Object continues to stir 2h.Reaction mixture filtering, solid are washed with ether (10mL), are dried under vacuum, and obtain brown ceramic powder
(0.4451g, 0.75mmol, 80% yield).
The mono-crystalline structures of III-1 are as shown in Figure 1, No. CCDC: 1525168
Embodiment 1: chiral CoX2The alkenyl silicon and silane Asymmetric hydrosilylation of-IIP complex catalysis
Under room temperature, argon gas, chiral CoX is sequentially added in a dry reaction tube2- IIP complex compound (0.015mol,
3mol%), toluene (2.0mL), three hydrogen silanes (0.55mmol) shown in formula IV, sodium triethylborohydride (0.045mol,
9mol%), alkenyl silicon (0.5mmol) shown in Formula V.(eluting solvent is petroleum ether to column chromatography for separation after stirring 2 hours at room temperature
Or the mixture of petroleum ether and ethyl acetate) obtain product.(in individual reaction conditions, chiral CoX2- IIP complex compound and three second
The dosage of base sodium borohydride changes, and specifically indicates under each product.)
VI-1:
(R)-benzyl (1- (phenyl silicon substrate) hexyl) silane
(R)-benzyl(1-(phenylsilyl)hexyl)silane
Oily liquids, 83% yield, regioselectivity > 19/1, [α]20 D=-8.3 (c 1.02, CHCl3), 98.8%ee,
IR(cm-1):2966,2921,2130,1598,1407,1060；1H NMR(400MHz,CDCl3):δ7.57-7.53(m,2H),
7.40-7.32(m,3H),7.24-7.19(m,2H),7.11-7.02(m,3H),4.39-4.33(m,2H),3.91-3.82(m,
2H),2.21-2.17(m,2H),1.61-1.52(m,2H),1.40-1.32(m,2H),1.27-1.16(m,4H),0.84(t,J
=7.2Hz, 3H), 0.48-0.40 (m, 1H)；13C NMR(101MHz,CDCl3):δ139.6,135.5,132.3,129.7,
128.5,128.2,128.0,124.6,31.7,31.1,27.9,22.4,19.1,14.0,3.2；HRMS(EI)calculated
for[C19H28Si2]+requires m/z 312.1730,found m/z 312.1731.
VI-2:
(S)-benzyl (1- (phenyl silicon substrate) hexyl) silane
(S)-benzyl(1-(phenylsilyl)hexyl)silane
Oily liquids, 85% yield, regioselectivity > 19/1, [α]20 D=+8.0 (c 1.03, CHCl3), 96.4%ee,
IR(cm-1):2966,2921,2130,1598,1407,1060；1H NMR(400MHz,CDCl3):δ7.57-7.53(m,2H),
7.40-7.32(m,3H),7.24-7.19(m,2H),7.11-7.02(m,3H),4.39-4.33(m,2H),3.91-3.82(m,
2H),2.21-2.17(m,2H),1.61-1.52(m,2H),1.40-1.32(m,2H),1.27-1.16(m,4H),0.84(t,J
=7.2Hz, 3H), 0.48-0.40 (m, 1H)；13C NMR(101MHz,CDCl3):δ139.6,135.5,132.3,129.7,
128.5,128.2,128.0,124.6,31.7,31.1,27.9,22.4,19.1,14.0,3.2；HRMS(EI)calculated
for[C19H28Si2]+requires m/z 312.1730,found m/z 312.1731.
VI-3:
(R)-benzyl (4- (benzyl oxygroup) -1 (phenyl silicon substrate) butyl) silane
(R)-benzyl(4-(benzyloxy)-1-(phenylsilyl)butyl)silane
Oily liquids, 77% yield, regioselectivity > 19/1, [α]20 D=-6.2 (c 0.98, CHCl3), 98.4%ee,
IR(cm-1):2972,2926,2131,1494,1157,1063；1H NMR(400MHz,CDCl3):δ7.56-7.53(m,2H),
7.38-7.28(m,8H),7.22-7.17(m,2H),7.10-7.01(m,3H),4.44-4.42(m,2H),4.39-4.34(m,
2H),3.92-3.83(m,2H),3.40-3.34(m,2H),2.20-2.16(m,2H),1.72-1.62(m,4H),0.48-0.40
(m,1H)；13C NMR(101MHz,CDCl3):δ139.5,138.6,135.5,132.0,129.8,128.5,128.3,128.2,
128.0,127.6,127.5,124.7,72.8,69.9,31.3,24.5,19.0,2.9；HRMS(ESI)calculated for
[M+Na]+[C17H24OSi2]+requires m/z 413.1733,found m/z 413.1738.
