CN105859765B - 一种烷基修饰的吡啶基芳基硅烷类化合物的制备方法 - Google Patents
一种烷基修饰的吡啶基芳基硅烷类化合物的制备方法 Download PDFInfo
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- CN105859765B CN105859765B CN201610265704.0A CN201610265704A CN105859765B CN 105859765 B CN105859765 B CN 105859765B CN 201610265704 A CN201610265704 A CN 201610265704A CN 105859765 B CN105859765 B CN 105859765B
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- Prior art keywords
- alkyl
- phenyl ring
- atom
- pyridyl group
- compound
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- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 31
- 125000004076 pyridyl group Chemical group 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- -1 acids compound Chemical class 0.000 claims abstract description 23
- 239000003446 ligand Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004471 Glycine Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- 150000004054 benzoquinones Chemical group 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 150000007529 inorganic bases Chemical group 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 2
- 229910001923 silver oxide Inorganic materials 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 1
- 229910052792 caesium Inorganic materials 0.000 claims 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 34
- 229910000077 silane Inorganic materials 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 238000010189 synthetic method Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 100
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 52
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 26
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 26
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 25
- 238000005160 1H NMR spectroscopy Methods 0.000 description 25
- 239000007788 liquid Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 24
- 239000011734 sodium Substances 0.000 description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 150000003961 organosilicon compounds Chemical class 0.000 description 8
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- MQUBEBJFHBANKV-UHFFFAOYSA-N di(propan-2-yl)silicon Chemical compound CC(C)[Si]C(C)C MQUBEBJFHBANKV-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- QPKFVRWIISEVCW-UHFFFAOYSA-N 1-butane boronic acid Chemical compound CCCCB(O)O QPKFVRWIISEVCW-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000006208 butylation Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 229940005561 1,4-benzoquinone Drugs 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- OKJIRPAQVSHGFK-UHFFFAOYSA-N N-acetylglycine Chemical compound CC(=O)NCC(O)=O OKJIRPAQVSHGFK-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- WIKQEUJFZPCFNJ-UHFFFAOYSA-N carbonic acid;silver Chemical compound [Ag].[Ag].OC(O)=O WIKQEUJFZPCFNJ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RROHLTDJOMFNNA-UHFFFAOYSA-N (2-butyl-4,5-dimethylphenyl)-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound C(CCC)C1=C(C=C(C(=C1)C)C)[Si](C1=NC=CC=C1)(C(C)C)C(C)C RROHLTDJOMFNNA-UHFFFAOYSA-N 0.000 description 1
- MMXKRFSZFHIHJP-UHFFFAOYSA-N (2-butyl-4-chlorophenyl)-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound C(CCC)C1=C(C=CC(=C1)Cl)[Si](C1=NC=CC=C1)(C(C)C)C(C)C MMXKRFSZFHIHJP-UHFFFAOYSA-N 0.000 description 1
- UWABHPRAWICYCC-UHFFFAOYSA-N (2-butyl-4-fluoro-5-methylphenyl)-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound C(CCC)C1=C(C=C(C(=C1)F)C)[Si](C1=NC=CC=C1)(C(C)C)C(C)C UWABHPRAWICYCC-UHFFFAOYSA-N 0.000 description 1
- NQJJQIIBDDXASO-UHFFFAOYSA-N (2-butyl-4-fluorophenyl)-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound C(CCC)C1=C(C=CC(=C1)F)[Si](C1=NC=CC=C1)(C(C)C)C(C)C NQJJQIIBDDXASO-UHFFFAOYSA-N 0.000 description 1
