CN115160355A - Method for efficiently synthesizing organic silicon compound - Google Patents
Method for efficiently synthesizing organic silicon compound Download PDFInfo
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- CN115160355A CN115160355A CN202210794445.6A CN202210794445A CN115160355A CN 115160355 A CN115160355 A CN 115160355A CN 202210794445 A CN202210794445 A CN 202210794445A CN 115160355 A CN115160355 A CN 115160355A
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- organic silicon
- trimethylsilyl
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- bicyclo
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 38
- 150000003377 silicon compounds Chemical class 0.000 title claims abstract description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims abstract description 43
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000004440 column chromatography Methods 0.000 claims abstract description 26
- 239000012044 organic layer Substances 0.000 claims abstract description 24
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims abstract description 24
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000654 additive Substances 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 239000012973 diazabicyclooctane Substances 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 24
- 239000003208 petroleum Substances 0.000 claims description 23
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 20
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- ZIQCCIAIROIHHR-UHFFFAOYSA-N benzene;boric acid Chemical class OB(O)O.C1=CC=CC=C1 ZIQCCIAIROIHHR-UHFFFAOYSA-N 0.000 claims 2
- GJPUXKDUNLNCRU-UHFFFAOYSA-N B(O)(O)O.C(C)C1=CC=CC=C1 Chemical compound B(O)(O)O.C(C)C1=CC=CC=C1 GJPUXKDUNLNCRU-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- QYUQPQJJMXISLT-UHFFFAOYSA-N anisole;boric acid Chemical compound OB(O)O.COC1=CC=CC=C1 QYUQPQJJMXISLT-UHFFFAOYSA-N 0.000 claims 1
- LFHUKUZPRPPASI-UHFFFAOYSA-N boric acid cumene Chemical compound B(O)(O)O.C(C)(C)C=1C=CC=CC1 LFHUKUZPRPPASI-UHFFFAOYSA-N 0.000 claims 1
- OOPSAZSKOMIGFX-UHFFFAOYSA-N boric acid;toluene Chemical compound OB(O)O.CC1=CC=CC=C1 OOPSAZSKOMIGFX-UHFFFAOYSA-N 0.000 claims 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 abstract description 11
- 238000000746 purification Methods 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 9
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 42
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 36
- -1 Organosilane compounds Chemical class 0.000 description 34
- 239000000047 product Substances 0.000 description 26
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 21
- 238000005481 NMR spectroscopy Methods 0.000 description 21
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 21
- 239000012043 crude product Substances 0.000 description 21
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 21
- 229910000027 potassium carbonate Inorganic materials 0.000 description 21
- 239000007788 liquid Substances 0.000 description 18
- 229940094989 trimethylsilane Drugs 0.000 description 18
- NLLGFYPSWCMUIV-UHFFFAOYSA-N (3-methoxyphenyl)boronic acid Chemical compound COC1=CC=CC(B(O)O)=C1 NLLGFYPSWCMUIV-UHFFFAOYSA-N 0.000 description 17
- 238000001035 drying Methods 0.000 description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 14
- 229910000077 silane Inorganic materials 0.000 description 11
- 238000001914 filtration Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006884 silylation reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XSZKVTREHGSCSV-QMMMGPOBSA-N (2S)-azasilolidine-2-carboxylic acid Chemical compound OC(=O)[Si@@H]1CCCN1 XSZKVTREHGSCSV-QMMMGPOBSA-N 0.000 description 2
- JIMVRUCDZGFJRE-UHFFFAOYSA-N (3-ethylphenyl)boronic acid Chemical compound CCC1=CC=CC(B(O)O)=C1 JIMVRUCDZGFJRE-UHFFFAOYSA-N 0.000 description 2
- BJQCPCFFYBKRLM-UHFFFAOYSA-N (3-methylphenyl)boronic acid Chemical compound CC1=CC=CC(B(O)O)=C1 BJQCPCFFYBKRLM-UHFFFAOYSA-N 0.000 description 2
- QSWLFBMVIGQONC-UHFFFAOYSA-N (3-propan-2-ylphenyl)boronic acid Chemical compound CC(C)C1=CC=CC(B(O)O)=C1 QSWLFBMVIGQONC-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- KLWPJMFMVPTNCC-UHFFFAOYSA-N Camptothecin Natural products CCC1(O)C(=O)OCC2=C1C=C3C4Nc5ccccc5C=C4CN3C2=O KLWPJMFMVPTNCC-UHFFFAOYSA-N 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- VSJKWCGYPAHWDS-FQEVSTJZSA-N camptothecin Chemical compound C1=CC=C2C=C(CN3C4=CC5=C(C3=O)COC(=O)[C@]5(O)CC)C4=NC2=C1 VSJKWCGYPAHWDS-FQEVSTJZSA-N 0.000 description 2
- 229940127093 camptothecin Drugs 0.000 description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 2
- VSJKWCGYPAHWDS-UHFFFAOYSA-N dl-camptothecin Natural products C1=CC=C2C=C(CN3C4=CC5=C(C3=O)COC(=O)C5(O)CC)C4=NC2=C1 VSJKWCGYPAHWDS-UHFFFAOYSA-N 0.000 description 2
- HCFDWZZGGLSKEP-UHFFFAOYSA-N doxylamine Chemical compound C=1C=CC=NC=1C(C)(OCCN(C)C)C1=CC=CC=C1 HCFDWZZGGLSKEP-UHFFFAOYSA-N 0.000 description 2
- 229960005178 doxylamine Drugs 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229960003088 loratadine Drugs 0.000 description 2
- JCCNYMKQOSZNPW-UHFFFAOYSA-N loratadine Chemical compound C1CN(C(=O)OCC)CCC1=C1C2=NC=CC=C2CCC2=CC(Cl)=CC=C21 JCCNYMKQOSZNPW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000012450 pharmaceutical intermediate Substances 0.000 description 2
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- WREVVZMUNPAPOV-UHFFFAOYSA-N 8-aminoquinoline Chemical compound C1=CN=C2C(N)=CC=CC2=C1 WREVVZMUNPAPOV-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 229940117803 phenethylamine Drugs 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
-
- 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
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a method for efficiently synthesizing an organic silicon compound, which comprises the following steps of: 3 to 5:2 to 3 portions of phenylboronic acid derivatives, hexamethyldisilane and norbornene, 3 to 4mL of solvent is added according to 0.5mmol of phenylboronic acid, and then the catalyst Pd (OAc) is added 2 Oxidant Cu (OAc) 2 Alkali K 2 CO 3 And the addition amount of the additive DABCO is respectively 10.0-15.0 percent, 300-500 percent, 200 percent and 100-200 percent of the molar amount of the phenylboronic acid, 4mL of acetonitrile, reacting for 24-30 h under the condition of oil bath at 120 ℃, cooling to room temperature, adding water, extracting for three times by using ethyl acetate, combining organic layers, concentrating under reduced pressure, and purifying a product by column chromatography to obtain the product organic silicon compound. The method has the characteristics of cheap reaction substrates, simple operation, high yield, good selectivity, easy separation and purification and less pollution.