VI-4:
(R)-benzyl (the chloro- 1- of 6- (phenyl silicon substrate) hexyl) silane
(R)-benzyl(6-chloro-1-(phenylsilyl)hexyl)silane
Oily liquids, 57% yield, regioselectivity > 19/1, [α]20 D=-8.4 (c 1.09, CHCl3), 97.6%ee,
IR(cm-1):3067,2925,2129,1599,1493,1206,1060；1H NMR(400MHz,CDCl3):δ7.60-7.53(m,
2H),7.44-7.33(m,3H),7.27-7.19(m,2H),7.14-7.03(m,3H),4.42-4.33(m,2H),3.96-3.82
(m,2H),3.50-3.43(m,2H),2.26-2.14(m,2H),1.73-1.63(m,2H),1.61-1.51(m,2H),1.40-
1.29(m,4H),0.50-0.40(m,1H)；13C NMR(101MHz,CDCl3):δ139.5,135.5,132.1,129.8,
128.5,128.2,128.1,124.7,45.0,32.3,30.6,27.8,26.7,19.1,3.1；HRMS(EI)calculated
for[C19H27ClSi2]+requires m/z 346.1340,found m/z 346.1337.
VI-5:
(R)-benzyl (5- methyl-1-(phenyl silicon substrate) hexyl) silane
(R)-benzyl(5-methyl-1-(phenylsilyl)hexyl)silane
Oily liquids, 72% yield, regioselectivity > 19/1, [α]20 D=-9.0 (c 1.05, CHCl3), 98.8%ee,
IR(cm-1):2956,2924,2130,1599,1493,1158,1116；1H NMR(400MHz,CDCl3):δ7.59-7.54(m,
2H),7.42-7.33(m,3H),7.25-7.19(m,2H),7.13-7.03(m,3H),4.41-4.34(m,2H),3.93-3.83
(m,2H),2.24-2.17(m,2H),1.60-1.51(m,2H),1.50-1.42(m,1H),1.40-1.32(m,2H),1.12-
1.05 (m, 2H), 0.83 (d, J=6.8Hz, 6H), 0.50-0.42 (m, 1H)；13C NMR(101MHz,CDCl3):δ139.6,
135.5,132.3,129.7,128.5,128.2,128.0,124.6,38.8,29.2,28.2,27.7,22.5,19.1,3.2；
HRMS(EI)calculated for[C20H30Si2]+requires m/z 326.1886,found m/z 326.1885.
VI-6:
(S) -9- (3- (naphthalene -1- first silicon substrate) -3- (phenyl silicon substrate) propyl) -9H carbazole
(S)-9-(3-(naphthalen-1-ylsilyl)-3-(phenylsilyl)propyl)-9H-carbazole
(5mol% chirality CoX2- IIP complex compound III-1,15mol% sodium triethylborohydride)
White solid, 73% yield, regioselectivity > 19/1, fusing point: 76.8-77.6 DEG C, 91.6%ee, IR (cm-1):
3050,2930,2867,2135,1595,1485,1458,1328,1150；1H NMR(400MHz,CDCl3):δ8.02-7.96
(m, 3H), 7.93 (d, J=8.4Hz, 2H), 7.90-7.85 (m, 1H), 7.76 (d, J=6.0Hz, 1H), 7.57-7.52 (m,
2H), 7.52-7.46 (m, 2H), 7.45-7.39 (m, 2H), 7.33 (dd, J=7.6,7.2Hz, 2H), 7.26 (dd, J=7.2,
7.2Hz, 2H), 7.14 (dd, J=7.6,7.2Hz, 2H), 6.78 (d, J=8.0Hz, 2H), 4.87 (dd, J=5.6Hz, 1H),
4.75 (dd, J=5.6,5.2Hz, 1H), 4.46-4.47 (m, 2H), 4.14-4.00 (m, 2H), 2.14-2.04 (m, 2H),
0.96-0.87(m,1H)；13C NMR(101MHz,CDCl3):δ139.9,137.0,136.6,135.5,133.2,131.1,
131.0,130.03,129.99,129.1,128.2,127.5,126.5,126.0,125.5,125.3,122.6,120.2,
118.7,108.3,44.1,26.5,1.3；HRMS(EI)calculated for[C31H29NSi2]+requires m/z
The mono-crystalline structures of 471.1839, found m/z 471.1837.VII-6 are as shown in Fig. 2, No. CCDC: 1876614
VI-7:
(R) -9- (3- (benzyl silicon) -3- (phenyl silicon substrate) propyl) -9H carbazole
(R)-9-(3-(benzylsilyl)-3-(phenylsilyl)propyl)-9H-carbazole
(5mol% chirality CoX2- IIP complex compound III-1,15mol% sodium triethylborohydride)
Oily liquids, 77% yield, regioselectivity > 19/1,97.0%ee, IR (cm-1):3053,3023,2927,
2870,2134,1626,1488,1457,1328,1155,1118；1H NMR(400MHz,CDCl3): δ 8.07 (d, J=7.6Hz,
2H),7.56-7.51(m,2H),7.45-7.33(m,5H),7.22-7.14(m,6H),7.12-7.07(m,1H),7.01(d,J
=7.6Hz, 2H), 4.46 (d, J=3.6Hz, 2H), 4.20 (t, J=8.0Hz, 2H), 4.01-3.96 (m, 2H), 2.19 (t, J
=4.0Hz, 2H), 2.09-2.01 (m, 2H), 0.53-0.45 (m, 1H)；13C NMR(101MHz,CDCl3):δ140.0,
138.9,135.5,131.1,130.1,128.6,128.3,128.2,125.6,124.9,122.8,120.4,118.9,
108.4,43.9,26.6,18.9,0.1；HRMS(ESI)calculated for[M+H]+[C28H30NSi2]+requires m/z
436.1917,found m/z 436.1928.
