CN115448941A - 一种烯丙基取代的芳基有机硅化合物制备方法 - Google Patents
一种烯丙基取代的芳基有机硅化合物制备方法 Download PDFInfo
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- -1 allyl substituted aryl organosilicon compound Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000005859 coupling reaction Methods 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 239000002841 Lewis acid Substances 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 150000007517 lewis acids Chemical class 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- OCMNCWNTDDVHFK-UHFFFAOYSA-L dichloronickel;1,2-dimethoxyethane Chemical compound Cl[Ni]Cl.COCCOC OCMNCWNTDDVHFK-UHFFFAOYSA-L 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 claims description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 2
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 2
- OXMGUTQVUIWQEK-UHFFFAOYSA-N [N].CC(=O)N(C)C Chemical group [N].CC(=O)N(C)C OXMGUTQVUIWQEK-UHFFFAOYSA-N 0.000 claims description 2
- CUTSCJHLMGPBEJ-UHFFFAOYSA-N [N].CN(C)C=O Chemical compound [N].CN(C)C=O CUTSCJHLMGPBEJ-UHFFFAOYSA-N 0.000 claims description 2
- ZFCODINDSKDSBA-UHFFFAOYSA-N [N].CNC(C)=O Chemical group [N].CNC(C)=O ZFCODINDSKDSBA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 claims description 2
- RRSIMIHTHWYRRA-UHFFFAOYSA-L dibromonickel;1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound Br[Ni]Br.COCCOCCOC RRSIMIHTHWYRRA-UHFFFAOYSA-L 0.000 claims description 2
- KDJHHFWQUAOVNB-UHFFFAOYSA-L dichloronickel tricyclohexylphosphane Chemical compound Cl[Ni]Cl.C1CCC(CC1)P(C1CCCCC1)C1CCCCC1 KDJHHFWQUAOVNB-UHFFFAOYSA-L 0.000 claims description 2
- MJFCDPLEATUOPF-UHFFFAOYSA-L dichloronickel;triphenylphosphane Chemical compound Cl[Ni]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MJFCDPLEATUOPF-UHFFFAOYSA-L 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 2
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims 1
- NPAXPTHCUCUHPT-UHFFFAOYSA-N 3,4,7,8-tetramethyl-1,10-phenanthroline Chemical compound CC1=CN=C2C3=NC=C(C)C(C)=C3C=CC2=C1C NPAXPTHCUCUHPT-UHFFFAOYSA-N 0.000 claims 1