Description
Technical Field
The invention relates to organic matter synthesis, in particular to a method for efficiently synthesizing an organic silicon compound.
Background
The organic silicon compound has unique biological, physical and chemical properties, and has wide application in the following aspects: 1. organosilicon compounds are important pharmaceutical intermediates and can be used in the synthesis of many drugs. Such as Doxylamine (Doxylamine), loratadine (Loratadine), cilazadirine (Sila-dimetracrine), amisilatrane (Amsilatrane), silaproline (Silaproline), silaalanine (TMS-alanine), and Camptothecin (Camptothecin). 2. Organosilane compounds are also important intermediates in organic chemistry, modifying the molecular skeleton. 3. Its derivatives are also widely used in polymersSemiconductor materials, drug design and the like. Since the organic silane compound has a wide application prospect and some special biological activities, such as important physiological and pharmacological activities, and other biological activities of anti-inflammation, anti-bacteria and the like, people have increasingly studied on the organic silane compound. There are three main methods for synthesizing organosilicon compounds: 1. a method for synthesizing silicon source of halosilane (org. Lett.2000,2,565, J. Org. Chem.2003,68,9384, org. Lett.2000,2,3221, org. Lett.2003,5,1899, org. Lett.2006,8,765, J. Org. Chem.2004,69, 8305) includes coupling reaction of organolithium reagent or Grignard reagent with halosilane to synthesize organosilicon compound. The method has the advantages that the synthetic route is simple, but the requirements on reaction conditions are severe, the reaction must be carried out under anhydrous and anaerobic conditions, the method has poor tolerance on a plurality of functional groups, and the expansion of the substrate range is limited to a certain extent. Therefore, the application of this synthetic route in organic synthesis is greatly limited. 2. The method for synthesizing the hydrosilane as the silicon source (J.Am.chem.Soc.2003, 125,13640, J.Am.chem.Soc.2003,125,30, org.Lett.2015,17,4538, ACS Catal.2018,8,5896, org.Lett.2018,20,5357, chem.Rev.2018,118 and 6516) has good selectivity, but the hydrosilane is expensive, high in toxicity, unstable in property and difficult to synthesize, and the practical application of the method is limited. 3. The method for synthesizing hexamethyldisilane as a silicon source (chem.Commun.2000, 1895, organometallics,2006,25,4665, org.Lett.2007,9,3785, J.Am.chem.Soc.2006,128,8152, J.Am.chem.Soc.2008,130,15982, J.Org.chem.1996,61,5779, org.Lett.2009,12,28, J.Am.chem.2008, 130,16382, J.Am.chem.Soc.2010,133, 387, org.Lett.2000,2, 7) has the advantages of high efficiency, good functional group tolerance and the like. Hexamethyldisilane is a commercially available, stable, low-toxicity disilane reagent that is widely used in the synthesis of silicon-based compounds. Compared with a hydrogen silane reagent, hexamethyldisilane has the advantages of low price, insensitivity to air and water, stable property, easy storage and the like. In recent years, organosilicon compounds have an important position in the creation of novel drugs, and research on synthesis methods thereof has been greatly advanced, in 2008, chatani and co-workers thereof have been developedPyridyl-oriented Rh catalyzes the ortho-silylation reaction of aryl C-H bonds with hexamethyldisilane (chem. Asian j.2008,3, 1585) to synthesize organosilicon compounds. This method, although high in yield, is poor in selectivity, and the product is a mixture of mono-and bis-silicon based. In 2014, motomu Kanai group used 8-aminoquinoline as a guide group to catalyze C (sp) of benzamide and carboxylic acid amide with palladium 2 ) -H and C (sp) 3 ) Regioselective activation of the-H bond followed by silylation reaction coupled with disilane to synthesize organosilanes (org. Lett.2014,16, 1968). The reaction functional group has better tolerance, but the substrate needs to be pre-functionalized, and the synthesis of raw materials is not easy. In 2015, the Yingsheng Zhao project performed a palladium catalyzed direct ortho-silylation of oxamide protected benzylamine and phenethylamine with hexamethyldisilane (org. Lett.2015,17, 3646). The method has good selectivity, but needs to protect amino, and has complicated steps. In the year of 2017, the method has the advantages that,Debabrata Maitithe group achieved a selective silicidation strategy for palladium-catalyzed meta-C-H bonds (Organometallics, 2017,36, 2418). The method has good selectivity, but the substrate is not easy to synthesize. In 2016, the group of Bing-Feng Shi subjects realized the Pd (II) catalyzed intermolecular silicidation of a-amino acids and simple fatty acid C-H bonds (Angew. Chem. Int. Ed.2016,55, 13859), and synthesized various β -silyl-a-amino acids. The method has excellent regioselectivity and stereoselectivity, but requires removal of auxiliary groups, and increases reaction steps. In 2018, the Yanghui Zhang group developed a method for efficiently synthesizing bis-silicon-based products by palladium-catalyzed halogenated aromatic hydrocarbons (Angew. Chem. Int. Ed.2018,57, 3233). The method has high yield, but narrow substrate range. These synthetic methods described above have a number of disadvantages: the reaction conditions are harsh, the substrates are difficult to synthesize and difficult to separate, the inert gas is used for protection in the reaction process, the requirements on equipment are high, and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for efficiently synthesizing an organic silicon compound, which has the advantages of simple operation, cheap used raw materials and low synthesis cost.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for efficiently synthesizing an organosilicon compound, comprising the following method steps:
in a reaction vessel, the molar ratio of 1:3 to 5:2 to 3 portions of phenylboronic acid derivatives, hexamethyldisilane and norbornene, 3 to 4mL of solvent is added according to 0.5mmol of phenylboronic acid, and then the catalyst Pd (OAc) is added 2 Oxidant Cu (OAc) 2 Alkali K 2 CO 3 The additive DABCO is added in an amount which is respectively 10.0-15.0 percent, 300-500 percent, 200 percent and 100-200 percent of the molar weight of the phenylboronic acid, 4mL of acetonitrile, the mixture reacts for 24-30 hours under the condition of oil bath at 120 ℃, the mixture is cooled to room temperature, water is added, ethyl acetate is used for extraction for three times, organic layers are combined, the mixture is decompressed and concentrated, and the product is purified by column chromatography to obtain the product organosilicon compound, wherein the reaction general formula of the synthetic method is as follows:
the chemical structural general formula of the organosilicon compound synthesized by the method is as follows:
wherein R is 1 Is hydrogen, ethyl, isopropyl, methoxy, fluoro, chloro, trifluoromethyl, phenyl or aryl; r is 2 Is hydrogen radical or methyl; r is 3 Hydrogen, methyl, fluoro or chloro; r 4 Hydrogen, methyl, fluoro or chloro.