Embodiment 2: chiral CoX2The asymmetric hydrosilation of the alkynes of-IIP complex catalysis and two kinds of three hydrogen silanes of difference
Reaction
Under room temperature, argon gas, Co (OAc) is sequentially added in a dry reaction tube2(0.01mmol), Dpephoes
(0.012mmol), toluene (2.0mL), three hydrogen silanes (0.50mmol) shown in Formula II, sodium triethylborohydride (0.03mol),
Alkynes shown in Formulas I (0.50mmol) stirs 3 hours at room temperature.Then, under protection of argon gas, CoX is added2-IIP
(0.015mol), three hydrogen silanes (0.50mmol) shown in Formula IV, it is small that sodium triethylborohydride (0.045mol) stirs 3 at room temperature
When after column chromatography for separation (mixture that eluting solvent is petroleum ether or petroleum ether and ethyl acetate) obtain product.
In embodiment 2, chiral CoX2Shown in the following formula III -1 of the chemical formula of-IIP complex compound:
Preparation method is the same as described in implementation 1.
VI-1:
(R)-benzyl (1- (phenyl silicon substrate) hexyl) silane
(R)-benzyl(1-(phenylsilyl)hexyl)silane
Oily liquids, 77% yield, regioselectivity > 19/1,98.6%ee, IR (cm-1):2966,2921,2130,
1598,1407,1060；1H NMR(400MHz,CDCl3):δ7.57-7.53(m,2H),7.40-7.32(m,3H),7.24-7.19
(m,2H),7.11-7.02(m,3H),4.39-4.33(m,2H),3.91-3.82(m,2H),2.21-2.17(m,2H),1.61-
1.52 (m, 2H), 1.40-1.32 (m, 2H), 1.27-1.16 (m, 4H), 0.84 (t, J=7.2Hz, 3H), 0.48-0.40 (m,
1H)；13C NMR(101MHz,CDCl3):δ139.6,135.5,132.3,129.7,128.5,128.2,128.0,124.6,
31.7,31.1,27.9,22.4,19.1,14.0,3.2；HRMS(EI)calculated for[C19H28Si2]+requires m/
z 312.1730,found m/z 312.1731.
VI-2:
(S)-benzyl (1- (phenyl silicon substrate) hexyl) silane
(S)-benzyl(1-(phenylsilyl)hexyl)silane
Oily liquids, 80% yield, regioselectivity > 19/1,98.4%ee, IR (cm-1):2966,2921,2130,
1598,1407,1060；1H NMR(400MHz,CDCl3):δ7.57-7.53(m,2H),7.40-7.32(m,3H),7.24-7.19
(m,2H),7.11-7.02(m,3H),4.39-4.33(m,2H),3.91-3.82(m,2H),2.21-2.17(m,2H),1.61-
1.52 (m, 2H), 1.40-1.32 (m, 2H), 1.27-1.16 (m, 4H), 0.84 (t, J=7.2Hz, 3H), 0.48-0.40 (m,
1H)；13C NMR(101MHz,CDCl3):δ139.6,135.5,132.3,129.7,128.5,128.2,128.0,124.6,
31.7,31.1,27.9,22.4,19.1,14.0,3.2；HRMS(EI)calculated for[C19H28Si2]+requires m/
z 312.1730,found m/z 312.1731.
VI-5:
(R)-benzyl (5- methyl-1-(phenyl silicon substrate) hexyl) silane
(R)-benzyl(5-methyl-1-(phenylsilyl)hexyl)silane
Oily liquids, 84% yield, regioselectivity > 19/1,97.6%ee, IR (cm-1):2956,2924,2130,
1599,1493,1158,1116；1H NMR(400MHz,CDCl3):δ7.59-7.54(m,2H),7.42-7.33(m,3H),
7.25-7.19(m,2H),7.13-7.03(m,3H),4.41-4.34(m,2H),3.93-3.83(m,2H),2.24-2.17(m,
2H),1.60-1.51(m,2H),1.50-1.42(m,1H),1.40-1.32(m,2H),1.12-1.05(m,2H),0.83(d,J
=6.8Hz, 6H), 0.50-0.42 (m, 1H)；13C NMR(101MHz,CDCl3):δ139.6,135.5,132.3,129.7,
128.5,128.2,128.0,124.6,38.8,29.2,28.2,27.7,22.5,19.1,3.2；HRMS(EI)calculated
for[C20H30Si2]+requires m/z 326.1886,found m/z 326.1885.