- JIVLDFFWTQYGSR-UHFFFAOYSA-N 4,7-dimethyl-[1,10]phenanthroline Chemical compound C1=CC2=C(C)C=CN=C2C2=C1C(C)=CC=N2 JIVLDFFWTQYGSR-UHFFFAOYSA-N 0.000 claims 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 claims 1
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 abstract description 13
- 239000010703 silicon Substances 0.000 abstract description 13
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract 2
- 150000003377 silicon compounds Chemical class 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 239000012300 argon atmosphere Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000010791 quenching Methods 0.000 description 9
- 230000000171 quenching effect Effects 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 150000001500 aryl chlorides Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005937 allylation reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- 150000001499 aryl bromides Chemical class 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
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- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000009509 drug development Methods 0.000 description 1
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- 239000012847 fine chemical Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000006578 reductive coupling reaction Methods 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical group OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic 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
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- C—CHEMISTRY; METALLURGY
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- 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
- C07F7/083—Syntheses without formation of a Si-C bond
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Abstract
本发明公开一种烯丙基取代有机硅化合物的制备方法。本发明以三氟甲磺酸取代的芳基硅试剂为原料,在镍催化下,通过与和烯丙醇的偶联反应,生成结构中带有烯丙基官能团的有机芳基硅试剂。本发明具有反应条件温和、原料简单易得、底物适用性广、反应官能团兼容性好等优点。
Description
技术领域
本发明涉及一种有机化合物的制备方法,确切讲是一种烯丙基取代的芳基有机硅化合物制备方法。
背景技术