- FYWKESYWJPXRJU-UHFFFAOYSA-N (2-butyl-4-methoxyphenyl)-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound C(CCC)C1=C(C=CC(=C1)OC)[Si](C1=NC=CC=C1)(C(C)C)C(C)C FYWKESYWJPXRJU-UHFFFAOYSA-N 0.000 description 1
- BEHYFQQXAJQYBW-UHFFFAOYSA-N (2-butyl-4-methylphenyl)-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound C(CCC)C1=C(C=CC(=C1)C)[Si](C1=NC=CC=C1)(C(C)C)C(C)C BEHYFQQXAJQYBW-UHFFFAOYSA-N 0.000 description 1
- GPLNXZXQNYCQQK-UHFFFAOYSA-N (2-butyl-4-phenylphenyl)-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound C(CCC)C=1C=C(C=CC1[Si](C1=NC=CC=C1)(C(C)C)C(C)C)C1=CC=CC=C1 GPLNXZXQNYCQQK-UHFFFAOYSA-N 0.000 description 1
- XDJMDQPVXORWIS-UHFFFAOYSA-N (2-butyl-5-chlorophenyl)-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound C(CCC)C1=C(C=C(C=C1)Cl)[Si](C1=NC=CC=C1)(C(C)C)C(C)C XDJMDQPVXORWIS-UHFFFAOYSA-N 0.000 description 1
- BZMCFKUBTKYWCG-UHFFFAOYSA-N (2-butyl-5-methoxyphenyl)-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound C(CCC)C1=C(C=C(C=C1)OC)[Si](C1=NC=CC=C1)(C(C)C)C(C)C BZMCFKUBTKYWCG-UHFFFAOYSA-N 0.000 description 1
- KWPZJAFPULHCCW-UHFFFAOYSA-N (2-butylphenyl)-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound CCCCc1ccccc1[Si](C(C)C)(C(C)C)c1ccccn1 KWPZJAFPULHCCW-UHFFFAOYSA-N 0.000 description 1
- ZIMBXLBCOOKBGO-UHFFFAOYSA-N (2-butylphenyl)-methyl-(2-methylpropyl)-pyridin-2-ylsilane Chemical compound C(CCC)C1=C(C=CC=C1)[Si](C1=NC=CC=C1)(C)CC(C)C ZIMBXLBCOOKBGO-UHFFFAOYSA-N 0.000 description 1
- LKGOCGGWQBJGBG-UHFFFAOYSA-N (2-hexylphenyl)-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound C(CCCCC)C1=C(C=CC=C1)[Si](C1=NC=CC=C1)(C(C)C)C(C)C LKGOCGGWQBJGBG-UHFFFAOYSA-N 0.000 description 1
- JSQOKQZXWOOMRX-UHFFFAOYSA-N (4-bromo-2-butylphenyl)-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound BrC1=CC(=C(C=C1)[Si](C1=NC=CC=C1)(C(C)C)C(C)C)CCCC JSQOKQZXWOOMRX-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OGMICDFRYBWIDS-UHFFFAOYSA-N 1-[4-[4-[2-[di(propan-2-yl)-pyridin-2-ylsilyl]phenyl]butoxy]phenyl]ethanone Chemical compound C(C)(C)[Si](C1=C(C=CC=C1)CCCCOC1=CC=C(C=C1)C(C)=O)(C1=NC=CC=C1)C(C)C OGMICDFRYBWIDS-UHFFFAOYSA-N 0.000 description 1
- YFGNYEKROBECAM-UHFFFAOYSA-N 2-[4-[2-[di(propan-2-yl)-pyridin-2-ylsilyl]phenyl]butyl]isoindole-1,3-dione Chemical compound C(C)(C)[Si](C1=C(C=CC=C1)CCCCN1C(C2=CC=CC=C2C1=O)=O)(C1=NC=CC=C1)C(C)C YFGNYEKROBECAM-UHFFFAOYSA-N 0.000 description 1
- DEIARXYVTAEEDT-UHFFFAOYSA-N 3-butyl-4-[di(propan-2-yl)-pyridin-2-ylsilyl]-N,N-di(propan-2-yl)benzamide Chemical compound C(CCC)C=1C=C(C(=O)N(C(C)C)C(C)C)C=CC1[Si](C1=NC=CC=C1)(C(C)C)C(C)C DEIARXYVTAEEDT-UHFFFAOYSA-N 0.000 description 1
- OFMLDNINBYAZOE-UHFFFAOYSA-N 5-[2-[di(propan-2-yl)-pyridin-2-ylsilyl]phenyl]pentanenitrile Chemical compound C(C)(C)[Si](C1=C(C=CC=C1)CCCCC#N)(C1=NC=CC=C1)C(C)C OFMLDNINBYAZOE-UHFFFAOYSA-N 0.000 description 1
- JPGNJCUIPLBCQX-UHFFFAOYSA-N 7-[4-[2-[di(propan-2-yl)-pyridin-2-ylsilyl]phenyl]butoxy]-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=C1C=CC(=C2)OCCCCC3=CC=CC=C3[Si](C4=CC=CC=N4)(C(C)C)C(C)C JPGNJCUIPLBCQX-UHFFFAOYSA-N 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OAVWMXJLUJCFSD-UHFFFAOYSA-N [2-(2-phenylethyl)phenyl]-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound C(C)(C)[Si](C1=NC=CC=C1)(C1=C(C=CC=C1)CCC1=CC=CC=C1)C(C)C OAVWMXJLUJCFSD-UHFFFAOYSA-N 0.000 description 1
- GAVHGUJGWJUXKR-UHFFFAOYSA-N [2-(4-methoxybutyl)phenyl]-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound C(C)(C)[Si](C1=NC=CC=C1)(C1=C(C=CC=C1)CCCCOC)C(C)C GAVHGUJGWJUXKR-UHFFFAOYSA-N 0.000 description 1
- YXMONCRHHFITBT-UHFFFAOYSA-N [2-(4-phenylbutyl)phenyl]-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound C(C)(C)[Si](C1=NC=CC=C1)(C1=C(C=CC=C1)CCCCC1=CC=CC=C1)C(C)C YXMONCRHHFITBT-UHFFFAOYSA-N 0.000 description 1