VI-4:
(R)-benzyl (the chloro- 1- of 6- (phenyl silicon substrate) hexyl) silane
(R)-benzyl(6-chloro-1-(phenylsilyl)hexyl)silane
Oily liquids, 72% yield, regioselectivity > 19/1,97.6%ee, IR (cm-1):3067,2925,2129,
1599,1493,1206,1060；1H NMR(400MHz,CDCl3):δ7.60-7.53(m,2H),7.44-7.33(m,3H),
7.27-7.19(m,2H),7.14-7.03(m,3H),4.42-4.33(m,2H),3.96-3.82(m,2H),3.50-3.43(m,
2H),2.26-2.14(m,2H),1.73-1.63(m,2H),1.61-1.51(m,2H),1.40-1.29(m,4H),0.50-0.40
(m,1H)；13C NMR(101MHz,CDCl3):δ139.5,135.5,132.1,129.8,128.5,128.2,128.1,124.7,
45.0,32.3,30.6,27.8,26.7,19.1,3.1；HRMS(EI)calculated for[C19H27ClSi2]+requires
m/z 346.1340,found m/z 346.1337.
Embodiment 3: product oxidative synthesis aldehyde compound (application example)
In 20mL reaction tube, VI (1.0mmol), chloroform (5mL), HBF is added4.OEt2(6mmol, 40%Wt) is mixed
It closes liquid to flow back 24 hours, solvent is removed in rotation, is then sequentially added into tetrahydrofuran (1mL), methanol (3mL), tetrabutyl ammonium fluoride
(8.0mmol), saleratus (8.0mmol), H2O210h is stirred at room temperature in (50mmol, 30%wt), is saturated NaHSO3Solution is dilute
It releases, ether extracts 3 times, saturated common salt water washing, and anhydrous sodium sulfate is dry, is spin-dried for, PE/EtOAc=20/1 crosses column and obtains chemical combination
Object A (experimental procedure bibliography: Chem.Commun.2002,114-115.)
Following product is oxidized to aldehyde compound referring to the above method, as shown in table 1.
1 chirality of table is together with two silicon substrate alkane products oxidative synthesis aldehyde compounds
Embodiment 4: the chiral polysubstituted silane compound (application example) of Product formation
Under the protection of argon gas, it is added and sequentially adds VI (0.5mmol) into dry Schlenk reaction tube, DCE (1,
2- dichloroethanes) (20mL), CH2I2After (2.0mL, 3.3g/mL, 25mmol), after being stirred 5 minutes at 0 DEG C, it is slowly added dropwise
ZnEt2(7.5mL, 2.0M, 15mmol), continuation are stirred 30 minutes at 0 DEG C.Later, it is stirred to react 36 hours in room temperature condition.
After completion of the reaction, NH is saturated in 0 DEG C of addition4Cl solution quenching reaction extracts product with DCM (methylene chloride) (60mL × 3), closes
And organic phase Na2SO4Dry, solvent is removed in rotation, and PE crosses column and obtains target product B.
B-1:
(R)-benzyl (1- (dimethyl (phenyl) silicyl) hexyl) dimethylsilane
(R)-benzyl(1-(dimethyl(phenyl)silyl)hexyl)dimethylsilane
Colourless oil liquid, 99% yield, [α]20 D=+3.3 (c 1.06, CHCl3)；IR(cm-1):3065,3023,
2956,2926,2855,1600,1492,1252；1H NMR(400MHz,CDCl3):δ7.54-7.47(m,2H),7.36-7.29
(m, 3H), 7.17 (dd, J=7.6,7.2Hz, 2H), 7.04 (dd, J=7.2,7.2Hz, 1H), 6.91 (d, J=8.0Hz, 2H),
1.99 (s, 2H), 1.53-1.45 (m, 2H), 1.27-1.09 (m, 6H), 0.82 (t, J=6.8Hz, 3H), 0.33 (d, J=
6.4Hz, 6H), 0.06 (t, J=5.2Hz, 1H), -0.15 (d, J=11.6Hz, 6H)；13C NMR(101MHz,CDCl3):δ
140.5,140.4,133.7,128.7,128.2,128.0,127.6,123.8,32.9,32.1,26.3,26.1,22.4,
14.1,12.3,-1.3,-1.7,-1.9,-2.6；HRMS(EI)calculatedfor[M-CH3]+[C22H33Si2]+requires
m/z 353.2121,found m/z 353.2121.