烯丙基化合物中众多生物活性分子和药物分子的重要结构片段,也是重要有机合成子,在药物研发、材料科学和精细化工等领域具有重要的应用(Chem.Commun.,2022,58,2866)。有机硅试剂作为重要的活泼有机金属试剂在有机合成,生物活性分子修饰有重要的应用(Angew.Chem.Int.Ed.,2016,55,15787)。烯丙基取代的有机芳基硅试剂兼备烯丙基化合物和有机硅试剂的双重特性,在有机合成,材料科学及精细化工等领域更有应用前景。烯丙基取代的有机芳基硅试剂兼备烯丙基化合物和有机硅试剂的双重特性,在材料领域和有机合成领域具有重要的应用前景。
目前,烯丙基化合物最为常用也是最经典的合成方案是利用格氏试剂与烯丙基化试剂的取代反应(J.Org.Chem.2002,67,5327),该方法反应条件剧烈,底物局限性大,因此不适用于含羟基、氨基、醛基等功能性有机硅化合物的合成,另外格氏试剂不易储存,也为该方法的使用带来了局限性。近年来,过渡金属催化的亲电偶联反应取得了很大的发展,带动了烯丙基有机硅试剂合成方法的革新。利用芳基氯代物或芳基溴代物通过与烯丙基试剂的还原偶联法合成烯丙基取代的有机芳基硅试剂(Chem.Sci.,2018,9,640;Org.Biomol.Chem.,2021,19,9723),由于芳基氯代物或溴代物具有较高的解离能,因此,该类方法也需要较高的反应条件,另外,芳基氯代物或溴代物具有较高的毒性,限制了此类方法的广泛应用。
烯丙醇廉价易得且环保,是理想的烯丙基化试剂,以4-(三甲基硅基)苯基三氟甲基磺酸盐为原料通过亲电交叉偶联反应的方法实现烯丙基取代的有机芳基硅试剂化合物制备是一条理想的途径。另一方面,烯丙醇作为天然产物中结构丰富的化合物,原料廉价易得,也是相对比较环保的偶联试剂。然而由于含有三氟甲磺酸酯和芳基硅试剂两个活性官能团的兼容问题,以及烯丙醇难于活化的问题,如何实现底物活性匹配和产物选择性仍然具有很大的挑战。
发明内容
本发明提供一种可克服现有技术不足、用于制备烯丙基取代的有机芳基硅化合物的方法。
本发明的一种如Ⅲ示的烯丙基取代的芳基有机硅化合物制备方法的反应式如下式所示,即(1)式所示的三氟甲磺酸取代芳基硅试剂为原料,在镍催化下,
以锰粉、锌粉、镁粉或铝粉中的任一种作为还原剂,联吡啶作为配体,Lewis酸作为添加剂,在有机溶剂中及惰性气体保护下,通过与如Ⅱ示烯丙醇的偶联反应,得到目标产物,式(1)中的standard conditions是指反应的温度为-10℃~100℃,其中:所述有机溶剂为氮氮甲基乙酰胺(DMA)、溶剂为氮氮二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、二乙醇二甲醚(DME)或N-甲基吡咯烷酮(NMP)中的任一种,R1为吲哚、吡啶、甲基、苯基、咔唑或取代的烷基或芳基的任一种;R2、R3为分别为氢或甲基中的任一种,且两者可以相同或不同。
优选地,本发明的烯丙基取代的有机芳基硅化合物制备方法中反应所用的催化剂为氯化镍或溴化镍或碘化镍或氟化镍或二茂镍或碳酸镍或三环己基膦氯化镍或三苯基膦氯化镍或二甲氧基乙烷氯化镍或(1,1'-双(二苯基膦)二茂铁)氯化镍或双-(1,5-环辛二烯)镍或二乙二醇二甲醚溴化镍或氯化镍(II)乙二醇二甲醚中的任一种。
优选地,本发明的有机芳基硅化合物制备方法中所述的配体氮杂配体为2,2'-联吡啶、6,6'-二甲基-2,2'-联吡啶、5,5'-二甲基-2,2-联吡啶、5,5'-二羧基-2,2-联吡啶、4,4'-二甲基-2,2'-联吡啶、4,4'-二甲氧基-2,2'-联吡啶、4,4'-二叔丁基-2,2'-联吡啶、4,4'-二苯基-2,2'-联吡啶、2,2'-联喹啉、1,10-菲罗啉、4,7-二苯基-1,10-菲罗啉、4,7-二甲基-1,10-菲咯啉、3,4,7,8-四甲基-1,10-菲罗啉或三联吡啶中的任一种。
优选地,本发明的有机芳基硅化合物制备方法中所述反应所用的Lewis酸为AlCl3、MgBr2、ZnCl2、BiBr3、InCl3、Mn(OTf)3、Cu(OTf)2、Ca(OTf)2、Sc(OTf)3、Ho(OTf)3、In(OTf)3或Ha(OTf)4中的任一种。
优选地,本发明的有机芳基硅化合物制备方法中所述反应所述化合物Ⅰ为三氟甲磺酸酯取代的芳基硅试剂。
优选地,本发明的有机芳基硅化合物制备方法中所述反应所用的还原剂为锰粉。
优选地,本发明的有机芳基硅化合物制备方法中所述反应所用的催化剂为氯化镍乙二醇二甲醚。
优选地,本发明的有机芳基硅化合物制备方法中所述反应所述溶剂为氮氮二甲基乙酰胺(DMA)。
优选地,本发明的有机芳基硅化合物制备方法中所述反应所述Lewis酸为AlCl3。
优选地,本发明的有机芳基硅化合物制备方法中所述反应所述的配体氮杂配体为2,2'-联吡啶。
优选地,本发明的有机芳基硅化合物制备方法中所述反应温度为30℃。
优选地,本发明的有机芳基硅化合物制备方法中所述反应所述式Ⅰ化合物与烯丙醇亲电试剂的摩尔比为1.5:1。