The phenylboronic acid derivatives are phenylboronic acid, 3-methylphenylboronic acid, 3-ethylphenylboronic acid, 3-isopropylphenylboronic acid and 3-methoxyphenylboronic acid.
The solvent is acetonitrile or N, N-dimethylformamide.
The column chromatography conditions are as follows: 200-300 mesh silica gel column, and the eluent is petroleum ether.
The method for efficiently synthesizing the organic silicon compound, which is designed by adopting the technical scheme, has the beneficial effects that:
1. the method utilizes the phenylboronic acid to replace the traditional raw materials of halogenated aromatic hydrocarbon and a substrate containing a guide group, and the reaction operation is simple; the reaction substrate is simple, the source is wide, the method is suitable for the phenylboronic acid substituted by various functional groups, and the influence of the steric effect on the reaction is small.
2. The invention has the advantages of cheap reaction substrate, high yield, good selectivity, easy separation and purification, less pollution and simple steps, can omit the steps of protection and deprotection synthesis of functional groups, and the target product of the organic silicon compound is widely applicable to the aspects of organic intermediates, pharmaceutical intermediates and electronic device materials of organic chemical reactions.
Detailed Description
The method for efficiently synthesizing an organosilicon compound according to the present invention will be described in detail with reference to examples.
Example 1
A method of synthesizing trimethyl (2- (1s, 2s,3s, 4r) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) phenyl) silane (2 a), comprising the steps of:
to a 25mL Schlenk reaction tube were added 0.5mmol (61 mg) of phenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by 1.5mmol of hexamethyldisilazane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylene diamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, after the reaction (monitored by TLC), the reaction solution was cooled to room temperature, the reaction solution was filtered, the organic layer was then dried under reduced pressure using a rotary evaporator, and finally the crude product was purified by column chromatography (petroleum ether unless otherwise specified) to obtain 123.7mg of the desired target product (2 a) as a colorless oily liquid, which was dried under vacuum conditions, and the yield was calculated to be 78% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.42-7.40(m,2H),7.33-7.29(m,1H),7.17-7.14(m,1H),3.17(d,J＝10.5Hz,1H),2.36(dd,J＝3.5Hz,11.0Hz,2H),1.99(d,J＝10.0Hz,1H),1.80-1.75(m,1H),1.64-1.59(m,1H),1.46-1.41(m,1H),1.39-1.34(m,2H),1.29-1.27(m,1H),0.34(s,9H),-0.35(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)152.7,138.9,134.2,129.2,126.6,125.1,51.1,44.9,43.5,38.9,38.5,32.8,32.2,1.0,-0.8.HRMS(ESI-TOF)m/z calcd for C 19 H 33 Si 2 + (M+H) + 317.2115,found 317.2116。
Wherein, the chemical structure general formula of trimethyl (2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) phenyl) silane (2 a) is as follows:
example 2
A method of synthesizing trimethyl (3-methyl-2- ((1s, 2s,3s, 4r) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) phenyl) silane (2 b), comprising the steps of:
to a 25mL Schlenk reaction tube were added 0.5mmol (67.5 mg) of 3-methylphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, followed by cooling to room temperature (monitored by TLC), the reaction solution was filtered, the organic layer was then spin-dried under reduced pressure using a rotary evaporator, and finally the crude product was purified by column chromatography (petroleum ether unless otherwise specified) to obtain 137.4mg of the desired objective product (2 b) as a colorless oily liquid, which was dried under vacuum conditions, and the yield was calculated to be 83% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.40(d,J＝5.0Hz,1H),7.14-7.10(m,2H),3.53(d,J＝11.0Hz,1H),2.75(s,1H),2.56(s,3H),2.42(s,1H),2.04(d,J＝9.5Hz,1H),1.91-1.85(m,1H),1.67-1.54(m,2H),1.48(d,J＝11.0Hz,1H),1.45-1.38(m,2H),0.41(s,9H),-0.34(s,9H).. 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)148.5,142.1,135.2,134.2,133.1,125.4,53.9,44.9,41.0,39.8,38.9,33.5,32.2,23.1,2.1,-0.6.HRMS(EI)m/z calcd for C 20 H 34 Si 2 + (M) + 330.2199,found 330.2196。
Wherein the chemical structural general formula of trimethyl (3-methyl-2- ((1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) phenyl) silane (2 b) is as follows:
example 3
A method of synthesizing (3-ethyl-2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) phenyl) trimethylsilane (2 c) comprising the steps of:
to a 25mL Schlenk reaction tube were added 0.5mmol (74.5 mg) of 3-ethylphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by addition of 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, followed by cooling to room temperature (monitored by TLC), filtration of the reaction solution, spin-drying of the organic layer under reduced pressure with a rotary evaporator, and finally purification of the crude product by column chromatography (petroleum ether unless otherwise specified) to obtain 141.0mg of the desired objective product (2 c) as a colorless oily liquid, and after drying under vacuum, the yield was calculated to be 82% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.35-7.34(m,1H),7.18-7.17(m,1H),7.15-7.12(m,1H),3.47(d,J＝11.0Hz,1H),3.16-3.09(m,1H),2.63-2.56(m,2H),2.38(s,1H),2.01(d,J＝9.5Hz,1H),1.87-1.82(m,1H),1.61-1.56(m,1H),1.53-1.49(m,1H),1.43(d,J＝11.0Hz,1H),1.40-1.36(m,2H),1.24-1.21(m,3H),0.36(s,9H),-0.42(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)147.7,142.3,141.9,133.0,131.9,125.5,53.6,45.2,41.7,40.2,38.8,33.8,31.9,27.1,17.3,2.2,-0.8.HRMS(EI)m/z calcd for C 21 H 36 Si 2 + (M) + 344.2356,found 344.2356。