B-2:
(S)-benzyl (1- (dimethyl (phenyl) silicon substrate) hexyl) dimethylsilane
(S)-benzyl(1-(dimethyl(phenyl)silyl)hexyl)dimethylsilane
Colourless oil liquid, 93% yield, [α]20 D=-3.3 (c 1.06, CHCl3)；IR(cm-1):3068,3022,
2953,2929,2852,1599,1492,1251；1H NMR(400MHz,CDCl3):δ7.54-7.47(m,2H),7.36-7.29
(m, 3H), 7.17 (dd, J=7.6,7.2Hz, 2H), 7.04 (dd, J=7.2,7.2Hz, 1H), 6.91 (d, J=8.0Hz, 2H),
(1.99 s, 2H), 1.53-1.45 (m, 2H), 1.27-1.09 (m, 6H), 0.82 (t, J=6.8Hz, 3H), 0.33 (d, J=
6.4Hz, 6H), 0.06 (t, J=5.2Hz, 1H), -0.15 (d, J=11.6Hz, 6H)；13C NMR(101MHz,CDCl3):δ
140.5,140.4,133.7,128.7,128.2,128.0,127.6,123.8,32.9,32.1,26.3,26.1,22.4,
14.1,12.3,-1.3,-1.7,-1.9,-2.6；HRMS(EI)calculated for[M-CH3]+[C22H33Si2]+requires
m/z 353.2121,found m/z 353.2122.
B-3:
(R)-benzyl (1- (dimethyl (phenyl) silicon substrate) -5- methylhexyl) dimethylsilane
(R)-benzyl(1-(dimethyl(phenyl)silyl)-5-methylhexyl)dimethylsilane
Colourless oil liquid, 95% yield, [α]20 D=-3.5 (c 1.02, CHCl3)；IR(cm-1):3067,2956,
2924,2853,1599,1498,1207,1061；1H NMR(400MHz,CDCl3):δ7.56-7.48(m,2H),7.39-7.30
(m, 3H), 7.17 (dd, J=7.6,7.2Hz, 2H), 6.94 (dd, J=7.2,7.2Hz, 1H), 6.86 (d, J=8.0Hz, 2H),
2.01(s,2H),1.52-1.45(m,2H),1.50-1.42(m,1H),1.40-1.32(m,2H),1.12-1.05(m,2H),
0.81 (d, 6.8H), 0.38 (d, J=6.4Hz, 6H), 0.09 (t, J=5.2Hz, 1H), -0.15 (d, J=11.6Hz, 6H)；13C
NMR(101MHz,CDCl3):δ140.7,140.6,133.8,128.6,128.2,127.9,127.5,123.8,39.9,30.2,
27.6,23.4,22.5,19.1,12.3,-1.3,-1.7,-1.8,-2.7.HRMS(EI)calculated for[M-CH3]+
[C23H35Si2]+requires m/z 367.2277,found m/z 367.2279.
B-4:
(R)-benzyl (the chloro- 1- of 6- (dimethyl (phenyl) silicon substrate) hexyl) dimethylsilane
(R)-benzyl(6-chloro-1-(dimethyl(phenyl)silyl)hexyl)dimethylsilane
Colourless oil liquid, 88% yield, [α]20 D=-3.4 (c 1.06, CHCl3)；IR(cm-1):3067,2925,
2912,2852,1599,1493,1206,1061；1H NMR(400MHz,CDCl3):δ7.57-7.51(m,2H),7.40-7.30
(m, 3H), 7.19 (dd, J=7.6,7.2Hz, 2H), 7.05 (dd, J=7.2,7.2Hz, 1H), 6.96 (d, J=8.0Hz, 2H),
3.42-3.38 (m, 2H), 2.20-2.12 (m, 2H), 1.63-1.53 (m, 2H), 1.46-1.28 (m, 6H), 0.30 (d, J=
6.4Hz, 6H), 0.07 (t, J=5.2Hz, 1H), -0.18 (d, J=11.6Hz, 6H)；13C NMR(101MHz,CDCl3):δ
143.5,140.6,133.2,128.8,128.1,128.0,127.7,123.7,46.3,33.3,30.8,29.3,26.7,
19.1,13.1,-1.2,-1.6,-1.8,-2.6；HRMS(EI)calculated for[M-CH3]+[C22H32ClSi2]+
requires m/z 387.1731,found m/z 387.1729.