- YHTYJYXQCNQXGL-UHFFFAOYSA-N [2-butyl-4-(trifluoromethyl)phenyl]-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound C(CCC)C1=C(C=CC(=C1)C(F)(F)F)[Si](C1=NC=CC=C1)(C(C)C)C(C)C YHTYJYXQCNQXGL-UHFFFAOYSA-N 0.000 description 1
- OGKQFTVEVDMDIT-UHFFFAOYSA-N [2-butyl-5-(trifluoromethyl)phenyl]-di(propan-2-yl)-pyridin-2-ylsilane Chemical compound C(CCC)C1=C(C=C(C=C1)C(F)(F)F)[Si](C1=NC=CC=C1)(C(C)C)C(C)C OGKQFTVEVDMDIT-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NPOMSUOUAZCMBL-UHFFFAOYSA-N dichloromethane;ethoxyethane Chemical compound ClCCl.CCOCC NPOMSUOUAZCMBL-UHFFFAOYSA-N 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 description 1
- PXIJGZGMRCQDFI-UHFFFAOYSA-N ethyl 3-butyl-4-[di(propan-2-yl)-pyridin-2-ylsilyl]benzoate Chemical compound C(CCC)C=1C=C(C(=O)OCC)C=CC=1[Si](C1=NC=CC=C1)(C(C)C)C(C)C PXIJGZGMRCQDFI-UHFFFAOYSA-N 0.000 description 1
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002518 isoindoles Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing 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
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J51/00—Normal steroids with unmodified cyclopenta(a)hydrophenanthrene skeleton not provided for in groups C07J1/00 - C07J43/00
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
Abstract
本发明涉及一种烷基修饰的吡啶基芳基硅烷类化合物及其制备方法，在有机溶剂中，控制反应温度为30～80℃，以有机硅烷和烷基硼酸化合物为原料，以Pd元素为催化剂，并在配体作用下，在氧化剂、添加剂条件下反应2～48h制得烷基修饰的吡啶基芳基硅烷类化合物。本发明首次完成烷基官能团化的吡啶基芳基硅烷化合物的合成方法，且与现有技术相比，本发明具有条件温和、产率良好、操作简单、底物适用范围广等优点。
Description
技术领域
本发明涉及有机合成领域，具体涉及一种烷基修饰的吡啶基芳基硅烷类化合物的制备方法。
背景技术
有机硅化合物是有机化合物类别中非常重要的一类物质，并随着材料化学的发展和有机硅材料的使用，对有机硅化合物的物化性质和有机硅化合物的合成越来越重视。特别是有机硅化合物基质的有机硅材料在发光二极管、薄膜晶体管、太阳能电池和防爆检测等领域具有重要用途，由此对于不同有机硅化合物的合成提出了新的要求。然而目前实现有机硅化合物的合成主要通过硅氯键在惰性气体环境中低温下与丁基锂反应后生成的锂试剂对相关底物的亲核取代反应，此类方法条件苛刻、操作复杂，且对底物的适用性窄，因此寻求条件温和、操作简单、底物范围广的有机硅化合物的合成方法具有重大的现实意义。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种合成方法简单、高效的烷基修饰的吡啶基芳基硅烷类化合物的制备方法。
本发明的目的可以通过以下技术方案来实现：一种烷基修饰的吡啶基芳基硅烷类化合物，该化合物的结构式如下：
其中，R1选自苯环、含取代基苯环、烷基或含取代基的烷基中的一种；
R2和R3相同或不同，R2和R3选自烷基或带杂原子的烷基；
R为苯环上的取代基，选自H、4-Me、4-OMe、3-OMe、4-CF3、3-CF3、4-F、4-Cl、3-Cl、4-Br、4-Ph、4-CO2Et、4-CON(i-Pr)2、3,4-diMe或3-Me-4-F中的一种，3代表苯环上与硅原子所连的碳原子的间位碳原子，4代表苯环上与硅原子所连的碳原子的对位碳原子。
所述的取代基包括芳基、甲氧基、卤素、羰基、酯基或氰基中的一种，所述的杂原子包括氧原子或氮原子。
一种如上所述烷基修饰的吡啶基芳基硅烷类化合物的制备方法，将有机硅烷、烷基硼酸化合物、配体、氧化剂、添加剂、促进剂、催化剂以1:(1～4):0.02:(1～3):(1～3):(0.5～2):0.01的摩尔比进行混合，溶于有机溶剂内，在30～80℃温度下反应2～48h，更优选的，60℃条件下反应48h，即得所述烷基修饰的吡啶基芳基硅烷类化合物。
本发明的方法是一种有效的以钯作为催化剂，在配体的促进下，加之氧化剂和添加剂的作用下，由吡啶基芳基硅烷与烷基硼酸的碳氢键活化偶联反应合成烷基修饰的吡啶基芳基硅烷类化合物的方法。
本方法中促进剂的作用非常关键，当不加入促进剂时，反应无法进行，这是基于反应机理中实现还原消除过程的作用；而氧化剂的作用在于将完成催化循坏的Pd(0)氧化成Pd(II)以实现催化循坏；添加剂在于增强底物C-H键的酸性，辅助C-H键的活化断裂；配体在此方法中的作用也是非常重要，当没有配体的参与时，反应产率非常低，这主要在于配体能够与钯催化剂配位之后增强钯催化的活性，提高底物与催化剂的活性匹配度。此外，该方法的最大的优点在于基于C-H键活化官能团化反应的原理，实现了原子经济性非常高的过程，反应底物中只离去了一个氢原子，这极大减少了反应废料的产生，而且反应在空气环境中以温和条件就能高效地实现。
本发明的烷基修饰的吡啶基芳基硅烷类化合物是以吡啶基芳基硅烷、烷基硼酸为原料，在有机溶剂的存在下，以Pd(OAc)2与配体作用下，在氧化剂、添加剂条件下发生偶联反应制得，反应式如下：
所述有机硅烷的结构式如下：
其中，R2和R3相同或不同，R2和R3选自烷基或带杂原子的烷基；
R为苯环上的取代基，选自H、4-Me、4-OMe、3-OMe、4-CF3、3-CF3、4-F、4-Cl、3-Cl、4-Br、4-Ph、4-CO2Et、4-CON(i-Pr)2、3,4-diMe或3-Me-4-F中的一种，3代表苯环上与硅原子所连的碳原子的间位碳原子，4代表苯环上与硅原子所连的碳原子的对位碳原子。
所述烷基硼酸化合物的结构式为R1-B-(OH)2，其中，R1选自苯环、含取代基苯环、烷基或含取代基的烷基中的一种。
所述催化剂为Pd(OAc)2、Pd(TFA)2、PdCl2或Pd(MeCN)Cl2中的一种。
所述配体为氮原子被保护的氨基酸，其结构式如下：
所述配体优选为氮原子被乙酰基保护的甘氨酸。
所述氧化剂包括碳酸银、氧化银、醋酸银、硫酸银或无水硫酸铜中的一种；
所述的添加剂为无机碱类物质，包括碳酸氢钠、碳酸氢钾、碳酸锂、碳酸钠、碳酸钾、碳酸铯或醋酸钾中的一种；
所述的反应促进剂为苯醌；
所述有机溶剂包括四氢呋喃、叔戊醇、叔丁醇、乙醚、1,4-二氧六环或N,N-二甲基甲酰胺中的一种。
采用本发明方法所得产物烷基修饰的吡啶基芳基硅烷类化合物可以经过薄层层析、柱层析或减压蒸馏的方法来分离。如用薄层层析、柱层析的方法，所用展开剂为非极性溶剂与极性溶剂的混合溶剂。推荐溶剂可为石油醚-二氯甲烷，石油醚-乙酸乙酯，石油醚-乙醚等混合溶剂，其体积比可以分别为：非极性溶剂：极性溶剂＝10：1。例如：石油醚/乙酸乙酯＝10/1。
与现有技术相比，本发明的有益效果体现在：
(1)该方法可适用于不同类型的芳基硅烷底物和烷基硼酸，反应条件温和，操作简便，反应的产率为40％-90％，高于现有的合成方法。
(2)本发明基于C-H键活化官能团化反应的过程，反应底物中只离去了一个氢原子，这极大减少了反应废料的产生，是一个原子经济性非常高的有机硅化合物的合成技术。