Wherein the chemical structure general formula of the (3-ethyl-2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) phenyl) trimethyl silane (2 c) is as follows:
example 4
A method of synthesizing (3-isopropyl-2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) phenyl) trimethylsilane (2 d) comprising the steps of:
to a 25mL Schlenk reaction tube were added 0.5mmol (82.0 mg) of 3-isopropylphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, after the reaction (monitored by TLC), cooled to room temperature, the reaction solution was filtered, the organic layer was then spin-dried under reduced pressure using a rotary evaporator, and finally the crude product was purified by column chromatography (petroleum ether unless otherwise specified) to obtain 114.9mg of the desired objective product (2 d) as a colorless oily liquid, which was dried under vacuum conditions, and the yield was calculated to be 64% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.37-7.31(m,2H),7.18-7.14(m,1H),3.60-3.52(m,2H),2.68(s,1H),2.39(s,1H),1.97(d,J＝12.0Hz,1H),1.88-1.82(m,1H),1.59(m,1H),1.53-1.47(m,2H),1.40(d,J＝12.0Hz,2H),1.34(d,J＝8.0Hz,3H),1.22(d,J＝7.5Hz,3H),0.38(s,9H),-0.36(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)147.4,147.1,142.5,133.2,128.0,125.6,53.8,44.5,42.0,40.5,39.2,34.0,31.9,28.3,27.9,23.5,2.4,-0.8.HRMS(EI)m/z calcd for C 22 H 38 Si 2 + (M) + 358.2512,found 358.2511。
Wherein the general chemical structure formula of the (3-isopropyl-2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) phenyl) trimethyl silane (2 d) is as follows:
example 5
A method for synthesizing (3-methoxy-2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) phenyl) trimethylsilane (2 e) comprises the following steps:
to a 25mL Schlenk reaction tube was added 0.5mmol (76.0 mg) of 3-methoxyphenylboronic acidBornylene 1.5mmol (141 mg), followed by addition of 1.5mmol hexamethyldisilane (219 mg), 11.3mg palladium acetate, 452.5mg anhydrous copper acetate, 138mg potassium carbonate, 112mg triethylene diamine, 4mL acetonitrile, stirring at 120 ℃ for 24 hours, after reaction (monitored by TLC), cooling to room temperature, filtering the reaction solution, followed by reduced pressure spin-drying of the organic layer using a rotary evaporator, and finally purification of the crude product (petroleum ether unless otherwise specified) by column chromatography to give 112.5mg of the desired target product (2 e) as a colorless oily liquid, which after drying under vacuum was calculated to have a yield of 65% and a purity of 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.18-7.15(m,1H),7.07(d,J＝7.0Hz,1H),6.85(d,J＝8.0Hz,1H),3.74(s,3H),3.22(d,J＝10.5Hz,1H),2.45(m,1H),2.33(m,1H),2.26(d,J＝9.5Hz,1H),1.83-1.78(m,1H),1.56-1.51(m,1H),1.44-1.40(m,1H),1.34-1.27(m,2H),1.18(d,J＝9.0Hz,1H),0.35(s,9H),-0.39(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)157.8,142.3,138.4,126.8,126.5,112.2,53.9,51.6,44.0,42.6,39.2,38.7,33.1,32.7,1.5,-0.9.HRMS(EI)m/z calcd for C 20 H 34 OSi 2 + (M) + 346.2148,found 358.2150。
Wherein the general chemical structure formula of the (3-methoxy-2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) phenyl) trimethyl silane (2 e) is as follows:
example 6
A method for synthesizing (3-fluoro-2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) phenyl) trimethylsilane (2 f) comprises the following steps:
to a 25mL Schlenk reaction tube were added 0.5mmol (70.0 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, then cooled to room temperature after the reaction (monitored by TLC), and the reaction mixture was cooled toFiltration, followed by spin-drying of the organic layer under reduced pressure using a rotary evaporator and finally purification of the crude product by column chromatography (petroleum ether unless otherwise specified) gave 138.6mg of the desired objective product (2 f) as a colorless oily liquid, which was dried under vacuum, and then calculated to have a yield of 83% and a purity of 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.26(d,J＝7.2Hz,1H),7.20-7.15(m,1H),7.04-7.00(m,1H),3.24(d,J＝10.4Hz,1H),2.52(s,1H),2.41(s,1H),2.20(d,J＝9.2Hz,1H),1.87-1.82(m,1H),1.67-1.61(m,1H),1.48-1.43(m,1H),1.36-1.26(m,2H),1.27(d,J＝10.0Hz,1H),0.39(s,9H),-0.30(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)161.3(d,J＝246.4Hz),143.6(d,J＝3.0Hz),137.0(d,J＝12.1Hz),130.2(d,J＝2.7Hz),127.1(d,J＝7.9Hz),117.6(d,J＝24.7Hz),50.1,44.0,42.8,39.3,38.2(d,J＝14.8Hz),33.0,32.5(d,J＝1.6Hz),1.3,-1.0(d,J＝1.0Hz).HRMS(EI)m/z calcd for C 19 H 31 FSi 2 + (M) + 334.1948,found.334.1951。
Wherein the chemical structural general formula of the (3-fluoro-2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) phenyl) trimethylsilane (2 f) is as follows:
example 7
A method of synthesizing (3-chloro-2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) phenyl) trimethylsilane (2 g) comprising the steps of:
to a 25mL Schlenk reaction tube was added 0.5mmol (78.0 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, after the reaction (monitored by TLC), cooled to room temperature, the reaction solution was filtered, the organic layer was then spin-dried under reduced pressure using a rotary evaporator, and the crude product was finally purified by column chromatography (petroleum ether unless otherwise specified) to give the desired targetThe title product (2 g) was 136.5mg as a colorless oily liquid, which was dried under vacuum, and was calculated to have a yield of 78% and a purity of 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.38(d,J＝7.5Hz,1H),7.31(d,J＝7.5Hz,1H),7.10-7.07(m,1H),3.42(d,J＝11.0Hz,1H),2.82(s,1H),2.39-2.35(m,2H),1.87-1.83(m,1H),1.62-1.57(m,1H),1.46-1.40(m,2H),1.38-1.34(m,1H),1.32(d,J＝10.0Hz,1H),0.37(s,9H),-0.33(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)147.0,145.0,133.5,133.0,132.9,126.7,53.3,45.1,41.2,40.1,38.9,33.3,32.4,1.8,-0.7.HRMS(EI)m/z calcd for C 19 H 31 ClSi 2 + (M) + 350.1653,found 350.1652。