Embodiment 5: chiral polysubstituted silane compound synthesis of chiral fluoro is together with two silicon substrate alkane compounds (application example)
It is added into 25mL reaction tube and sequentially adds B-1 (0.0926g, 0.25mmol), CHCl3(chloroform) (2.5mL), three
It is fluorinated borate ether (0.3575g, 2.5mmol), back flow reaction 16 is small at 65 DEG C for acetic acid (572 μ L, 1.05g/mL, 10mmol)
When.After completion of the reaction, methylene chloride (60mL) is added, is washed with saturated sodium carbonate (60mL), organic phase is dry with anhydrous sodium sulfate
Dry, solvent is removed in rotation, and PE crosses column and obtains colourless liquid C-1 (0.0708g, yield 91%).95.6%ee；IR(cm-1):3065,
3033,2957,2928,2845,1600,1492,1201；1H NMR(400MHz,CDCl3): 7.22 (dd, J=7.6,7.2Hz,
2H), 7.08 (dd, J=7.2,7.2Hz, 1H), 7.01 (d, J=7.2Hz, 2H), 2.17 (s, 2H), 1.54-1.46 (m, 2H),
1.38-1.21 (m, 6H), 0.90 (t, J=6.8Hz, 3H), 0.25 (d, J=7.6Hz, 6H), 0.11-0.06 (m, 1H), 0.01
(s,6H)；13CNMR(101MHz,CDCl3): δ 140.2,128.2,128.1,124.0,32.8,32.1,25.9,24.9 (d, J=
2.2Hz, 1C), 22.5,14.8 (d, J=14.8Hz, 1C), 14.1,0.8 (d, J=15.8Hz, 1C), -0.4 (d, J=
15.4Hz,1C),-2.3,-2.9；19F NMR:(376MHz,CDCl3):δ-153.8；HRMS(EI)calculated for
[C17H31FSi2]+requires m/z 310.1948,found m/z 310.1950.
Embodiment 6: chiral fluoro is together with two silicon substrate alkane compound synthesis of chiral silicon alcohol compounds (application example)
It is added and sequentially adds C-1 (0.0623g, 0.20mmol) into 25mL reaction tube, anhydrous potassium fluoride (0.0582g,
1.0mmol), anhydrous DMF (0.8mL), m-CPBA (metachloroperbenzoic acid) (0.2279g, 75%, 1.0mmol) DMF solution
(1.2mL) is stirred at room temperature 36 hours.After completion of the reaction, methylene chloride (80mL) is added, with saturated sodium thiosulfate solution
(30mL), saturated sodium carbonate solution (30mL), saturated common salt water washing (30 × 3mL), and it is dry with anhydrous sodium sulfate, and rotation is gone molten
Agent separates to obtain product D-1 (0.0371g, yield 74%) through column chromatography PE/EA=15/1.91.8%ee；IR(cm-1):3431,
3062,3024,2923,2851,1465,1492,1245；1H NMR(400MHz,CDCl3): 7.22 (dd, J=7.6,7.2Hz,
2H), 7.10-7.01 (m, 3H), 3.35 (dd, J=9.6,3.6Hz, 1H), 2.24-2.12 (m, 2H), 1.55-1.48 (m, 2H),
1.36-1.21 (m, 6H), 1.04 (s, 1H), 0.89 (t, J=6.8Hz, 3H), 0.01 (d, J=14.4Hz, 6H)；HRMS(ESI)
calculated for[M+Na]+[C15H26NaOSi]+requires m/z 273.1651,found m/z 273.1656.
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 (10)
1. a kind of chirality containing there are four si-h bond is together with two silicon substrate alkane compounds, as shown in Formula IV:
In Formula IV, R2,R3For different group；
In Formula IV, * represents asymmetric carbon atom；
In Formula IV, R1Optionally from the silylation of the naphthenic base or C1~C16 of the alkyl of H, C1-C16 or C3-C16；The alkyl, ring
H on alkyl or silylation is not substituted or is replaced by 1 or more substituent A, and the substituent A includes the alkene of C1-C10
Base, nitro, halogen, aryl A, heterocyclic aryl A, phthalimide-based, methoxycarbonyl group, trifluoromethyl, hydroxyl, C1~C3
Aldehyde radical, the carboxyl of C1~C3, amino, the ester group of C1~C16, the silylation of C1-C16, the siloxy of C1-C16, C1-C16 alkane
Oxygroup, the sulfonyl of C1~C16, benzyloxy or C1-C10 amide groups；The aryl A includes phenyl or naphthyl；The heterocycle
Aryl A includes indyl, thienyl, pyridyl group, piperidyl, quinolyl, group shown in carbazyl or Formula VII；The alkenyl,
H on aryl A, heterocyclic aryl A is not substituted or is replaced by 1 or more substituent B, and the substituent B includes C1~C6's
Alkyl, the alkoxy of C1~C3, halogen, trifluoromethyl, hydroxyl, the aldehyde radical of C1~C3, the carboxyl of C1~C3, amino, C1~C3
Ester group, phenyl or amide groups；
In Formula VII, right end horizontal line "-" indicates the connecting key of group and carbon atom, without indicating methyl；