更优选地,本发明的有机芳基硅化合物制备方法中所述反应温度为30℃。
本发明利用镍催化的亲电偶联反应来实现烯丙基取代的有机芳基硅试的合成,反应条件简单温和,底物适用性广。更重要的是,烯丙醇廉价易得且环保,是理想的烯丙基化试剂,以4-(三甲基硅基)苯基三氟甲基磺酸盐为原料通过亲电交叉偶联反应的方法实现烯丙基取代的有机芳基硅试剂化合物制备是一条理想的途径。4-(三甲基硅基)苯基三氟甲基磺酸盐相比于芳基溴代物或芳基氯代物廉价易得,且毒性小,更重要的是解离能小,因此所需反应条件也相对比较温和。
附图说明
图1、图2、图3分别为(E)-(4-(3-(4-甲氧基苯基)烯丙基)苯基)三甲基硅烷的核磁H谱图、核磁C谱和核磁硅谱。
具体实施方式
本发明提供以下的实施例。
实施例1
standard conditions:反应在氩气氛围的手套箱中进行。向反应管中依次加入Ni(dme)Cl2(4.4mg,0.02mmol),锰粉(33.4mg,0.6mmol),2,2-联吡啶(3.1mg,0.02mmol),AlCl3(2.7mg,0.02mmol),然后加入1a(89.4mg,0.3mmol)和2a(32.8mg,0.2mmol),在用注射器加入1mL的DMA溶液于反应管中。反应室温下搅拌36h之后,用水淬灭,用乙酸乙酯萃取,无水硫酸钠干燥,过滤、浓缩,硅胶柱层析(200~300目硅胶)制备得到目标产物3a。(白色固体,mp:95-97℃,53.3mg,产率90%)。
产物检测数据如下:
1H NMR(400MHz,CDCl3):δ7.46(d,J=8.0Hz,2H),7.29-7.23(m,4H),6.82(d,J=8.8Hz,2H),6.41(d,J=15.6Hz,1H),6.24-6.16(m,1H),3.77(s,3H),3.51(d,J=6.8Hz,2H),0.25(s,9H).13C NMR(100MHz,CDCl3):δ159.0,141.3,137.9,133.7,130.6,130.4,128.2,127.4,127.0,114.0,55.4,39.5,-0.9.29Si NMR(79MHz,CDCl3):δ-3.74.IR(neat,cm-1):3413,2956,1705,1600,1461,1247,1107,968,839,752.HRMS(EI):[M]+calcd forC19H24OSi 296.1596,found:296.1600.。
实施例2
standard conditions:反应在氩气氛围的手套箱中进行。向反应管中依次加入Ni(dme)Cl2(4.4mg,0.02mmol),锰粉(33.4mg,0.6mmol),2,2-联吡啶(3.1mg,0.02mmol),AlCl3(2.7mg,0.02mmol),然后加入1a(89.4mg,0.3mmol)和2b(30.4mg,0.2mmol),在用注射器加入1mL的DMA溶液于反应管中。反应室温下搅拌36h之后,用水淬灭,用乙酸乙酯萃取,无水硫酸钠干燥,过滤、浓缩,硅胶柱层析(200~300目硅胶)制备得到目标产物3b。(无色油状液体,42.6mg,产率75%)。产物检测数据如下:
1H NMR(400MHz,CDCl3):δ7.47(d,J=8.0Hz,2H),7.32-7.28(m,2H),7.24-7.22(m,2H),6.99-6.94(m,2H),6.42(d,J=15.6Hz,1H),6.29-6.22(m,1H),3.52(d,J=6.8Hz,2H),0.26(s,9H).13C NMR(100MHz,CDCl3):δ162.2(d,JC-F=245Hz),140.7138.2,133.8,130.1,129.0,129.0,128.3,127.7(d,JC-F=0.8Hz),115.1(d,JC-F=2.2Hz),39.4,-0.9.29Si NMR(79MHz,CDCl3):δ-3.86.19F NMR(376MHz,CDCl3):δ-111.93.IR(neat,cm-1):3411,2958,1598,1458,1247,1112,1110,966,839,748.GC-MS(EI)calcd for C18H21FSi 284.13,found:284.14.。
实施例3
standard conditions:反应在氩气氛围的手套箱中进行。向反应管中依次加入Ni(dme)Cl2(4.4mg,0.02mmol),锰粉(33.4mg,0.6mmol),2,2-联吡啶(3.1mg,0.02mmol),AlCl3(2.7mg,0.02mmol),然后加入1a(89.4mg,0.3mmol)和2c(30.0mg,0.2mmol),在用注射器加入1mL的DMA溶液于反应管中。反应室温下搅拌36h之后,用水淬灭,用乙酸乙酯萃取,无水硫酸钠干燥,过滤、浓缩,硅胶柱层析(200~300目硅胶)制备得到目标产物3c。(白色固体,mp:101-103℃。38.4mg,产率68%)。