Wherein the general chemical structure formula of the (3-chloro-2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) phenyl) trimethylsilane (2 g) is as follows:
example 8
Trimethyl (3- (trifluoromethyl) -2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo
A method for synthesizing [2.2.1] heptan-2-yl) phenyl) silane (2 h), comprising the following steps:
to a 25mL Schlenk reaction tube were added 0.5mmol (95.0 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, after the reaction (monitored by TLC), cooled to room temperature, the reaction solution was filtered, the organic layer was then spin-dried under reduced pressure using a rotary evaporator, and finally the crude product was purified by column chromatography (petroleum ether unless otherwise specified) to give the desired objective product (2 h) of 136.3mg as a colorless oily liquid, which was dried under vacuum, and the yield was calculated to be 71% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.71(d,J＝7.6Hz,2H),7.26(t,J＝7.6Hz,1H),3.66(d,J＝11.2Hz,1H),2.37(s,1H),2.89(s,1H),1.99(d,J＝10.0Hz,1H),1.82(d,J＝11.6Hz,1H),1.62-1.58(m,1H),1.52(d,J＝11.6Hz,1H),1.48-1.43(m,1H),1.39-1.34(m,1H),1.25(d,J＝10.0Hz,1H),0.41(s,9H),-0.41(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)150.0,146.0,139.1,128.6(q,J＝7.4Hz),127.8(d,J＝30.2Hz),125.2,124.7(q,J＝271.0Hz),54.4,44.9,41.5(q,J＝5.0Hz),39.3,38.9(q,J＝15.6Hz),34.3,31.7,2.4,-0.8.HRMS(EI)m/z calcd for C 20 H 31 F 3 Si 2 + (M) + 384.1916,found.384.1917。
Wherein the general chemical structure formula of trimethyl (3- (trifluoromethyl) -2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) phenyl) silane (2 h) is as follows:
example 9
A method of synthesizing trimethyl (4-methyl-2- ((1s, 2s,3s, 4r) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) phenyl) silane (2 i), comprising the steps of:
to a 25mL Schlenk reaction tube were added 0.5mmol (68.0 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by addition of 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, followed by cooling to room temperature (monitored by TLC), filtration of the reaction solution, spin-drying of the organic layer under reduced pressure with a rotary evaporator, and finally purification of the crude product by column chromatography (petroleum ether unless otherwise specified) to obtain 102.3mg of the desired objective product (2 i) as a colorless oily liquid, which was dried under vacuum, and the yield was calculated to be 62% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.32(d,J＝7.5Hz,1H),7.22(s,1H),6.99(d,J＝7.5Hz,1H),3.16(d,J＝10.5Hz,1H),2.37-2.34(m,5H),2.02(d,J＝10.0Hz,1H),1.80-1.76(m,1H),1.64-1.59(m,1H),1.46-1.36(m,3H),1.28(d,J＝10.0Hz,1H),0.33(s,9H),-0.35(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)152.8,138.8,135.6,134.3,127.7,125.9,51.0,44.9,43.6,39.0,38.5,32.8,32.2,21.4,1.0,-0.8.HRMS(EI)m/z calcd for C 20 H 34 Si 2 + (M) + 330.2199,found 330.2195。
Wherein the chemical structural general formula of trimethyl (4-methyl-2- ((1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) phenyl) silane (2 i) is as follows:
example 10
A method for synthesizing trimethyl (5-methyl-2- ((1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) phenyl) silane (2 j) comprises the following steps:
to a 25mL Schlenk reaction tube were added 0.5mmol (68.0 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by addition of 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, followed by cooling to room temperature (monitored by TLC), filtration of the reaction solution, spin-drying of the organic layer under reduced pressure with a rotary evaporator, and finally purification of the crude product by column chromatography (petroleum ether unless otherwise specified) to obtain 104.0mg of the desired objective product (2 j) as a colorless oily liquid, and after drying under vacuum, the yield was calculated to be 63% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.30(d,J＝8.0Hz,1H),7.21(s,1H),7.12(d,J＝7.5Hz,1H),3.14(d,J＝10.0Hz,1H),2.36-2.32(m,5H),1.98(d,J＝9.5Hz,1H),1.79-1.74(m,1H),1.63-1.57(m,1H),1.45-1.40(m,1H),1.37-1.35(m,2H),1.27-1.25(m,1H),0.34(s,9H),-0.34(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)149.7,138.7,134.8,134.1,130.0,126.5,50.7,45.0,43.5,38.8,38.5,32.8,32.1,21.1,1.0,-0.7.HRMS(EI)m/z calcd for C 20 H 34 Si 2 + (M) + 330.2199,found 330.2196。
Wherein the chemical structure general formula of trimethyl (5-methyl-2- ((1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) phenyl) silane (2 j) is as follows:
example 11
A method of synthesizing trimethyl (5-fluoro-2- ((1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) phenyl) silane (2 k) comprising the steps of:
to a 25mL Schlenk reaction tube were added 0.5mmol (70.0 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by 1.5mmol (219 mg) of hexamethyldisilane, 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, followed by cooling to room temperature (monitored by TLC), the reaction solution was filtered, the organic layer was then spin-dried under reduced pressure using a rotary evaporator, and finally the crude product was purified by column chromatography (petroleum ether unless otherwise specified) to obtain 85.2mg of the desired objective product (2 k) as a colorless oily liquid, which was dried under vacuum conditions, and the yield was calculated to be 51% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.36-7.34(m,1H),7.08-7.07(m,1H),6.98-6.95(m,1H),3.13(d,J＝10.5Hz,1H),2.36(s,1H),2.28(s,1H),1.93(d,J＝10.0Hz,1H),1.78-1.73(m,1H),1.63-1.58(m,1H),1.43-1.26(m,4H),0.33(s,9H),-0.35(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)160.7(d,J＝244.3Hz),148.4(d,J＝2.8Hz),141.9(d,J＝2.8Hz),128.0(d,J＝6.3Hz),120.2(d,J＝17.9Hz),115.6(d,J＝21.1Hz),50.4,45.0,43.5,38.7,38.6,32.7,32.1,0.7,-0.7.HRMS(ESI)m/z calcd for C 19 H 31 FSi 2 + (M) + 334.1948,found 334.1950。