R2,R3Optionally from benzyl, phenylethyl, the alkyl of C1-C16, aryl B or heterocyclic aryl B, the aryl B such as Formula X or
Shown in Formula XI:
In Formula X, R4、R5、R6、R7、R8Optionally from H, halogen, the alkyl of C1-C16, the alkoxy of C1-C16, C1-C16 alkane sulphur
Base, phenyl, trifluoromethyl, methoxycarbonyl group, nitro, hydroxyl, the aldehyde radical of C1~C3, the carboxyl of C1~C3, amino, C1~C16
Ester group, the silylation of C1-C16, the siloxy of C1-C16, benzyloxy, amide groups, acetyl-o-methyl, 2- methyl-1,3-dioxy ring
Any one in amyl；R4、R5、R6、R7、R8When being all H, group shown in Formula X is phenyl；
In Formula XI, R9、R10、R11、R12、R13、R14、R15Optionally from H, halogen, the alkyl of C1-C16, the alkoxy of C1-C16, C1-
The alkylthio group of C16, phenyl, trifluoromethyl, methoxycarbonyl group, nitro, hydroxyl, the aldehyde radical of C1~C3, the carboxyl of C1~C3, amino,
The ester group of C1~C16, the silylation of C1-C16, the siloxy of C1-C16, benzyloxy, amide groups, acetyl-o-methyl, 2- methyl-
Any one in 1,3- dioxy cyclopenta；R9、R10、R11、R12、R13、R14、R15When being all H, group shown in Formula XI is naphthalene
Base；
The heterocyclic aryl B is indyl, thienyl, pyridyl group, piperidyl, carbazyl or quinolyl.
2. the chirality as described in claim 1 containing there are four si-h bond is together with two silicon substrate alkane compounds, it is characterised in that the R1
For the silylation of the alkyl of H, C1-C16, the naphthenic base of C3-C16 or C1~C16；H on the alkyl is not substituted or by 1
Above substituent A replaces, and the substituent A includes alkenyl, halogen, phenyl, naphthalene, thienyl, indyl, pyridyl group, quinoline
Quinoline base, piperidyl, carbazyl, methoxycarbonyl group, trifluoromethyl, hydroxyl, amino, the ester group of C1~C10, tertiary butyl dimethyl Si
Base, benzyloxy, amide groups, tolysulfonyl amido, mesyl, N, group shown in N- diethylamide carbonyl or Formula VII；Institute
State phenyl, the H on naphthalene is not substituted or is replaced by 1 or more substituent B, the substituent B include C1~C3 alkyl,
Alkoxy, halogen, trifluoromethyl, hydroxyl, the carboxyl of C1~C3, amino, the ester group of C1~C3, phenyl or the amide of C1~C3
Base；
The R2、R3For benzyl, phenylethyl or aryl B, wherein aryl B is as shown in Formula X or Formula XI:
Group shown in Formula XI is phenyl or the substituted-phenyl containing 1~2 or less substituent group: alkyl, phenyl, the C1 of C1~C4
Alkoxy, methyl mercapto, F, Cl, Br, trifluoromethyl, methoxycarbonyl group, the acetyl-o-methyl of~C4；
Group shown in Formula XII is naphthalene or the substituted naphthyl containing 1~2 or less substituent group: the alkyl of C1~C4, phenyl,
Alkoxy, methyl mercapto, F, Cl, Br, trifluoromethyl, methoxycarbonyl group, the acetyl-o-methyl of C1~C4.
3. the chirality as described in claim 1 containing there are four si-h bond is together with two silicon substrate alkane compounds, it is characterised in that the R1
For the alkyl of H, C1-C10, the naphthenic base of C3-C10 or trimethyl silicon substrate, the alkyl is indicated by following formula: CnH2n+1Or
Person RA—(CH2)n-, the integer that n is 1~10, CnH2n+1Indicate that the H on alkyl is not substituted, RA—(CH2)n- in RAFor carbon
Substituent group on chain, RAIncluding ethylenyl, halogen, phenyl, naphthalene, thienyl, piperidyl, indyl, carbazyl, hydroxyl,
Methoxycarbonyl group, tertiary butyl dimethyl Si base, benzyloxy, amide groups, ethyoxyl oxalic acid ester group, tosyl amido, methylsulfonyl
Base, N, group shown in N- diethylamide carbonyl or Formula VII, the H on the phenyl are not substituted or by 1~2 substituent B
Replace, the substituent B includes alkyl, halogen, trifluoromethyl or the phenyl of C1~C3；
R2, R3Optionally benzyl, phenylethyl, phenyl, naphthalene, rubigan or p-methoxyphenyl.
