CN107033179B - 催化吲哚硅烷化及质子转移氢化的方法 - Google Patents
催化吲哚硅烷化及质子转移氢化的方法 Download PDFInfo
- Publication number
- CN107033179B CN107033179B CN201710306120.8A CN201710306120A CN107033179B CN 107033179 B CN107033179 B CN 107033179B CN 201710306120 A CN201710306120 A CN 201710306120A CN 107033179 B CN107033179 B CN 107033179B
- Authority
- CN
- China
- Prior art keywords
- hydrogenation
- silane
- methyl
- minutes
- proton translocation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002444 silanisation Methods 0.000 title claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 19
- 230000005945 translocation Effects 0.000 title claims abstract description 15
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 title claims abstract description 14
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 12
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 150000002475 indoles Chemical class 0.000 claims abstract description 21
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000077 silane Inorganic materials 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 13
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims description 2
- 238000003818 flash chromatography Methods 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- 239000002243 precursor Substances 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052796 boron Inorganic materials 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000010970 precious metal Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 22
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 12
- -1 4- pyrenyl Chemical group 0.000 description 11
- 230000005311 nuclear magnetism Effects 0.000 description 9
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 8
- 238000004293 19F NMR spectroscopy Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- RQENMYLIJFVENG-UHFFFAOYSA-N 1-methylindole quinoline Chemical compound N1=CC=CC2=CC=CC=C12.CN1C=CC2=CC=CC=C12 RQENMYLIJFVENG-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 208000012839 conversion disease Diseases 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 238000007171 acid catalysis Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229910052805 deuterium Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- BLRHMMGNCXNXJL-UHFFFAOYSA-N 1-methylindole Chemical compound C1=CC=C2N(C)C=CC2=C1 BLRHMMGNCXNXJL-UHFFFAOYSA-N 0.000 description 2