Wherein the chemical structural general formula of trimethyl (5-fluoro-2- ((1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) phenyl) silane (2 k) is as follows:
example 12
A method of synthesizing (3, 4-dimethyl-2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) phenyl) trimethylsilane (2 l) comprising the steps of:
to a 25mL Schlenk reaction tube were added 0.5mmol (75.0 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by addition of 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, after the reaction (monitored by TLC), cooled to room temperature, the reaction solution was filtered, the organic layer was then spin-dried under reduced pressure using a rotary evaporator, and finally the crude product was purified by column chromatography (petroleum ether unless otherwise specified) to obtain 129.0mg of the desired objective product (2 l) as a colorless oily liquid, which was dried under vacuum, and the yield was calculated to be 75% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.27(d,J＝7.2Hz,1H),7.03(d,J＝7.2Hz,1H),3.52(d,J＝10.8Hz,1H),2.74(s,1H),2.40(s,4H),2.28(s,3H),2.05(d,J＝9.6Hz,1H),1.87(t,J＝11.6Hz,1H),1.62-1.61(m,1H),1.55-1.50(m,1H),1.7-1.39(m,3H),0.37(s,9H),-0.39(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)148.5,139.7,139.6,134.4,132.8,127.3,54.1,45.1,42.0,40.1,38.9,33.6,32.3,21.4,17.7,2.1,-0.7.HRMS(EI)m/z calcd for C 21 H 36 Si 2 + (M) + 344.2356,found 344.2357。
Wherein the chemical structural general formula of the (3, 4-dimethyl-2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) phenyl) trimethyl silane (2 l) is as follows:
example 13
A method of synthesizing (3, 5-dimethyl-2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) phenyl) trimethylsilane (2 m) comprising the steps of:
to a 25mL Schlenk reaction tube were added 0.5mmol (75.0 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by addition of 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, followed by cooling to room temperature (monitored by TLC), filtration of the reaction solution, spin-drying of the organic layer under reduced pressure with a rotary evaporator, and finally purification of the crude product by column chromatography (petroleum ether unless otherwise specified) to obtain 135.9mg of the desired objective product (2 m) as a colorless oily liquid, and after drying under vacuum, the yield was calculated to be 79% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.11(s,1H),6.88(s,1H),3.43-3.41(d,J＝10.8Hz,1H),2.63(s,1H),2.44(s,3H),2.33(s,1H),2.24(s,3H),1.95(d,J＝10.0Hz,1H),1.83-1.77(m,1H),1.59-1.53(m,1H),1.48-1.43(m,1H),1.40(d,J＝11.2Hz,1H),1.35-1.28(m,2H),0.32(s,9H),-0.40(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)145.4,141.9,134.9,134.8,134.3,133.8,53.3,44.9,41.1,39.7,38.8,33.5,32.2,23.0,20.7,2.1,0.6.HRMS(EI)m/z calcd for C 21 H 36 Si 2 + (M) + 344.2356,found 344.2356。
Wherein the chemical structural general formula of the (3, 5-dimethyl-2- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) phenyl) trimethyl silane (2 m) is as follows:
example 14
A method of synthesizing ((1r, 2s,3s, 4s) -3- (4-fluoro-2-methyl-6- (trimethylsilyl) phenyl) bicyclo [2.2.1] heptan-2-yl) trimethylsilane (2 n) comprising the steps of:
to a 25mL Schlenk reaction tube were added 0.5mmol (77.0 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethyleneacetateEnediamine, 4mL acetonitrile, was stirred at 120 ℃ for 24 hours, after the reaction (monitored by TLC), cooled to room temperature, the reaction solution was filtered, then the organic layer was spin-dried under reduced pressure using a rotary evaporator, and finally the crude product was purified by column chromatography (petroleum ether unless otherwise specified) to give 127.1mg of the desired target product (2 n) as a colorless oily liquid, which was dried under vacuum, and the yield was calculated to be 73% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.03(d,J＝9.0Hz,1H),6.79(d,J＝9.0Hz,1H),3.45(d,J＝11.0Hz,1H),2.65(s,1H),2.50(s,3H),2.37(s,1H),1.96(d,J＝9.5Hz,1H),1.86-1.82(m,1H),1.61-1.57(m,1H),1.48-1.46(m,1H),1.42(d,J＝11.0Hz,1H),1.35-1.34(m,2H),0.36(s,9H),-0.35(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)160.6(d,J＝244.5Hz),145.1(d,J＝2.6Hz),144.2(d,J＝2.6Hz),137.6(d,J＝2.5Hz),119.8(d,J＝19.8Hz),119.1(d,J＝18.1Hz),53.1,45.0,41.1,39.8,38.9,33.5,32.2,23.1,1.8,-0.6.HRMS(EI)m/z calcd for C 20 H 33 FSi 2 + (M+H) + 348.2105,found 348.2101。
Wherein the chemical structure general formula of ((1R, 2S,3S, 4S) -3- (4-fluoro-2-methyl-6- (trimethylsilyl) phenyl) bicyclo [2.2.1] heptane-2-yl) trimethylsilane (2 n) is as follows:
example 15
A method of synthesizing ((1r, 2s,3s, 4s) -3- (4-chloro-2-fluoro-6- (trimethylsilyl) phenyl) bicyclo [2.2.1] heptan-2-yl) trimethylsilane (2 o) comprising the steps of:
to a 25mL Schlenk reaction tube were added 0.5mmol (87.0 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, cooled to room temperature after the reaction (monitored by TLC), the reaction solution was filtered, and the organic layer was then spin-dried under reduced pressure using a rotary evaporator to obtain a final productThe crude product was then purified by column chromatography (petroleum ether, unless otherwise specified) to give the desired target product (2 o) as 110.4mg as a colorless oily liquid, which was dried under vacuum to calculate 60% yield and 99.9% purity. 1 H NMR(500MHz,CDCl 3 ,δppm)7.18(d,J＝2.0Hz,1H),7.02(dd,J＝1.5Hz,11.5Hz,1H),3.16(d,J＝11.0Hz,1H),2.43-2.37(m,2H),2.09(d,J＝9.5Hz,1H),1.81-1.77(m,1H),1.62-1.57(m,1H),1.41-1.37(m,1H),1.33-1.26(m,2H),1.22(d,J＝10.0Hz,1H),0.35(s,9H),-0.32(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)161.0(d,J＝250.9Hz),145.5(d,J＝3.8Hz),135.6(d,J＝12.7Hz),131.9(d,J＝9.0Hz),130.0(d,J＝2.6Hz),117.8(d,J＝28.1Hz),49.7(d,J＝1.5Hz),44.0,42.7(d,J＝1.4Hz),39.2,38.2(d,J＝14.2Hz),33.0,32.4,1.0,-0.9.HRMS(EI)m/z calcd for C 19 H 30 ClFSi 2 + (M) + 368.1559,found 368.1550。