产物检测数据如下:
1H NMR(600MHz,CDCl3):δ7.47(d,J=7.8Hz,2H),7.25-7.23(m,4H),6.76(d,J=8.4Hz,2H),6.40(d,J=15.6Hz,1H),6.22-6.17(m,1H),4.73(s,1H),3.51(d,J=7.2Hz,2H),0.26(s,9H).13C NMR(150MHz,CDCl3):δ154.9,141.2,138.0,133.7,130.7,130.5,128.2,127.6,127.1,115.5,39.5,-0.9.29Si NMR(79MHz,CDCl3):δ-4.05.IR(neat,cm-1):3529,3442,2854,1600,1512,1394,1247,1109,966,839.HRMS(EI):[M]+calcd forC18H22OSi 282.1440,found:282.1446.。
实施例4
standard conditions:反应在氩气氛围的手套箱中进行。向反应管中依次加入Ni(dme)Cl2(4.4mg,0.02mmol),锰粉(33.4mg,0.6mmol),2,2-联吡啶(3.1mg,0.02mmol),AlCl3(2.7mg,0.02mmol),然后加入1a(89.4mg,0.3mmol)和2d(35.6mg,0.2mmol),在用注射器加入1mL的DMA溶液于反应管中。反应室温下搅拌36h之后,用水淬灭,用乙酸乙酯萃取,无水硫酸钠干燥,过滤、浓缩,硅胶柱层析(200~300目硅胶)制备得到目标产物3d。(白色固体,mp:79-81℃,50.2mg,产率81%)。
产物检测数据如下:
1H NMR(600MHz,CDCl3):δ7.46(d,J=7.8Hz,2H),7.23(d,J=7.2Hz,2H),6.89(s,1H),6.78-6.71(m,2H),6.37(d,J=15.6Hz,1H),6.19-6.14(m,1H),5.91(s,2H),3.50(d,J=6.6Hz,2H),0.26(s,9H).13C NMR(150MHz,CDCl3):δ148.1,146.9,141.1,138.0,133.7,132.2,130.8,128.2,127.5,120.7,108.3,105.7,101.1,39.4,-0.9.29Si NMR(79MHz,CDCl3):δ-3.78.IR(neat,cm-1):3529,3444,2954,1658,1600,1514,1359,1247,1143,839.HRMS(EI):[M]+calcd for C19H22O2Si,310.1389,found:310.1385.。
实施例5
standard conditions:反应在氩气氛围的手套箱中进行。向反应管中依次加入Ni(dme)Cl2(4.4mg,0.02mmol),锰粉(33.4mg,0.6mmol),2,2-联吡啶(3.1mg,0.02mmol),AlCl3(2.7mg,0.02mmol),然后加入1a(89.4mg,0.3mmol)和2e(24.8mg,0.2mmol),在用注射器加入1mL的DMA溶液于反应管中。反应室温下搅拌36h之后,用水淬灭,用乙酸乙酯萃取,无水硫酸钠干燥,过滤、浓缩,硅胶柱层析(200~300目硅胶)制备得到目标产物3e。(淡黄色油状液体,42.3mg,产率83%)。
产物检测数据如下:
1H NMR(400MHz,CDCl3):δ7.47(d,J=8.0Hz,2H),7.29(s,1H),7.22(d,J=7.6Hz,2H),6.34-6.22(m,3H),6.16-6.15(m,1H),3.50(d,J=6.4Hz,2H),0.25(s,9H).13C NMR(100MHz,CDCl3):δ153.1,141.6,140.6,138.1,133.7,128.3,122.8,119.9,111.3,106.8,39.2,-0.9.29Si NMR(79MHz,CDCl3):δ-3.75.IR(neat,cm-1):3066,2954,1600,1460,1394,12471109,966,840,750.HRMS(EI):[M]+calcd for C16H20OSi 256.1283,found:256.1287.。
实施例6
standard conditions:反应在氩气氛围的手套箱中进行。向反应管中依次加入Ni(dme)Cl2(4.4mg,0.02mmol),锰粉(33.4mg,0.6mmol),2,2-联吡啶(3.1mg,0.02mmol),AlCl3(2.7mg,0.02mmol),然后加入1a(89.4mg,0.3mmol)和2f(27.0mg,0.2mmol),在用注射器加入1mL的DMA溶液于反应管中。反应室温下搅拌36h之后,用水淬灭,用乙酸乙酯萃取,无水硫酸钠干燥,过滤、浓缩,硅胶柱层析(200~300目硅胶)制备得到目标产物3f。(淡黄色油状液体,36.8mg,产率69%)。