具体实施方式
下面对本发明的实施例作详细说明，本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例1
钯催化吡啶基芳基硅烷与丁基硼酸反应合成丁基修饰的吡啶基芳基硅烷化合物：
在35mL的反应管中依次加入搅拌子，4.5mg Pd(OAc)2(10mol％)，相应的吡啶基芳基硅烷(0.2mmol)，30.6mg丁基硼酸(0.6mmol)，4.6mg Ac-Gly-OH(20mol％)，21.8mg BQ(1.2equiv)，110.2mg Ag2CO3(2.0equiv)，16.8mg NaHCO3(1.0equiv)和1.0mL THF。然后用配套的聚四氟乙烯塞密闭反应管，置于60℃的磁力搅拌器中反应48h。反应结束时将反应管移离加热装置并冷却至室温，反应液用乙酸乙酯稀释并通过硅藻土抽滤，乙酸乙酯洗涤数次后得到的滤液用旋转蒸发仪浓缩，得到的粗产物通过硅胶板纯化分离得到相应的丁基化产物，称重确定产率，并用NMR和HRMS作定性检测。
其中BQ为1,4-对苯醌，THF为四氢呋喃。
经NMR和HRMS检测，各实验组产物表征数据如下：
实验1：2-((2-丁基苯基)二异丙基硅基)吡啶
2-((2-butylphenyl)diisopropylsilyl)pyridine
无色液体，90％收率。
1H NMR(400MHz,CDCl3)δ8.81(d,J＝4.6Hz,1H),7.56(td,J＝7.6,1.7Hz,1H),7.48(dd,J＝7.4,1.4Hz,2H),7.36–7.31(m,1H),7.26–7.14(m,3H),2.42–2.34(m,2H),1.73(dd,J＝14.8,7.4Hz,2H),1.45–1.36(m,2H),1.06(d,J＝7.4Hz,6H),1.03–0.97(m,8H),0.71(t,J＝7.3Hz,3H).13C NMR(100MHz,CDCl3)δ165.10,149.96,149.87,136.82,133.32,131.39,131.18,129.26,128.62,124.65,122.49,36.87,33.62,22.96,18.22,17.96,13.81,11.23.HRMS(ESI-TOF)m/z:calcd for C21H31NNaSi+:348.2118(M+Na)+,found:348.2118。
实验2：2-((2-丁基-4-甲基苯基)二异丙基硅基)吡啶
2-((2-butyl-4-methylphenyl)diisopropylsilyl)pyridine
无色液体，83％收率。
1H NMR(400MHz,CDCl3)δ8.81(d,J＝4.7Hz,1H),7.56(td,J＝7.6,1.6Hz,1H),7.47(d,J＝7.5Hz,1H),7.38(d,J＝7.6Hz,1H),7.21(ddd,J＝7.5,4.9,1.3Hz,1H),7.08(s,1H),7.01(d,J＝7.6Hz,1H),2.38–2.30(m,5H),1.71(dt,J＝14.7,7.4Hz,2H),1.50–1.31(m,2H),1.05(d,J＝7.4Hz,6H),1.03–0.97(m,8H),0.72(t,J＝7.3Hz,3H).13C NMR(100MHz,CDCl3)δ165.33,149.87,139.02,136.92,133.34,132.07,131.27,129.59,127.77,125.67,122.46,36.77,33.68,22.99,21.40,18.26,18.02,13.79,11.28.HRMS(ESI-TOF)m/z:calcdfor C22H33NNaSi+:362.2274(M+Na)+,found:362.2265。
实验3：2-((2-丁基-4-甲氧基苯基)二异丙基硅基)吡啶
2-((2-butyl-4-methoxyphenyl)diisopropylsilyl)pyridine
无色液体，42％收率。
1H NMR(400MHz,CDCl3)δ8.80(d,J＝4.5Hz,1H),7.55(t,J＝7.0Hz,1H),7.47(d,J＝7.4Hz,1H),7.40(d,J＝8.3Hz,1H),7.23–7.16(m,1H),6.81(d,J＝2.0Hz,1H),6.78–6.71(m,1H),3.81(s,3H),2.41–2.32(m,2H),1.69(dt,J＝14.5,7.4Hz,4H),1.47–1.36(m,2H),1.05(d,J＝7.4Hz,6H),1.02–0.95(m,8H),0.71(t,J＝7.3Hz,3H).13C NMR(100MHz,CDCl3)δ165.35,160.57,151.84,149.93,138.26,133.27,131.20,122.42,114.53,110.25,54.86,36.84,33.46,22.91,18.24,17.96,13.80,11.27.HRMS(ESI-TOF)m/z:calcd forC22H33NNaOSi+:378.2224(M+Na)+,found:378.2230。
实验4：2-((2-丁基-5-甲氧基苯基)二异丙基硅基)吡啶
2-((2-butyl-5-methoxyphenyl)diisopropylsilyl)pyridine
无色液体，51％收率。
1H NMR(400MHz,CDCl3)δ8.84–8.77(m,1H),7.56(td,J＝7.6,1.7Hz,1H),7.51–7.45(m,1H),7.23–7.15(m,2H),7.03(d,J＝2.8Hz,1H),6.89(dd,J＝8.5,2.8Hz,1H),3.77(s,3H),2.36–2.26(m,2H),1.71(dt,J＝14.7,7.4Hz,2H),1.37(ddd,J＝11.7,10.1,6.5Hz,2H),1.08(d,J＝7.4Hz,6H),1.05–0.95(m,8H),0.71(t,J＝7.3Hz,3H).13C NMR(100MHz,CDCl3)δ165.04,156.48,149.97,141.83,133.32,133.01,131.21,129.52,122.51,122.41,114.35,55.11,35.84,33.83,22.89,18.29,18.08,13.80,11.37.HRMS(ESI-TOF)m/z:calcdfor C22H33NNaOSi+:378.2224(M+Na)+,found:378.2216。
实验5：2-((2-丁基-4-三氟甲基苯基)二异丙基硅基)吡啶
2-((2-butyl-4-(trifluoromethyl)phenyl)diisopropylsilyl)pyridine
无色液体，76％收率。
1H NMR(400MHz,CDCl3)δ8.81(d,J＝4.6Hz,1H),7.59(dt,J＝7.5,3.9Hz,2H),7.48(d,J＝7.6Hz,2H),7.41(d,J＝7.9Hz,1H),7.24(ddd,J＝7.6,4.9,1.3Hz,1H),2.47–2.40(m,2H),1.72(dd,J＝14.8,7.4Hz,2H),1.47–1.36(m,2H),1.07(d,J＝7.4Hz,6H),1.04–0.96(m,8H),0.73(t,J＝7.3Hz,3H).13C NMR(100MHz,CDCl3)δ164.21,150.67,150.18,137.11,136.82,133.56,131.07(q,JCF＝10.1Hz),124.93(q,JCF＝11.6Hz),122.78(q,JCF＝220.1Hz),121.15(q,JCF＝10.2Hz),99.96,36.69,33.34,22.88,18.18,17.93,13.72,11.29.HRMS(ESI-TOF)m/z:calcd for C22H31F3NSi+:394.2172(M+H)+,found:394.2176。
实验6：2-((2-丁基-5-三氟甲基苯基)二异丙基硅基)吡啶
2-((2-butyl-5-(trifluoromethyl)phenyl)diisopropylsilyl)pyridine
无色液体，60％收率。
