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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- silane
- boryl
- silane compound
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 30
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 15
- -1 sodium triethylborohydride Chemical compound 0.000 claims abstract description 33
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000085 borane Inorganic materials 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052796 boron Inorganic materials 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract 4
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 5
- 238000004809 thin layer chromatography Methods 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 229910052703 rhodium Inorganic materials 0.000 abstract description 2
- 239000010948 rhodium Substances 0.000 abstract description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000006197 hydroboration reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
本方法公开了一种速合成α‑硼基硅烷类化合物的方法。以炔烃为原料，以硅烷为硅源，以硼烷为硼源，以CoX2‑OIP络合物为催化剂，在三乙基硼氢化钠存在下，‑30℃～80℃温度下，反应30分钟～4小时制得烯基硅烷，所述的炔烃、硅烷、硼烷、CoCl2‑OIP络合物、三乙基硼氢化钠的摩尔比为1：1：1.2：0.0005‑0.05：0.0015‑0.15；与现有方法相比，该方法适用于多种不同类型的炔烃，反应条件温和，操作简便，原子经济性100％。另外，反应无需其他任何的有毒过渡金属(如钌、铑、钯等)盐类的加入，在药物合成上具有较大的实际应用价值。且反应的官能团容忍性好，区域选择性也较高，一般为>20:1。The method discloses a method for rapidly synthesizing α-boron silane compounds. Using alkyne as raw material, using silane as silicon source, using borane as boron source, using CoX 2 -OIP complex as catalyst, in the presence of sodium triethylborohydride, at a temperature of -30 ℃ ~ 80 ℃, the reaction is carried out The alkenyl silane is prepared in 30 minutes to 4 hours, and the molar ratio of the alkyne, silane, borane, CoCl 2 -OIP complex and sodium triethylborohydride is 1:1:1.2:0.0005-0.05: 0.0015-0.15; compared with the existing method, the method is suitable for many different types of alkynes, the reaction conditions are mild, the operation is simple, and the atom economy is 100%. In addition, the reaction does not require the addition of any other toxic transition metal (such as ruthenium, rhodium, palladium, etc.) salts, and has great practical application value in drug synthesis. And the functional group tolerance of the reaction is good, and the regioselectivity is also high, 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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| CN105229016A (en) * | 2013-05-06 | 2016-01-06 | 莫门蒂夫性能材料股份有限公司 | By the saturated and unsaturated silahydrocarbons of the olefinic silane of iron and the catalysis of cobalt pyridine diimine |
| CN105294667A (en) * | 2014-07-28 | 2016-02-03 | 中国科学院上海有机化学研究所 | NNN ligand, metal complexes thereof, preparation methods and application |
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| CN105229016A (en) * | 2013-05-06 | 2016-01-06 | 莫门蒂夫性能材料股份有限公司 | By the saturated and unsaturated silahydrocarbons of the olefinic silane of iron and the catalysis of cobalt pyridine diimine |
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