产物检测数据如下:
1H NMR(600MHz,CDCl3):δ8.51(s,1H),8.48(d,J=4.8Hz,1H),7.55(d,J=7.8Hz,1H),7.46(d,J=7.8Hz,2H),7.33(d,J=7.8Hz,2H),7.24-7.22(m,1H),6.46(d,J=15.6Hz,1H),6.37-6.32(m,1H),3.55(d,J=6.6Hz,2H),0.25(s,9H).13C NMR(150MHz,CDCl3):δ150.2,147.9,139.8,137.6,136.3,135.6,133.8,132.2,128.2,125.6,123.6,36.6,-1.0.29Si NMR(79MHz,CDCl3):δ-3.75.IR(neat,cm-1):3525,3024,2954,1600,1512,1394,1247,1109,966,840.HRMS(EI):[M]+calcd for C17H21NSi 267.1443,found:267.1448。
实施例7
standard conditions:反应在氩气氛围的手套箱中进行。向反应管中依次加入Ni(dme)Cl2(4.4mg,0.02mmol),锰粉(33.4mg,0.6mmol),2,2-联吡啶(3.1mg,0.02mmol),AlCl3(2.7mg,0.02mmol),然后加入1a(89.4mg,0.3mmol)和2g(34.6mg,0.2mmol),在用注射器加入1mL的DMA溶液于反应管中。反应室温下搅拌36h之后,用水淬灭,用乙酸乙酯萃取,无水硫酸钠干燥,过滤、浓缩,硅胶柱层析(200~300目硅胶)制备得到目标产物3g。(淡黄色固体,mp:94-96℃,43.3mg,产率71%)。
产物检测数据如下:
1H NMR(600MHz,CDCl3):δ7.98(s,1H),7.58(s,1H),7.47(d,J=7.8Hz,1H),7.28-7.26(m,5H),7.11-7.10(m,1H),6.58(d,J=15.6Hz,1H),6.48(d,J=1.8Hz,1H),6.31-6.36(m,1H),3.55(d,J=6.6Hz,2H),0.26(s,9H).13C NMR(150MHz,CDCl3):δ141.6,137.8,135.4,133.7,132.3,129.8,128.3,128.2,126.4,124.7,120.5,118.9,111.2,102.9,39.6,-0.9.29Si NMR(79MHz,CDCl3):δ-3.81.IR(neat,cm-1):3410,2958,1598,1494,1448,1247,1110,964,839,746.HRMS(EI):[M]+calcd for C20H23NSi 305.1600,found:305.1605.。
实施例8
standard conditions:反应在氩气氛围的手套箱中进行。向反应管中依次加入Ni(dme)Cl2(4.4mg,0.02mmol),锰粉(33.4mg,0.6mmol),2,2-联吡啶(3.1mg,0.02mmol),AlCl3(2.7mg,0.02mmol),然后加入1a(89.4mg,0.3mmol)和2h(29.6mg,0.2mmol),在用注射器加入1mL的DMA溶液于反应管中。反应室温下搅拌36h之后,用水淬灭,用乙酸乙酯萃取,无水硫酸钠干燥,过滤、浓缩,硅胶柱层析(200~300目硅胶)制备得到目标产物3h。(无色油状液体,31.3mg,产率56%)。产物检测数据如下:
1H NMR(400MHz,CDCl3):δ7.48(d,J=8.0Hz,2H),7.35(d,J=7.6Hz,3H),7.29-7.26(m,4H),7.20-7.16(m,1H),7.30-7.26(m,3H),6.45-6.34(m,2H),3.66-3.59(m,1H),1.46(d,J=6.8Hz,3H),0.26(s,9H).13C NMR(100MHz,CDCl3):δ146.4,138.1,137.7,135.3,133.7,128.7,128.6,127.2,126.9,126.3,42.7,21.3,-0.9.29Si NMR(79MHz,CDCl3):δ-3.86.IR(neat,cm-1):2954,1598,1469,1415,1247,1107,964,839,759,732.GC-MS(EI)calcd for C19H24Si 280.16,found:280.16.。
实施例9