1H NMR(400MHz,CDCl3)δ8.81(d,J＝4.8Hz,1H),7.72(s,1H),7.63–7.54(m,2H),7.48(d,J＝7.5Hz,1H),7.35(d,J＝8.1Hz,1H),7.26–7.21(m,1H),2.45–2.36(m,2H),1.74(dt,J＝14.8,7.4Hz,2H),1.43–1.35(m,2H),1.06(d,J＝7.4Hz,6H),1.01(d,J＝7.3Hz,6H),0.99–0.94(m,2H),0.70(t,J＝7.3Hz,3H).13C NMR(100MHz,CDCl3)δ164.09,154.01,150.18,133.60,133.11(q,JCF＝8.4Hz),132.89,131.01,128.87,128.59(q,JCF＝9.6Hz),125.96(q,JCF＝15.1Hz),122.81(q,JCF＝274.2Hz),36.79,33.30,22.88,18.14,17.85,13.72,11.15.HRMS(ESI-TOF)m/z:calcd for C22H30F3NNaSi+:416.1992(M+Na)+,found:416.1986。
实验7：2-((2-丁基-4-氟苯基)二异丙基硅基)吡啶
2-((2-butyl-4-fluorophenyl)diisopropylsilyl)pyridine
无色液体，87％收率。
1H NMR(400MHz,CDCl3)δ8.84–8.79(m,1H),7.58(td,J＝7.6,1.7Hz,1H),7.50–7.41(m,2H),7.22(ddd,J＝7.6,4.9,1.3Hz,1H),6.96(dd,J＝11.1,2.5Hz,1H),6.88(td,J＝8.5,2.6Hz,1H),2.42–2.34(m,2H),1.69(dq,J＝14.6,7.3Hz,2H),1.45–1.35(m,2H),1.05(d,J＝7.4Hz,6H),1.03–0.96(m,8H),0.72(t,J＝7.3Hz,3H).13C NMR(100MHz,CDCl3)δ165.29,164.84,162.83,152.87,150.07,138.57(d,JCF＝7.6Hz),133.43(d,JCF＝233.0Hz),131.10,122.60,115.39(d,JCF＝19.4Hz),111.93(d,JCF＝19.5Hz),36.60,33.16,22.81,18.21,17.94,13.74,11.31.HRMS(ESI-TOF)m/z:calcd for C21H30FNNaSi+:366.2024(M+Na)+,found:366.2002。
实验8：2-((2-丁基-4-氯苯基)二异丙基硅基)吡啶
2-((2-butyl-4-chlorophenyl)diisopropylsilyl)pyridine
无色液体，72％收率。
1H NMR(400MHz,CDCl3)δ8.81(d,J＝4.8Hz,1H),7.58(t,J＝7.6Hz,1H),7.47(d,J＝7.5Hz,1H),7.40(d,J＝8.1Hz,1H),7.23(t,J＝6.0Hz,2H),7.16(dd,J＝8.0,1.5Hz,1H),2.40–2.32(m,2H),1.73–1.67(m,2H),1.44–1.37(m,2H),1.05(d,J＝7.4Hz,6H),1.03–0.96(m,8H),0.72(t,J＝7.3Hz,3H).13C NMR(100MHz,CDCl3)δ164.54,151.94,150.05,138.06,135.65,133.53,131.13,130.04,128.70,124.98,122.69,36.56,33.28,22.84,18.18,17.93,13.73,11.25.HRMS(ESI-TOF)m/z:calcd for C21H30ClNNaSi+:382.1728(M+Na)+,found:382.1721。
实验9：2-((2-丁基-5-氯苯基)二异丙基硅基)吡啶
2-((2-butyl-5-chlorophenyl)diisopropylsilyl)pyridine
无色液体，80％收率。
1H NMR(400MHz,CDCl3)δ8.80(dd,J＝3.3,1.1Hz,1H),7.58(td,J＝7.6,1.7Hz,1H),7.47(d,J＝7.6Hz,1H),7.41(d,J＝2.3Hz,1H),7.28(dd,J＝8.3,2.3Hz,1H),7.22(ddd,J＝7.6,4.9,1.3Hz,1H),7.18(d,J＝8.3Hz,1H),2.37–2.29(m,2H),1.71(dt,J＝14.8,7.4Hz,2H),1.40–1.31(m,2H),1.07(d,J＝7.4Hz,6H),1.04–0.96(m,8H),0.70(t,J＝7.3Hz,3H).13C NMR(100MHz,CDCl3)δ164.35,150.11,148.12,136.01,134.51,133.52,131.09,130.94,130.11,129.25,122.72,36.17,33.50,22.85,18.21,17.99,13.74,11.29.HRMS(ESI-TOF)m/z:calcd for C21H30ClNNaSi+:383.1728(M+Na)+,found:382.1718。
实验:10：2-((4-溴-2-丁基苯基)二异丙基硅基)吡啶
2-((4-bromo-2-butylphenyl)diisopropylsilyl)pyridine
无色液体，51％收率。
1H NMR(400MHz,CDCl3)δ8.81(d,J＝4.7Hz,1H),7.59(td,J＝7.6,1.5Hz,1H),7.47(d,J＝7.6Hz,1H),7.40(d,J＝1.2Hz,1H),7.36–7.28(m,2H),7.26–7.19(m,1H),2.41–2.30(m,2H),1.74–1.66(m,4H),1.44–1.34(m,2H),1.05(d,J＝7.4Hz,6H),0.99(d,J＝7.4Hz,6H),0.72(t,J＝7.3Hz,3H).13C NMR(100MHz,CDCl3)δ156.66,152.16,150.05,138.26,136.65,133.57,131.66,131.16,127.89,124.37,122.72,36.55,33.32,22.85,18.18,17.93,13.73,11.23.HRMS(ESI-TOF)m/z:calcd for C21H30BrNNaSi+:426.1223(M+Na)+,found:426.1224。
实验11：2-((3-丁基-[1,1’-联苯基]-4-基)二异丙基硅基)吡啶
2-((3-butyl-[1,1'-biphenyl]-4-yl)diisopropylsilyl)pyridine
无色液体，82％收率。
1H NMR(400MHz,CDCl3)δ8.83(d,J＝4.7Hz,1H),7.65–7.58(m,3H),7.55(dt,J＝10.5,4.6Hz,2H),7.48(d,J＝1.5Hz,1H),7.46–7.39(m,3H),7.34(t,J＝7.3Hz,1H),7.25–7.20(m,1H),2.50–2.40(m,2H),1.82-1.74(m,2H),1.48(ddd,J＝11.9,10.1,6.6Hz,2H),1.10(d,J＝7.4Hz,6H),1.08–1.01(m,8H),0.74(t,J＝7.3Hz,3H).13C NMR(101MHz,CDCl3)δ165.11,150.33,150.00,141.81,141.23,137.37,133.37,131.23,130.39,128.66,127.42,127.23,127.11,123.46,122.53,36.95,33.71,23.00,18.29,18.05,13.81,11.37.HRMS(ESI-TOF)m/z:calcd for C27H35NNaSi+:424.2431(M+Na)+,found:424.2430。
实验12：乙基30丁基-4-(二异丙基(吡啶-2-基)硅基)苯甲酸酯
ethyl 3-butyl-4-(diisopropyl(pyridin-2-yl)silyl)benzoate
无色液体，87％收率。
1H NMR(400MHz,CDCl3)δ8.80(d,J＝4.8Hz,1H),7.90(d,J＝1.3Hz,1H),7.81(dd,J＝7.8,1.5Hz,1H),7.58(td,J＝7.8,1.9Hz,2H),7.46(d,J＝7.6Hz,1H),7.22(ddd,J＝7.6,4.9,1.3Hz,1H),4.37(q,J＝7.1Hz,2H),2.47–2.39(m,2H),1.74(dd,J＝14.8,7.4Hz,2H),1.50–1.36(m,5H),1.06(d,J＝7.4Hz,6H),1.03–0.95(m,8H),0.72(t,J＝7.3Hz,3H).13CNMR(100MHz,CDCl3)δ167.00,164.46,150.20,150.10,138.10,136.81,133.47,131.12,131.07,129.25,125.27,122.69,60.85,36.69,33.51,22.92,18.18,17.95,14.35,13.74,11.30.HRMS(ESI-TOF)m/z:calcd for C24H35NNaO2Si+:420.2329(M+Na)+,found:420.2333。