- DPFWUAYMRGTMAM-UHFFFAOYSA-N 2-fluoro-1-methylindole Chemical compound C1=CC=C2N(C)C(F)=CC2=C1 DPFWUAYMRGTMAM-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- BJMUOUXGBFNLSN-UHFFFAOYSA-N 1,2-dimethylindole Chemical compound C1=CC=C2N(C)C(C)=CC2=C1 BJMUOUXGBFNLSN-UHFFFAOYSA-N 0.000 description 1
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007876 drug discovery Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Chemical group 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
- C07F7/0814—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 said ring is substituted at a C ring atom by Si
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
-
- 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
- C07F7/0829—Hydrosilylation reactions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Indole Compounds (AREA)
Abstract
本发明的高效的催化吲哚硅烷化及质子转移氢化的催化体系属于有机合成技术领域,以吲哚、硅烷作为原料,以三(五氟苯基)硼B(C6F5)3为催化剂,在室温下反应10分钟同时实现吲哚的3位选择性硅烷化及质子转移氢化,或在100~140℃情况下反应10~1440分钟实现高效专一的催化吲哚3位硅烷化。本发明的催化体系具有原料易得、操作方便、反应条件温和、快速、转化率高、无需贵重金属、催化剂使用量少、催化中间体稳定性高,适用于多种溶剂体系或者不需要任何溶剂的本体体系等优点。
Description
技术领域
本发明属于有机合成技术领域,具体涉及一种高效的催化吲哚硅烷化及质子转移氢化的催化体系。
背景技术
近年来吲哚类硅烷化产物在各个领域都有比较广阔的应用,特别是在有机的电子和光子学,制药和分子材料合成方面应用日趋广泛.(J.Org.Chem.2007,72,6241.J.Chem.2008,86,230.Drug Discovery Today 2003,8,551.J.Med.Chem.2013,56,388.Chem.Rev.1995,95,1375.Chem.Soc.Rev.Science 2012,337,1644)。吲哚啉类化合物主要用于合成吲哚类的衍生产品,例如吲哚啉类染料、太阳能电池的敏剂,具有良好的光电转化性能。它也是医药、植物生长调节剂的中间体。因此,吲哚类硅烷化产物及吲哚啉类化合物一直是化学、医用高分子材料等相关领域的研究热点。
目前合成吲哚类硅烷化产物的主要方法有:金属(过渡金属、碱金属、碱土金属)催化、布朗斯特酸催化及路易斯酸催化。目前的技术现状是反应条件苛刻,如反应需要加热、催化剂用量大、使用贵重金属催化等,常常伴随硅氢化副反应,产物转化率不高。而吲哚啉类化合物的合成主要是以金属催化和路易斯酸催化,氢源主要是通过硅烷或氢气提供,反应条件存在高温、高压、反应时间较长等缺点。(Martin Oestreich等,Angew.Chem.Int.Ed.2016,55,3204–3207,J.Am.Chem.Soc.,2016,138(25),pp 7868–7871,Michael J.Ingleson等,Chem.Commun.,2014,50,5270—5272,候召民等,J.Am.Chem.Soc.,2016,138(11),pp 3663–3666,Yugen Zhang等,Tetrahedron Letters 50(2009)4912–4915)
发明内容
本发明要解决的技术问题在于,提供一种室温下高效快速地同时实现吲哚3位硅烷化及质子转移氢化的催化,以及在100-140℃下高效专一催化吲哚3位硅烷化体系。
本发明的技术方案如下:
一种室温下高效快速催化吲哚硅烷化及质子转移氢化的催化体系,其特征在于,以吲哚、硅烷作为原料,吲哚、硅烷的摩尔比在6:1到1:5之间,以三(五氟苯基)硼B(C6F5)3为催化剂,在室温下反应10分钟同时实现吲哚的3位选择性硅烷化及质子转移氢化,或在100-140℃情况下反应10分钟到1440分钟实现高效专一的催化吲哚3位硅烷化。
具体过程:
在手套箱中,将吲哚先加入到在核磁管中,再加入三(五氟苯基)硼B(C6F5)3或三(五氟苯基)硼B(C6F5)3的溶液,然后加入硅烷,在室温下反应10分钟得到3位硅烷化产物及取代吲哚啉,或在100-140℃反应10分钟到1440分钟得到3位硅烷化产物;将反应混合物用Et3N淬灭,用体积比为100:10:1的环己烷/三乙胺/叔丁基甲基醚作为洗脱液,通过硅胶快速柱色谱进一步纯化。
按摩尔计,所述的三(五氟苯基)硼B(C6F5)3的用量优选为哚吲的0.01%~20%,所述的硅烷的用量优选为哚吲的1/6~5倍。
所述的吲哚原料,结构式如下:
R1是H,4-甲基,5-甲基,6-甲基,7-甲基,4-氟,5-氟,6-氟,7-氟,4-氯,5-氯,6-氯,7-氯,4-溴,5-溴,6-溴,7-溴,4-萘基,5-萘基,6-萘基,7-萘基,4-芘基,5-芘基,6-芘基,7-芘基,4-苝基,5-苝基,6-苝基,7-苝基,4-异恶唑基,5-异恶唑基,6-异恶唑基,7-异恶唑基,4-噻吩基,5-噻吩基,6-噻吩基,7-噻吩基,4-咔唑基,5-咔唑基,6-咔唑基或7-咔唑基;