standard conditions:反应在氩气氛围的手套箱中进行。向反应管中依次加入Ni(dme)Cl2(4.4mg,0.02mmol),锰粉(33.4mg,0.6mmol),2,2-联吡啶(3.1mg,0.02mmol),AlCl3(2.7mg,0.02mmol),然后加入1a(89.4mg,0.3mmol)和2i(17.2mg,0.2mmol),在用注射器加入1mL的DMA溶液于反应管中。反应室温下搅拌36h之后,用水淬灭,用乙酸乙酯萃取,无水硫酸钠干燥,过滤、浓缩,硅胶柱层析(200~300目硅胶)制备得到目标产物3i。(无色油状液体,22.2mg,产率51%)。产物检测数据如下:
1H NMR(600MHz,CDCl3):δ7.44(d,J=7.8Hz,2H),7.18(d,J=7.8Hz,3H),5.33(t,J=7.2Hz,2H),3.33(d,J=7.2Hz,3H),1.73(d,J=12.6Hz,6H),0.26(s,9H).13C NMR(150MHz,CDCl3):δ142.7,137.4,133.6,132.7,128.0,123.2,34.5,25.9,18.0,-0.9.29SiNMR(79MHz,CDCl3):δ-3.74.IR(neat,cm-1):2979,1610,1398,1321,1274,1143,1089,964,860,752.GC-MS(EI)calcd for C14H22Si 218.15,found:218.16.。
以上为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围。
Claims (13)
1.一种如Ⅲ示的烯丙基取代的芳基有机硅化合物制备方法,其特征在于反应式如下式所示,即以如Ⅰ示的三氟甲磺酸取代芳基硅试剂为原料,在镍催化
下,以锰粉、锌粉、镁粉或铝粉中的任一种作为还原剂,联吡啶作为配体,Lewis酸作为添加剂,在有机溶剂中及惰性气体保护下,通过与如Ⅱ示烯丙醇的偶联反应,得到目标产物,反应的温度为-10℃~100℃,其中:所述有机溶剂为氮氮甲基乙酰胺(DMA)、溶剂为氮氮二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、二乙醇二甲醚(DME)或N-甲基吡咯烷酮(NMP)中的任一种,R1为吲哚、吡啶、甲基、苯基、咔唑或取代的烷基或芳基的任一种;R2、R3为分别为氢或甲基中的任一种,且两者可以相同或不同。
2.根据权利要求1所述的烯丙基取代的有机芳基硅化合物制备方法,其特征在于所述反应所用的催化剂为氯化镍或溴化镍或碘化镍或氟化镍或二茂镍或碳酸镍或三环己基膦氯化镍或三苯基膦氯化镍或二甲氧基乙烷氯化镍或(1,1'-双(二苯基膦)二茂铁)氯化镍或双-(1,5-环辛二烯)镍或二乙二醇二甲醚溴化镍或氯化镍(II)乙二醇二甲醚中的任一种。
3.根据权利要求2所述的有机芳基硅化合物制备方法,其特征在于:所述的配体氮杂配体为2,2'-联吡啶、6,6'-二甲基-2,2'-联吡啶、5,5'-二甲基-2,2-联吡啶、5,5'-二羧基-2,2-联吡啶、4,4'-二甲基-2,2'-联吡啶、4,4'-二甲氧基-2,2'-联吡啶、4,4'-二叔丁基-2,2'-联吡啶、4,4'-二苯基-2,2'-联吡啶、2,2'-联喹啉、1,10-菲罗啉、4,7-二苯基-1,10-菲罗啉、4,7-二甲基-1,10-菲咯啉、3,4,7,8-四甲基-1,10-菲罗啉或三联吡啶中的任一种。
4.根据权利要求3所述的有机芳基硅化合物制备方法,其特征在于:所述反应所用的Lewis酸为AlCl3、MgBr2、ZnCl2、BiBr3、InCl3、Mn(OTf)3、Cu(OTf)2、Ca(OTf)2、Sc(OTf)3、Ho(OTf)3、In(OTf)3或Ha(OTf)4中的任一种。
5.根据权利要求1至4所述的任一种烯丙基取代的有机芳基硅化合物制备方法,其特征在于所述化合物Ⅰ为三氟甲磺酸酯取代的芳基硅试剂。
6.根据权利要求5所述的任一种有机芳基硅化合物制备方法,其特征在于所用的还原剂为锰粉。
7.根据权利要求6所述的有机芳基硅化合物制备方法,所用的催化剂为氯化镍乙二醇二甲醚。
8.根据权利要求7所述的有机芳基硅化合物制备方法,其特征在于所述溶剂为氮氮二甲基乙酰胺(DMA)。
9.根据权利要求8所述的有机芳基硅化合物制备方法,其特征在于所述Lewis酸为AlCl3。
10.根据权利要求9所述的有机芳基硅化合物制备方法,其特征在于所述的配体氮杂配体为2,2'-联吡啶。
11.根据权利要求10所述的有机芳基硅化合物制备方法,其特征在于反应温度为30℃。
12.根据权利要求11所述的有机芳基硅化合物制备方法,其特征在于所述式Ⅰ化合物与烯丙醇亲电试剂的摩尔比为1.5:1。
13.根据权利要求11所述的有机芳基硅化合物制备方法,其特征在于制备过程中的反应温度为30℃。
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