实验13：3-丁基-4-(二异丙基(吡啶-2-基)硅基)-N,N-二异丙基苯甲酰胺
3-butyl-4-(diisopropyl(pyridin-2-yl)silyl)-N,N-diisopropylbenzamide
无色液体，75％收率。
1H NMR(400MHz,CDCl3)δ8.80(d,J＝4.5Hz,1H),7.59(td,J＝7.6,1.7Hz,1H),7.51(d,J＝7.5Hz,1H),7.46(d,J＝7.6Hz,1H),7.22(ddd,J＝7.5,4.9,1.3Hz,1H),7.18(d,J＝1.2Hz,1H),7.10(dd,J＝7.6,1.5Hz,1H),3.96(s,1H),3.50(s,1H),2.42–2.34(m,2H),1.69(d,J＝7.4Hz,2H),1.49(s,6H),1.44–1.38(m,2H),1.15(s,6H),1.06(d,J＝7.4Hz,6H),1.03–0.94(m,8H),0.71(t,J＝7.3Hz,3H).13C NMR(100MHz,CDCl3)δ171.38,164.76,150.20,150.01,139.44,136.90,133.54,132.34,131.12,125.81,122.61,121.80,36.79,33.42,29.68,22.90,20.75,18.18,17.89,13.73,11.29.HRMS(ESI-TOF)m/z:calcd forC28H44N2NaOSi+:475.3115(M+Na)+,found:475.3113。
实验14：2-((2-丁基-4,5-二甲基苯基)二异丙基硅基)吡啶
2-((2-butyl-4,5-dimethylphenyl)diisopropylsilyl)pyridine
无色液体，77％收率。
1H NMR(400MHz,CDCl3)δ8.80(d,J＝4.5Hz,1H),7.54(d,J＝1.7Hz,1H),7.47(s,1H),7.22(s,1H),7.19(ddd,J＝7.4,4.9,1.3Hz,1H),7.03(s,1H),2.34–2.27(m,2H),2.25(s,3H),2.23(s,3H),1.71(dd,J＝14.7,7.4Hz,2H),1.42–1.35(m,2H),1.06(d,J＝7.4Hz,6H),1.03–0.94(m,8H),0.71(t,J＝7.3Hz,3H).13C NMR(100MHz,CDCl3)δ165.55,149.89,147.37,138.04,137.69,133.18,132.55,131.22,130.15,128.28,122.35,36.37,33.82,22.99,19.78,19.41,18.31,18.08,13.80,11.32.HRMS(ESI-TOF)m/z:calcd forC23H35NNaSi+:376.2431(M+Na)+,found:376.2422。
实验15：2-((2-丁基-4-氟-5-甲基苯基)二异丙基硅基)吡啶
2-((2-butyl-4-fluoro-5-methylphenyl)diisopropylsilyl)pyridine
无色液体，52％收率。
1H NMR(400MHz,CDCl3)δ8.80(d,J＝4.6Hz,1H),7.57(td,J＝7.6,1.7Hz,1H),7.47(d,J＝7.5Hz,1H),7.21(ddd,J＝7.5,6.6,3.5Hz,2H),6.90(d,J＝11.8Hz,1H),2.37–2.28(m,2H),2.23(s,3H),1.70(dd,J＝14.8,7.4Hz,2H),1.42–1.32(m,2H),1.05(d,J＝7.4Hz,6H),0.99(d,J＝7.4Hz,6H),0.94(dd,J＝12.7,5.5Hz,2H),0.71(t,J＝7.3Hz,3H).13C NMR(100MHz,CDCl3)δ164.93,163.76,161.31,150.03,139.90(d,JCF＝5.4Hz),133.38(d,JCF＝232.0Hz),131.05,126.52(d,JCF＝4.4Hz)122.53,120.83(d,JCF＝15.9Hz),115.02(d,JCF＝20.3Hz),36.23,33.28,22.80,18.22,17.95,14.32(d,JCF＝3.2Hz),13.76,11.25.HRMS(ESI-TOF)m/z:calcd forC22H33FNSi+:358.2361(M+H)+,found:358.2356。
实验16：2-((2-丁基苯基)(异丁基)(甲基)硅基)吡啶
2-((2-butylphenyl)(isobutyl)(methyl)silyl)pyridine
无色液体，40％收率。
1H NMR(400MHz,CDCl3)δ8.78(d,J＝4.8Hz,1H),7.56–7.49(m,2H),7.40(d,J＝7.5Hz,1H),7.35–7.30(m,1H),7.21–7.15(m,3H),2.54–2.46(m,2H),1.80(dt,J＝13.3,6.6Hz,1H),1.25(dd,J＝6.8,2.7Hz,4H),1.16–1.08(m,2H),0.88(t,J＝6.1Hz,6H),0.74(t,J＝7.2Hz,3H),0.66(s,3H).13C NMR(100MHz,CDCl3)δ167.66,150.07,149.19,135.52,134.86,133.83,129.96,129.55,128.57,125.02,122.54,36.22,34.09,26.34,26.20,24.87,24.28,22.81,13.91.HRMS(ESI-TOF)m/z:calcd for C20H29NNaSi+:334.1961(M+Na)+,found:334.1956。
实施例2
钯催化对吡啶基苯基二异丙基硅烷烷基化修饰的反应：
在35mL的反应管中依次加入搅拌子，4.5mg Pd(OAc)2(10mol％)，相应的吡啶基芳基硅烷(0.2mmol)，烷基硼酸(0.6mmol)，4.6mg Ac-Gly-OH(20mol％)，21.8mg BQ(1.2equiv)，110.2mg Ag2CO3(2.0equiv)，16.8mg NaHCO3(1.0equiv)和1.0mL THF。然后用配套的聚四氟乙烯塞密闭反应管，置于60℃的磁力搅拌器中反应48h。反应结束时将反应管移离加热装置并冷却至室温，反应液用乙酸乙酯稀释并通过硅藻土抽滤，乙酸乙酯洗涤数次后得到的滤液用旋转蒸发仪浓缩，得到的粗产物通过硅胶板纯化分离得到相应的烷基化产物，称重确定产率，并用NMR和HRMS作定性检测。
其中BQ为1,4-对苯醌，THF为四氢呋喃。
经NMR和HRMS检测，各实验组产物表征数据如下：
实验17：2-((2-己基苯基)二异丙基硅基)吡啶
2-((2-hexylphenyl)diisopropylsilyl)pyridine
无色液体，82％收率。
1H NMR(400MHz,CDCl3)δ8.81(d,J＝4.5Hz,1H),7.56(td,J＝7.6,1.7Hz,1H),7.51–7.45(m,2H),7.36–7.30(m,1H),7.26–7.14(m,3H),2.42–2.34(m,2H),1.76–1.69(m,2H),1.47–1.37(m,2H),1.19(dd,J＝14.6,7.3Hz,2H),1.12–1.05(m,8H),1.04–0.95(m,8H),0.82(t,J＝7.2Hz,3H).13C NMR(100MHz,CDCl3)δ165.25,149.97,149.92,136.81,133.32,131.54,131.18,129.26,128.61,124.66,122.48,37.17,31.62,31.52,29.56,22.54,18.27,18.03,14.04,11.33.HRMS(ESI-TOF)m/z:calcd for C23H35NNaSi+:376.2431(M+Na)+,found:376.2419。
实验18：2-(二异丙基(2-苯乙基苯基)硅基)吡啶
2-(diisopropyl(2-phenethylphenyl)silyl)pyridine
无色液体，58％收率。