Wherein the chemical structure general formula of ((1R, 2S,3S, 4S) -3- (4-chloro-2-fluoro-6- (trimethylsilyl) phenyl) bicyclo [2.2.1] heptane-2-yl) trimethylsilane (2 o) is as follows:
example 16
A method for synthesizing trimethyl (1- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) naphthalene-2-silane (2 p) comprises the following steps:
to a 25mL Schlenk reaction tube were added 0.5mmol (86.0 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by 1.5mmol (219 mg) of hexamethyldisilane, 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, cooled to room temperature after the reaction (monitored by TLC), the reaction solution was filtered, the organic layer was then spin-dried under reduced pressure using a rotary evaporator, and finally the crude product was purified by column chromatography (petroleum ether unless otherwise specified) to give 104.3mg of the desired target product (2 p) as a white solid, and dried under vacuumThereafter, the yield was calculated to be 57% and the purity was calculated to be 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)8.65(d,J＝7.5Hz,1H),7.82(d,J＝7.0Hz,1H),7.70(d,J＝8.0Hz,1H),7.59(d,J＝8.0Hz,1H),7.45-7.44(m,2H),3.85(d,J＝11.0Hz,1H),3.10(s,1H),2.48(s,1H),2.37(d,J＝9.0Hz,1H),1.98-1.93(m,1H),1.73-1.72(m,1H),1.64-1.62(m,1H),1.60-1.58(m,1H),1.49-1.47(m,2H),0.46(s 9H),-0.68(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)148.4,139.0,135.3,132.4,131.4,128.6,126.7,126.1,125.5,124.4,54.2,45.7,42.7,40.4,39.3,34.0,32.2,2.1,-1.0.HRMS(EI)m/z calcd for C 23 H 34 Si 2 + (M) + 366.2199,found 366.2196。
Wherein the chemical structural general formula of trimethyl (1- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) naphthalene-2-silane (2 p) is as follows:
example 17
A method for synthesizing trimethyl (3- ((1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) naphthalen-2-yl) silane (2 q) comprising the steps of:
to a 25mL Schlenk reaction tube were added 0.5mmol (86.0 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by addition of 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, followed by cooling to room temperature (monitored by TLC), filtration of the reaction solution, spin-drying of the organic layer under reduced pressure with a rotary evaporator, and finally purification of the crude product by column chromatography (petroleum ether unless otherwise specified) to obtain 69.6mg of the desired objective product (2 q) as a colorless oily liquid, and after drying under vacuum, the yield was calculated to be 38% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.94(s,1H),7.8(s,1H),7.80(d,J＝8.0Hz,1H),7.76(d,J＝8..0Hz,1H),7.48-7.40(m,2H),3.30(d,J＝10.0Hz,1H),2.47(dd,J＝3.0Hz,11.0Hz,2H),2.20(d,J＝10.0Hz,1H),1.84-1.79(m,1H),1.70-1.64(m,1H),1.52-1.46(m,2H),1.43-1-1.40(m,1H),1.38(dd,J＝2.0Hz,10.5Hz,1H),0.44(s,9H),-0.39(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)149.7,138.8,134.7,133.9,131.3,127.8,127.1,126.3,125.0,124.7,51.0,45.5,44.0,39.0,38.7,32.8,32.2,1.0,-0.7.HRMS(EI)m/z calcd for C 23 H 34 Si 2 + (M) + 366.2199,found 366.2194。
Wherein the chemical structural general formula of trimethyl (3- ((1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) naphthalene-2-yl) silane (2 q) is as follows:
example 18
A method of synthesizing trimethyl (2- (1S, 2R,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) thiophen-3-yl) silane (2 r) comprising the steps of:
to a 25mL Schlenk reaction tube were added 0.5mmol (64.0 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by addition of 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, followed by cooling to room temperature (monitored by TLC), filtration of the reaction solution, spin-drying of the organic layer under reduced pressure with a rotary evaporator, and finally purification of the crude product by column chromatography (petroleum ether unless otherwise specified) to obtain 66.1mg of the desired objective product (2 r) as a colorless oily liquid, and after drying under vacuum, the yield was calculated to be 41% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.11(d,J＝5.0Hz,1H),6.90(d,J＝4.5Hz,1H),3.50(d,J＝10.0Hz,1H),2.31(d,J＝19.0Hz,2H),1.90(d,J＝9.5Hz,1H),1.71-1.69(m,1H),1.66-1.63(m,1H),1.38-1.33(m,3H),1.20(d,J＝10.0Hz,1H),0.29(s,9H),-0.23(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)157.9,135.7,131.4,121.9,48.3,46.1,41.9,39.0,37.6,32.7,31.2,0.5,-1.1.HRMS(ESI-TOF)m/z calcd for C 17 H 31 SSi 2 + (M+H) + 323.1680,found 323.1684。
Wherein, the chemical structural general formula of trimethyl (2- (1S, 2R,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-group) thiophene-3-group) silane (2 r) is as follows:
example 19
A method of synthesizing trimethyl (3- ((1s, 2s,3s, 4r) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) thiophen-2-yl) silane (2 s) comprising the steps of:
to a 25mL Schlenk reaction tube were added 0.5mmol (64.0 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by addition of 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, followed by cooling to room temperature (monitored by TLC), filtration of the reaction solution, spin-drying of the organic layer under reduced pressure with a rotary evaporator, and finally purification of the crude product by column chromatography (petroleum ether unless otherwise specified) to obtain 79.1mg of the desired objective product (2 s) as a colorless oily liquid, and after drying under vacuum, the yield was calculated to be 49% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.46(d,J＝4.4Hz,1H),7.19(d,J＝4.4Hz,1H),3.23(d,J＝10.0Hz,1H),2.36(s,1H),2.25(s,1H),1.89(d,J＝9.6Hz,1H),1.75-1.72(m,1H),1.66-1.63(m,1H),1.39-1.31(m,3H),1.19(d,J＝10.4Hz,1H),0.36(s,9H),-0.28(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)154.1,133.2,129.7,128.5,47.4,44.2,41.7,38.8,37.8,32.9,31.7,0.7,-0.9.HRMS(ESI-TOF)m/z calcd for C 17 H 31 SSi 2 + (M+H) + 323.1680,found 323.1681。