R2是甲基,乙基,烯丙基,苄基,异丙基,乙烯基或苯基。
所述的硅烷原料如下:
所述的三(五氟苯基)硼B(C6F5)3的溶液优选为三(五氟苯基)硼B(C6F5)3的苯、甲苯、二氯甲烷、氯仿、乙腈或N,N-二甲基甲酰胺溶液,浓度优选为0.005~0.05mol/L。
本发明催化体系在三(五氟苯基)硼B(C6F5)3的协同下,通过三(五氟苯基)硼B(C6F5)3与硅烷的结合,形成活性物种,常温或100-140℃该活性物种在催化过程中不易失活,连续加入原料50次,催化活性仍保持在很高的水平,实现了在室温快速高效的同时合成吲哚3位硅烷化产物及质子转移氢化的产物吲哚啉两种产物,或者在100-140℃的条件下高效专一合成吲哚3位硅烷化产物。
综上,本发明有以下有益效果:
1、本发明的B(C6F5)3催化体系原料易得、操作方便、反应条件温和、快速、转化率高、无需贵重金属。
2、本发明的B(C6F5)3催化体系催化剂使用量少(在无溶剂的条件下,单体与催化剂的摩尔比可以达到10000:1以上),底物适用性广泛。
3、本发明的B(C6F5)3催化体系,催化中间体稳定性高,连续加料50次,催化体系的活性仍然保持在很高的水平。
4、本发明的B(C6F5)3催化体系,在室温下可高效快速地同时实现吲哚3位硅烷化及质子转移氢化,在100-140℃的情况下可高效专一催化吲哚3位硅烷化。
附图说明
图1是实施例1原位核磁生成C9H11N·PhSiH2·B(C6F5)3(3e),1H NMR图。
图2是实施例1原位核磁生成C9H11N·PhSiH2·B(C6F5)3(3e),19F NMR图。
图3是实施例2原位核磁生成C9H11N·C21H18NSiH·B(C6F5)3(3f),1H NMR图。
图4是实施例2原位核磁生成C9H11N·C21H18NSiH·B(C6F5)3(3f),19F NMR图。
图5是实施例4室温催化剂活性检测前10次的转化率及3位硅烷化产物及吲哚啉产率柱状图。
图6是实施例5在120℃催化剂活性检测前10次的3位硅烷化产物产率柱状图。
图7是实施例6 6ga的X射线单晶衍射结构表征。
图8是实施例6 4ab的X射线单晶衍射结构表征。
图9是实施例6 7aa的X射线单晶衍射结构表征。
具体实施方式
通过以下实施例可以进一步说明本发明,实施例是为了说明本发明而不是限制本发明,本发明的保护范围不限制于此。
实施例1原位核磁生成C9H11N·PhSiH2·B(C6F5)3(3e)
在J.Young-type核磁管中加入B(C6F5)3(12.8mg,0.025mmol)和0.3mL of CD2Cl2,用注射器向其中分别加入0.1mL Ph2SiH2(4.6mg,0.025mmol)和0.2ml 1-甲基吲哚啉(3.3mg,0.025mmol)的CD2Cl2溶液,混合均匀,反应十分钟后溶液为无色,进行核磁测试,从核磁氢谱上可以明显看出生成的主要产物为C9H11N·PhSiH2·B(C6F5)3(3e)。(1H/19F NMR图见附图1和2)1H NMR(500MHz,CD2Cl2)δ7.78–7.71(m,3H,HAr),7.71–7.67(m,2H,HAr),7.60–7.54(m,6H,HAr),7.42–7.33(m,4H,HAr),7.27(t,J=8.5Hz,1H,HAr),7.13(t,J=8.0Hz 1H,HAr),6.92(d,J=8.0Hz,1H,HAr),6.45(d,J=8.5Hz,1H,HAr),4.92(ddd,J=11.6,9.4,4.0Hz,1H,NCH2),3.92(s,3H,NCH3),3.90–3.84(m,1H,NCH2),3.66(br q,1H,BH),3.58(s,3H,NCH3),3.21–3.12(m,1H,NCH2),2.34(dt,J=17.2,9.1Hz,1H,NCH2).19F NMR(471MHz,CD2Cl2)δ-133.87–-134.35(m,6F,o-F),-164.06–-164.71(m,3F,p-F),-167.02–-167.72(m,6F,m-F).
实施例2原位核磁生成C9H11N·C21H18NSiH·B(C6F5)3(3f)
在J.Young-type核磁管中加入B(C6F5)3(12.8mg,0.025mmol)和0.3mL of CD2Cl2,用注射器向其中分别加入0.1mL C21H18NSiH(4aa)(7.8mg,0.025 mmol)和0.2ml 1-甲基吲哚啉(3.3mg,0.025mmol)的CD2Cl2溶液,混合均匀,反应十分钟后溶液为无色,进行核磁测试,从核磁氢谱上可以明显看出生成的主要产物为C9H11N·C21H18NSiH·B(C6F5)3(3f)。(1H/19F NMR图见附图3和4)1H NMR(500MHz,CD2Cl2)δ7.78–7.71(m,3H,HAr),7.71–7.67(m,2H,HAr),7.60–7.54(m,6H,HAr),7.42–7.33(m,4H,HAr),7.27(t,J=8.5Hz,1H,HAr),7.13(t,J=8.0Hz1H,HAr),6.92(d,J=8.0Hz,1H,HAr),6.45(d,J=8.5Hz,1H,HAr),4.92(ddd,J=11.6,9.4,4.0Hz,1H,NCH2),3.92(s,3H,NCH3),3.90–3.84(m,1H,NCH2),3.66(br q,1H,BH),3.58(s,3H,NCH3),3.21–3.12(m,1H,NCH2),2.34(dt,J=17.2,9.1Hz,1H,NCH2).19F NMR(471MHz,CD2Cl2)δ-133.87–-134.35(m,6F,o-F),-164.06–-164.71(m,3F,p-F),-167.02–-167.72(m,6F,m-F).