1H NMR(400MHz,CDCl3)δ8.82(d,J＝4.6Hz,1H),7.59–7.50(m,3H),7.38(d,J＝6.6Hz,2H),7.21–7.09(m,5H),6.82(d,J＝7.0Hz,2H),2.76(s,4H),1.72(dd,J＝14.7,7.4Hz,2H),1.09(d,J＝7.4Hz,6H),1.01(d,J＝7.3Hz,6H).13C NMR(100MHz,CDCl3)δ165.07,150.14,148.66,141.94,136.99,133.50,131.76,131.19,129.41,128.94,128.17,128.01,125.66,125.07,122.64,38.49,37.52,18.31,18.05,11.37.HRMS(ESI-TOF)m/z:calcd for C25H31NNaSi+:396.2118(M+Na)+,found:396.2115。
实验19：2-(二异丙基(2-(4-苯基丁基)苯基)硅基)吡啶
2-(diisopropyl(2-(4-phenylbutyl)phenyl)silyl)pyridine
无色液体，65％收率。
1H NMR(400MHz,CDCl3)δ8.79(d,J＝4.8Hz,1H),7.48(dd,J＝14.2,7.4Hz,3H),7.37–7.30(m,1H),7.28–7.23(m,2H),7.23–7.12(m,4H),7.08(d,J＝7.1Hz,2H),2.41(dd,J＝14.9,7.2Hz,4H),1.75–1.70(m,2H),1.47(dd,J＝8.1,3.6Hz,2H),1.27(d,J＝6.6Hz,2H),1.06(d,J＝7.4Hz,6H),1.01(t,J＝6.2Hz,6H).13C NMR(100MHz,CDCl3)δ165.12,149.97,149.55,142.54,136.79,133.39,131.47,131.13,129.30,128.64,128.34,128.18,125.57,124.76,122.53,37.02,35.76,31.73,31.18,18.22,17.96,11.23.HRMS(ESI-TOF)m/z:calcd for C27H35NNaSi+:424.2431(M+Na)+,found:424.2437。
实验20：2-(二异丙基(2-(4-甲氧基丁基)苯基)硅基)吡啶
2-(diisopropyl(2-(4-methoxybutyl)phenyl)silyl)pyridine
无色液体，70％收率。
1H NMR(400MHz,CDCl3)δ8.81(d,J＝4.4Hz,1H),7.56(dd,J＝7.6,1.7Hz,1H),7.51–7.46(m,2H),7.36–7.30(m,1H),7.26(t,J＝3.5Hz,1H),7.23–7.14(m,2H),3.26(s,3H),3.17(t,J＝6.7Hz,2H),2.44–2.37(m,2H),1.72(dt,J＝14.7,7.4Hz,2H),1.54–1.44(m,2H),1.26(dd,J＝9.3,5.5Hz,2H),1.08–1.05(m,6H),1.00(d,J＝7.4Hz,6H).13C NMR(100MHz,CDCl3)δ171.38,164.76,150.01,139.44,136.90,133.54,132.34,131.12,125.81,122.61,121.80,36.79,33.42,22.90,20.75,18.18,17.89,13.73,11.29.HRMS(ESI-TOF)m/z:calcd for C22H33NNaOSi+:378.2224(M+Na)+,found:378.2225。
实验21：5-(2-(二异丙基(吡啶-2-基)硅基)苯基)戊腈
5-(2-(diisopropyl(pyridin-2-yl)silyl)phenyl)pentanenitrile
无色液体，71％收率。
1H NMR(400MHz,CDCl3)δ8.82(d,J＝4.7Hz,1H),7.61(td,J＝7.6,1.7Hz,1H),7.51(dd,J＝11.3,7.6Hz,2H),7.38–7.31(m,1H),7.26–7.19(m,3H),2.42–2.35(m,2H),2.10(t,J＝7.2Hz,2H),1.74–1.69(m,2H),1.53(ddd,J＝11.7,10.1,6.5Hz,2H),1.26(dd,J＝15.2,7.4Hz,2H),1.06(d,J＝7.4Hz,6H),1.01(d,J＝7.4Hz,6H).13C NMR(100MHz,CDCl3)δ165.23,150.07,148.19,136.82,133.63,131.66,131.05,129.48,128.55,125.15,122.68,119.48,36.07,30.40,25.42,18.20,17.96,16.84,11.24.HRMS(ESI-TOF)m/z:calcd forC22H30N2NaSi+:373.2070(M+Na)+,found:373.2045。
实验22：2-(4-(2-(二异丙基(吡啶-2-基)硅基)苯基)丁基)异吲哚-1,3-二酮
2-(4-(2-(diisopropyl(pyridin-2-yl)silyl)phenyl)butyl)isoindoline-1,3-dione
无色液体，46％收率。
1H NMR(400MHz,CDCl3)δ8.78(d,J＝4.5Hz,1H),7.83(dd,J＝5.3,3.1Hz,2H),7.71(dd,J＝5.3,3.1Hz,2H),7.55(t,J＝7.3Hz,1H),7.48(t,J＝8.2Hz,2H),7.32(t,J＝7.4Hz,1H),7.24–7.14(m,3H),3.49(t,J＝7.2Hz,2H),2.43–2.34(m,2H),1.74–1.66(m,2H),1.43(dt,J＝15.9,9.0Hz,2H),1.29(d,J＝7.2Hz,2H),1.04(d,J＝7.4Hz,6H),0.98(d,J＝7.3Hz,6H).13C NMR(100MHz,CDCl3)δ174.39,168.26,150.06,149.00,136.74,133.84,133.48,132.13,131.05,129.86,129.39,128.77,124.91,123.11,122.76,37.73,36.62,29.68,28.82,18.20,17.95,11.21.HRMS(ESI-TOF)m/z:calcd for C29H34N2NaO2Si+:493.2282(M+Na)+,found:493.2282。
实验23：1-(4-(4-(2-(二异丙基(吡啶-2-基)硅基)苯基)丁氧基)苯基)乙酮
1-(4-(4-(2-(diisopropyl(pyridin-2-yl)silyl)phenyl)butoxy)phenyl)ethanone
无色液体，52％收率。
1H NMR(400MHz,CDCl3)δ8.80(d,J＝4.6Hz,1H),7.92(d,J＝8.8Hz,2H),7.53(dt,J＝16.6,7.2Hz,3H),7.35(t,J＝7.4Hz,1H),7.27(d,J＝4.7Hz,1H),7.19(dd,J＝12.3,5.1Hz,2H),6.85(d,J＝8.8Hz,2H),3.82(t,J＝6.4Hz,2H),2.56(s,3H),2.49–2.42(m,2H),1.72(dt,J＝14.8,7.4Hz,4H),1.53–1.45(m,2H),1.06(d,J＝7.4Hz,6H),1.00(d,J＝7.3Hz,6H).13C NMR(100MHz,CDCl3)δ196.81,165.17,162.94,162.48,150.03,149.00,136.89,133.45,131.54,131.12,130.54,129.39,128.58,124.97,122.58,114.06,67.78,36.65,29.19,27.81,26.34,18.22,17.97,11.25.HRMS(ESI-TOF)m/z:calcd forC29H37NNaO2Si+:482.2486(M+Na)+,found:482.2493。
实验24：7-(4-(2-(二异丙基(吡啶-2-基)硅基)苯基)丁氧基)-4-甲基-2H-苯并吡喃-2-酮
7-(4-(2-(diisopropyl(pyridin-2-yl)silyl)phenyl)butoxy)-4-methyl-2H-chromen-2-one
无色液体，69％收率。