4. the chiral synthesis side together with two silicon substrate alkane compounds of si-h bond containing there are four as described in one of claims 1 to 3
Method, it is characterised in that the method is one of the following: under method (one) inert gas, with alkenyl silanes class chemical combination shown in Formula V
Three hydrogen silanes shown in object and formula IV are raw material, with chiral CoX2- IIP complex compound is catalyst, in the presence of a reducing agent, reaction
It is made shown in Formula IV containing the chirality there are four si-h bond together with two silicon substrate alkane compounds；
Shown in reaction equation such as following formula (1):
Under method (two) inert gas, with three hydrogen silanes shown in three hydrogen silanes, formula IV shown in alkynes shown in Formulas I and Formula II
For raw material, with CoY2, bis- (2- diphenylphosphine phenyl) ethers and chirality CoX2- IIP complex compound is catalyst, in the presence of a reducing agent,
It reacts and is made shown in Formula IV containing the chirality there are four si-h bond together with two silicon substrate alkane compounds；
Shown in reaction equation such as following formula (2):
CoY2In Y be F, Cl, Br, I, acetate anion, any one in acyl acetone anion；
The chirality CoX2The structural formula of-IIP complex compound is formula III compound represented or its enantiomer, in formula III, R16,
R17, R18, R19, R20, R21, R22, R23, R24, R25,R26,R27,R28Optionally from the alkyl of H, C1-C16, the alkoxy of C1-C16, benzene
Base, naphthalene or benzyl: the H on the alkyl, alkoxy is not substituted or is replaced by 1 or more substituent group E, the substituent group
E includes nitro, halogen, phenyl, methoxycarbonyl group, trifluoromethyl, hydroxyl, the aldehyde radical of C1~C3, the carboxyl of C1~C3, amino, C1
The ester group or amide groups of~C3；
The phenyl, benzyl, the H on naphthalene are not substituted or are replaced by 1 or more substituent group D, and the substituent group D includes C1
The alkyl of~C3, the alkoxy of C1~C3, nitro, halogen, phenyl, methoxycarbonyl group, trifluoromethyl, hydroxyl, C1~C3 aldehyde radical,
The carboxyl of C1~C3, amino, C1~C3 ester group or amide groups；
X is F, Cl, Br, I, OAc, CF3SO3In any one.
5. method as claimed in claim 4, it is characterised in that the chirality CoX2The structural formula of-IIP complex compound is formula III institute
The compound shown, in formula III, R16、R17、R18、R26、R27It is H；R19For methyl；R20For C1-C4Alkyl, R21For H, R22For
H、C1-C4Alkyl, C1-C4Alkoxy or halogen；R23For H；R24For C1-C4Alkyl；R25For C1-C4Alkyl, benzyl or
Phenyl；R28For C1-C4Alkyl, benzyl or phenyl；X is Cl.
6. method as claimed in claim 5, it is characterised in that the chirality CoX2- IIP complex compound is as shown in formula III -1
7. method as claimed in claim 4, it is characterised in that in the method (two), reaction carries out by the following method: inertia
Under gas, three hydrogen silanes, CoY shown in alkynes and Formula II shown in Formulas I2, bis- (2- diphenylphosphine phenyl) ethers deposit in reducing agent
Under, after reaction 0.5~60 hour, chiral CoX is added2Three hydrogen silanes shown in-IIP complex compound catalyst, formula IV and also
Former agent is reacted 0.5~60 hour, is made shown in Formula IV containing the chirality there are four si-h bond together with two silicon substrate alkane compounds.
8. method as claimed in claim 4, it is characterised in that in the method (one), alkenyl silanes class chemical combination shown in Formula V
Three hydrogen silanes shown in object, formula IV, chirality CoX2The ratio between amount of substance of-IIP complex compound, reducing agent is 1:0.1-10:
0.0000005-0.1:0.000003-0.33；In the method (two), three hydrogen silanes shown in alkynes, Formula II shown in Formulas I,
Three hydrogen silanes, CoY shown in formula IV2, bis- (2- diphenylphosphine phenyl) ethers, chirality CoX2The substance of-IIP complex compound, reducing agent
The ratio between amount is 1:0.1-10:0.1-10:0.0000005-0.1:0.0000005-0.1:0.0000005-0. 1:0.000003-
0.33。
9. the method as described in one of claim 4~6, it is characterised in that the reducing agent is sodium triethylborohydride, three secondary
Butyl sodium borohydride, lithium triethylborohydride, sodium tert-butoxide, potassium tert-butoxide, tert-butyl alcohol lithium, sodium tert-amyl alcohol, sodium ethoxide, methanol
Any one in sodium, potassium methoxide.
10. chirality shown in the Formula IV as described in one of claims 1 to 3 is together with two silicon substrate alkane compounds in oxidative synthesis fat
Aldehyde compound, chiral silicon alcohol compound, the application in chiral polysubstituted silane compound.
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