上述实施例1和实施例2,得到了在室温下,三(五氟苯基)硼B(C6F5)3催化的反应中间体。
实施例3无溶剂的条件下制备3-(二苯基甲硅烷基)-1-甲基吲哚和1-甲基吲哚啉
在手套箱中,称取1-甲基吲哚(13.1g 0.1mol),B(C6F5)3(0.01mmol,5.6mg)在30mL的反应瓶中充分搅拌均匀,当B(C6F5)3完全溶解后,加入Ph2SiH2(9.2g0.05mol),室温搅拌24h,用移液枪取0.2mL反应液溶于氘代苯中,通过核磁氢谱上原料与产物氮甲基的积分面积算出反应的转化率为96.9%,3-(二苯基甲硅烷基)-1-甲基吲哚和1-甲基吲哚啉的产率分别为46.1%和45.2%。后处理方法:将反应混合物倒入300mL的己烷中,搅拌30分钟,过滤得到白色固体,用(3×30mL)己烷洗涤抽干,得到白色固体3-(二苯基甲硅烷基)-1-甲基吲哚12.76g。滤液浓缩,以己烷为洗脱剂,通过柱色谱分离得到1-甲基吲哚啉5.36g。
实施例4室温催化剂活性检测
催化剂活性检测实验在手套箱中进行,称取B(C6F5)3(5mol%,6.4mg)加入到核磁管中,用注射器加入5-氟-1-甲基吲哚(0.25mmol 37.3mg)的0.2mL氘苯溶液中,立即加入Ph2SiH2(0.15mmol,27.6mg),10分钟后进行核磁测试,计算反应转化率。立刻再依次向核磁管中加入等当量的5-氟-1-甲基吲哚及Ph2SiH2,10分钟后再次进行核磁测试,计算反应转化率。此过程总共进行50次。将前十次核磁反应的转化率及产率作图(见附图5)。
实施例5 120℃催化剂活性检测
在手套箱中,称取B(C6F5)3(0.3mmol%,1.6mg)加入到核磁管中,用注射器加入5-甲基-1-甲基吲哚(0.06mmol 9.1mg)的0.2mL氘苯溶液中,立即加入Ph2SiMeH(0.12mmol,24.8mg),120℃加热60分钟后进行核磁测试,计算反应转化率。立刻再依次向核磁管中加入以上等当量的5-甲基-1-甲基吲哚及Ph2SiMeH,60分钟后再次进行核磁测试,计算反应转化率。此过程总共进行50次。前10次的3位硅烷化产物产率柱状图如附图6所示。
实施例6室温吲哚的3位C-H键硅烷化及质子转移氢化及120℃及3位C-H键专一硅烷化的一般过程
在手套箱中,向核磁管中加入1-甲基吲哚(0.25mmol),然后加入0.5mL(1.0%eq或5.0%eq)B(C6F5)3的氘苯溶液。然后加入硅烷(0.25eq或0.5eq或2.0eq)。室温或者120℃反应完成后,将反应混合物用0.5mL三乙胺淬灭。混合物使用环己烷/三乙胺/叔丁基甲基醚(100/10/1)作为洗脱液,通过硅胶快速柱色谱法进一步纯化得到3位硅烷化产物及取代吲哚啉。
1)
表1:以Ph2SiH2为原料室温进行吲哚的C-H键硅烷化及氢化
产物6ga和产物7aa的X射线单晶衍射结构如附图7和附图9所示。
2)
表2:以Ph3SiH为原料室温进行吲哚的C-H键硅烷化及氢化
产物4ab的X射线单晶衍射结构如附图8所示。
3)
表3:以PhSiH3为原料室温进行吲哚的C-H键硅烷化及氢化
5)
表5:以不同种类的硅烷为原料室温进行吲哚的C-H键硅烷化及氢化
6)
表6:以不同种类的硅烷为原料120℃进行吲哚的C-H键硅烷化
所述的3位硅烷化产物结构式如下:
所述的取代吲哚啉结构式如下:
Claims (3)
1.一种催化吲哚硅烷化及质子转移氢化的方法,其特征在于,以吲哚类化合物、硅烷作为原料,以摩尔计,所述的硅烷的用量为吲哚类化合物的1/6~2倍,以B(C6F5)3为催化剂,按摩尔计,所述的B(C6F5)3的用量为吲哚类化合物的0.01%~20%,在室温下反应10分钟同时实现吲哚的3位选择性硅烷化及质子转移氢化,或在100-140℃情况下反应10分钟到1440分钟实现专一的催化吲哚3位硅烷化;所述的吲哚类化合物的结构式为:当所述的硅烷是Ph2SiH2,Ph3SiH或PhSiH3时,结构式中的R1是H,5-甲基,6-甲基,5-氟,5-氯,6-氯,5-溴,6-溴,5-苯基;R2是甲基;当所述的硅烷是MePh2SiH,Me2PhSiH,Et2SiH2或Ph2SiHCl时,结构式中的R1是H,R2是甲基。
2.根据权利要求1所述的一种催化吲哚硅烷化及质子转移氢化的方法,其特征在于,具体反应过程如下:
在手套箱中,将吲哚类化合物先加入到在核磁管中,再加入B(C6F5)3或B(C6F5)3的溶液,然后加入硅烷,在室温下反应10分钟得到3位硅烷化产物及取代吲哚啉,或在100~140℃反应10~1440分钟得到3位硅烷化产物;将反应混合物用Et3N淬灭,用体积比为100:10:1的环己烷/三乙胺/叔丁基甲基醚作为洗脱液,通过硅胶快速柱色谱进一步纯化。
3.根据权利要求1或2所述的一种催化吲哚硅烷化及质子转移氢化的方法,其特征在于,所述的B(C6F5)3的溶液为B(C6F5)3的苯、甲苯、二氯甲烷、氯仿、乙腈或N,N-二甲基甲酰胺溶液,浓度为0.005~0.05mol/L。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710306120.8A CN107033179B (zh) | 2017-05-04 | 2017-05-04 | 催化吲哚硅烷化及质子转移氢化的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710306120.8A CN107033179B (zh) | 2017-05-04 | 2017-05-04 | 催化吲哚硅烷化及质子转移氢化的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107033179A CN107033179A (zh) | 2017-08-11 |
CN107033179B true CN107033179B (zh) | 2019-08-13 |
Family
ID=59536985
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710306120.8A Active CN107033179B (zh) | 2017-05-04 | 2017-05-04 | 催化吲哚硅烷化及质子转移氢化的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107033179B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110590822B (zh) * | 2019-09-26 | 2021-07-06 | 吉林大学 | 一锅法合成硼(硅)烷化吲哚与四氢喹啉的方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2784808B2 (ja) * | 1989-08-09 | 1998-08-06 | 三井化学株式会社 | 新規な有機ケイ素化合物 |