Wherein the chemical structural general formula of trimethyl (3- ((1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) thiophene-2-yl) silane (2 s) is as follows:
example 20
A method for synthesizing 6- (trimethylsilyl) -5- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptan-2-yl) quinoline (2 t), comprising the steps of:
to a 25mL Schlenk reaction tube were added 0.5mmol (86.5 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, after the reaction (monitored by TLC), cooled to room temperature, the reaction solution was filtered, the organic layer was then spin-dried under reduced pressure using a rotary evaporator, and finally the crude product was purified by column chromatography (petroleum ether unless otherwise specified) to obtain 84.4mg of the desired objective product (2 t) as a yellow solid, which was dried under vacuum, and the yield was calculated to be 46% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)8.98(d,J＝8.5Hz,1H),8.86(dd,J＝1.5Hz,4Hz,1H),7.95(d,J＝8.5Hz,1H),7.80(d,J＝8.5Hz,1H),7.34-7.31(m,1H),3.83(d,J＝11.0Hz,1H),3.00(s,1H),2.47(d,J＝4.0Hz,1H),2.22(d,J＝9.5Hz,1H),1.96-1.89(m,1H),1.73-1.67(m,1H),1.62-1.56(m,2H),1.48-1.42(m,2H),0.43(s,9H),-0.71(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)149.8,149.7,140.0,135.0,134.8,127.3,127.1,119.2,53.8,45.6,42.8,40.4,39.4,33.9,32.1,1.9,-1.0.HRMS(ESI-TOF)m/z calcd for C 22 H 34 NSi 2 + (M+H) + 368.2224,found 368.2227。
Wherein the chemical structural general formula of the 6- (trimethylsilyl) -5- (1S, 2S,3S, 4R) -3- (trimethylsilyl) bicyclo [2.2.1] heptane-2-yl) quinoline (2 t) is as follows:
example 21
A method of synthesizing trimethyl ((1r, 2s,3s, 4s) -3- (3- (trimethylsilyl) - [1,1' -biphenyl ] -2-yl) bicyclo [2.2.1] heptan-2-yl) silane (2 u), comprising the steps of:
to a 25mL Schlenk reaction tube were added 0.5mmol (99.0 mg) of 3-methoxyphenylboronic acid, 1.5mmol (141 mg) of norbornene, followed by 1.5mmol of hexamethyldisilane (219 mg), 11.3mg of palladium acetate, 452.5mg of anhydrous copper acetate, 138mg of potassium carbonate, 112mg of triethylenediamine, and 4mL of acetonitrile, and the mixture was stirred at 120 ℃ for 24 hours, after the reaction (monitored by TLC), cooled to room temperature, the reaction solution was filtered, the organic layer was then spin-dried under reduced pressure using a rotary evaporator, and finally the crude product was purified by column chromatography (petroleum ether unless otherwise specified) to obtain 115.7mg of the desired objective product (2 u) as a white solid, which was dried under vacuum, and the yield was calculated to be 59% and the purity was 99.9%. 1 H NMR(500MHz,CDCl 3 ,δppm)7.51(d,J＝7.0Hz,1H),7.42(d,J＝7.0Hz,1H),7.38-7.30(m,3H),7.28-7.26(m,1H),7.17-7.14(m,1H),7.03(d,J＝7.0Hz,1H),3.58(d,J＝11.0Hz,1H),2.65(s,1H),2.00(s,1H),1.63-1.58(m,1H),1.49-1.44(m,1H),1.35(d,J＝11.0Hz,1H),1.30-1.23(m,2H),0.54(d,J＝9.5Hz,1H),0.42,(s,9H),0.35(d,J＝9.0Hz,1H),-0.37(s,9H). 13 C{1H}NMR(125MHz,CDCl 3 ,δppm)148.4,144.4,142.6,141.3,134.9,134.5,131.8,129.8,127.4,126.6,126.4,124.4,55.1,43.8,43.3,38.7,37.8,33.0,32.8,2.1,-0.5.HRMS(EI)m/z calcd for C 25 H 36 Si 2 + (M) + 392.2356,found 392.2355。
Wherein, the chemical structure general formula of trimethyl ((1R, 2S,3S, 4S) -3- (3- (trimethylsilyl) - [1,1' -biphenyl ] -2-yl) bicyclo [2.2.1] heptane-2-yl) silane (2 u) is as follows:
Claims (4)
1. a method for efficiently synthesizing an organic silicon compound is characterized by comprising the following steps:
in a reaction vessel, the molar ratio of 1:3 to 5:2 to 3Adding phenylboronic acid derivative, hexamethyldisilane and norbornene in sequence, adding 3-4 mL of solvent according to 0.5mmol of phenylboronic acid, and then adding catalyst Pd (OAc) 2 Cu (OAc) 2 Alkali K 2 CO 3 The additive DABCO is added with the amount of 10.0-15.0 percent, 300-500 percent, 200 percent, 100-200 percent and 4mL of acetonitrile in the molar amount of phenylboronic acid respectively, the mixture reacts for 24-30 h under the condition of oil bath at 120 ℃, the mixture is cooled to room temperature, water is added, ethyl acetate is used for extraction for three times, organic layers are combined and concentrated under reduced pressure, and a product is purified by column chromatography to obtain the product organosilicon compound, wherein the reaction general formula of the synthetic method is shown as follows:
the chemical structural general formula of the organosilicon compound synthesized by the method is as follows:
wherein R is 1 Is hydrogen radical, ethyl, isopropyl, methoxy, fluoro, chloro, trifluoromethyl, phenyl or aryl; r 2 Is hydrogen or methyl; r 3 Hydrogen, methyl, fluoro or chloro; r 4 Is hydrogen radical, methyl radical, fluorine radical or chlorine radical.
2. The method for efficiently synthesizing organic silicon compounds according to claim 1, wherein the benzene boric acid derivatives are benzene boric acid, 3-methyl benzene boric acid, 3-ethyl benzene boric acid, 3-isopropyl benzene boric acid, 3-methoxy benzene boric acid.
3. The method for efficiently synthesizing organic silicon compounds according to claim 1, wherein the solvent is acetonitrile or N, N-dimethylformamide.
4. The method for efficiently synthesizing the organic silicon compound according to claim 1, wherein the column chromatography conditions are as follows: 200-300 mesh silica gel column, and petroleum ether as eluent.
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| 李文广: "基于六甲基二硅 烷与钯杂环中间体的反 应研究", 湖南师范大学博士学位论文, pages 1 - 5 * |
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