1H NMR(400MHz,CDCl3)δ8.81(d,J＝4.6Hz,1H),7.57(t,J＝7.0Hz,1H),7.49(dd,J＝14.9,8.4Hz,3H),7.35(t,J＝7.4Hz,1H),7.28(s,1H),7.20(t,J＝7.5Hz,2H),6.79(dd,J＝8.8,2.3Hz,1H),6.72(d,J＝2.2Hz,1H),6.13(s,1H),3.80(t,J＝6.3Hz,2H),2.51–2.42(m,2H),2.40(s,3H),1.72(dt,J＝14.7,7.3Hz,2H),1.62(dd,J＝10.2,5.8Hz,2H),1.51(dd,J＝13.8,6.6Hz,2H),1.06(d,J＝7.4Hz,6H),1.01(d,J＝7.3Hz,6H).13C NMR(100MHz,CDCl3)δ165.19,162.06,161.37,155.26,152.57,150.07,148.96,136.88,133.48,131.57,131.10,129.40,128.59,125.42,124.98,122.61,113.39,112.66,111.83,101.21,68.11,36.62,29.07,27.79,18.66,18.22,17.97,11.25.HRMS(ESI-TOF)m/z:calcd forC31H37NNaO3Si+:522.2435(M+Na)+,found:522.2430。
实验25：(8S，9S，13S，14S)-3-(4-(2-(二异丙基(吡啶-2-基)硅基)苯基)丁氧基)-7，8，9，11，12，13，15，16-八氢-6H-环戊[a]菲-17(14H)-酮
(8S,9S,13S,14S)-3-(4-(2-(diisopropyl(pyridin-2-yl)silyl)phenyl)butoxy)-7,8,9,11,12,13,15,16-octahydro-6H-cyclopenta[a]phenanthren-17(14H)-one
无色液体，71％收率。
1H NMR(400MHz,CDCl3)δ8.80(d,J＝4.6Hz,1H),7.55(t,J＝7.5Hz,1H),7.49(t,J＝6.8Hz,2H),7.34(t,J＝7.2Hz,1H),7.27(s,1H),7.19(t,J＝7.1Hz,3H),6.64(d,J＝8.4Hz,1H),6.58(s,1H),3.74(t,J＝6.5Hz,2H),2.88(d,J＝9.4Hz,2H),2.55–2.48(m,1H),2.48–2.42(m,2H),2.39(d,J＝9.6Hz,1H),2.23(d,J＝11.8Hz,1H),2.06(dddd,J＝23.4,20.4,12.2,3.6Hz,6H),1.72(dt,J＝14.8,7.4Hz,3H),1.47–1.42(m,3H),1.06(d,J＝7.4Hz,6H),1.00(t,J＝7.0Hz,6H),0.97(d,J＝7.5Hz,1H),0.91(s,4H).13C NMR(100MHz,CDCl3)δ165.10,156.97,156.71,150.01,149.24,137.62,136.85,133.46,131.80,131.49,131.14,129.35,128.61,126.24,124.87,122.58,114.45,112.03,67.45,50.37,48.01,43.95,38.36,36.73,35.87,31.55,29.65,29.45,27.88,26.55,25.91,21.57,18.22,17.97,13.84,11.24.HRMS(ESI-TOF)m/z:calcd for C38H50NO2Si+:580.3605(M+H)+,found:580.3630。
实施例3
将吡啶基芳基硅烷、丁基硼酸、氮原子被乙酰基保护的甘氨酸、AgO、KHCO3、苯醌、Pd(TFA)2以1:1:0.02:1:1:0.5:0.01的摩尔比混合，溶于溶剂叔戊醇中，然后用配套的聚四氟乙烯塞密闭反应管，置于30℃的磁力搅拌器中反应48h。反应结束时将反应管移离加热装置并冷却至室温，反应液用乙酸乙酯稀释并通过硅藻土抽滤，乙酸乙酯洗涤数次后得到的滤液用旋转蒸发仪浓缩，得到的粗产物通过硅胶板纯化分离得到相应的丁基化产物，称重并计算产率。最终的产物为：
产率为75％。
实施例4
将吡啶基芳基硅烷、丁基硼酸、氮原子被乙酰基保护的甘氨酸、醋酸银、碳酸锂、苯醌、PdCl2以1:4:0.02:3:3:2:0.01的摩尔比混合，溶于溶剂乙醚中，然后用配套的聚四氟乙烯塞密闭反应管，置于80℃的磁力搅拌器中反应2h。反应结束时将反应管移离加热装置并冷却至室温，反应液用乙酸乙酯稀释并通过硅藻土抽滤，乙酸乙酯洗涤数次后得到的滤液用旋转蒸发仪浓缩，得到的粗产物通过硅胶板纯化分离得到相应的丁基化产物，称重并计算产率。最终的产物为：
产率为53％。
Claims (3)
1.一种烷基修饰的吡啶基芳基硅烷类化合物的制备方法，该化合物的结构式如下：
其中，R1选自苯环、含取代基苯环、烷基或含取代基的烷基中的一种；
R2和R3相同或不同，R2和R3选自烷基或带杂原子的烷基；
R为苯环上的取代基，选自H、4-Me、4-OMe、3-OMe、4-CF3、3-CF3、4-F、4-Cl、3-Cl、4-Br、4-Ph、4-CO2Et、4-CON(i-Pr)2、3,4-diMe或3-Me-4-F中的一种，3代表苯环上与硅原子所连的碳原子的间位碳原子，4代表苯环上与硅原子所连的碳原子的对位碳原子；
所述的取代基包括芳基、甲氧基、卤素、羰基、酯基或氰基中的一种，所述的杂原子包括氧原子或氮原子，其特征在于，包括以下步骤：
将有机硅烷、烷基硼酸化合物、配体、氧化剂、添加剂、促进剂、催化剂以1:(1～4):0.02:(1～3):(1～3):(0.5～2):0.01的摩尔比进行混合，溶于有机溶剂内，在30～80℃温度下反应2～48h，即得所述烷基修饰的吡啶基芳基硅烷类化合物；
其中，所述有机硅烷的结构式如下：
其中，R2和R3相同或不同，R2和R3选自烷基或带杂原子的烷基；
R为苯环上的取代基，选自H、4-Me、4-OMe、3-OMe、4-CF3、3-CF3、4-F、4-Cl、3-Cl、4-Br、4-Ph、4-CO2Et、4-CON(i-Pr)2、3,4-diMe或3-Me-4-F中的一种，3代表苯环上与硅原子所连的碳原子的间位碳原子，4代表苯环上与硅原子所连的碳原子的对位碳原子；
所述烷基硼酸化合物的结构式为R1-B-(OH)2，其中，R1选自苯环、含取代基苯环、烷基或含取代基的烷基中的一种；
所述催化剂为Pd(OAc)2、Pd(TFA)2、PdCl2或Pd(MeCN)Cl2中的一种；
所述配体为氮原子被保护的氨基酸，其结构式如下：
所述配体为氮原子被乙酰基保护的甘氨酸；
所述氧化剂包括碳酸银、氧化银、醋酸银、硫酸银或无水硫酸铜中的一种；
所述的添加剂为无机碱类物质，包括碳酸氢钠、碳酸氢钾、碳酸锂、碳酸钠、碳酸钾、碳酸铯或醋酸钾中的一种；
所述的反应促进剂为苯醌。
2.根据权利要求1所述的一种烷基修饰的吡啶基芳基硅烷类化合物的制备方法，其特征在于，所述有机溶剂包括四氢呋喃、叔戊醇、叔丁醇、乙醚、1,4-二氧六环或N,N-二甲基甲酰胺中的一种。
3.根据权利要求1所述的一种烷基修饰的吡啶基芳基硅烷类化合物的制备方法，其特征在于，所述的反应温度为60℃，所述的反应时间为48h。
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| A General Strategy Toward Aromatic 1,2-Ambiphilic Synthons:Palladium-Catalyzed ortho-Halogenation of PyDipSi-Arenes;Alexander S. Dudnik等，;《Angew. Chem. Int. Ed.》;20100930;第49卷;第8729-8732页 |
| PyDipSi: A General and Easily Modifiable/Traceless Si-Tethered Directing Group for C-H Acyloxylation of Arenes;Natalia Chernyak等，;《J. AM. CHEM. SOC.》;20100528;第132卷;第8270–8272页 |
| The Pyridyldiisopropylsilyl Group: A Masked Functionality and Directing Group for Monoselective ortho-Acyloxylation and ortho-Halogenation Reactions of Arenes;Chunhui Huang等，;《Adv. Synth. Catal.》;20110517;第353卷;第1285-1305页，尤其是第1296页化合物11 |
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