-
2017
- 2017-05-04 CN CN201710306120.8A patent/CN107033179B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2784808B2 (ja) * | 1989-08-09 | 1998-08-06 | 三井化学株式会社 | 新規な有機ケイ素化合物 |
Non-Patent Citations (3)
Title |
---|
competitive dehydrosilylation, hydrosilylation and hydrogenation.《Chem. Commum.》.2013,第5270-5272页,尤其是第5272页以及第S57页. |
Frustrated Lewis Pair Catalyzed Dehydrogenative Oxidation of Indolines and Other Heterocycles;Alexander F. G. Maier等,;《Angew. Chem. Int. Ed.》;20161231;第1-6页,尤其是第2页 |
Liam D.Curless等,.E-H (E=R3Si or H) bond activation by B(C6F5)3 and heteroarenes |
Also Published As
Publication number | Publication date |
---|---|
CN107033179A (zh) | 2017-08-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Hase et al. | Mechanistic aspects of the carboxylative cyclization of propargylamines and carbon dioxide catalyzed by gold (I) complexes bearing an N-heterocyclic carbene ligand | |
Jenter et al. | 2, 5-Bis {N-(2, 6-diisopropylphenyl) iminomethyl} pyrrolyl complexes of the heavy alkaline earth metals: synthesis, structures, and hydroamination catalysis | |
Xu et al. | Mechanistic considerations of the catalytic guanylation reaction of amines with carbodiimides for guanidine synthesis | |
Kim et al. | Copper-catalyzed enantiotopic-group-selective allylation of gem-diborylalkanes | |
Cao et al. | Activation of carbodiimide and transformation with amine to guanidinate group by Ln (OAr) 3 (THF) 2 (Ln: Lanthanide and yttrium) and Ln (OAr) 3 (THF) 2 as a novel precatalyst for addition of amines to carbodiimides: Influence of aryloxide group | |
Tarrieu et al. | Readily accessible unsymmetrical unsaturated 2, 6-diisopropylphenyl N-heterocyclic carbene ligands. Applications in enantioselective catalysis | |
Cheng et al. | Palladium catalyzed acetoxylation of benzylic C–H bonds using a bidentate picolinamide directing group | |
Zhu et al. | Efficient and versatile transfer hydrogenation catalysts: Iridium (III) and ruthenium (II) complexes with 4-acetylbenzyl-N-heterocyclic carbenes | |
Vitanova et al. | Linked bis (β-diketiminato) yttrium and lanthanum complexes as catalysts in asymmetric hydroamination/cyclization of aminoalkenes (AHA) | |
Li et al. | Redox Chemistry between Europium (III) Amide and Pyrrolyl-Functionalized Secondary Amines. Synthesis and Structural Characterization of Lithium and Novel Lanthanide Complexes Incorporating Functionalized Pyrrolyl Ligands | |
Wang et al. | Synthesis, Characterization, and Reactivity of Lanthanide Amides Incorporating Neutral Pyrrole Ligand. Isolation and Characterization of Active Catalyst for Cyanosilylation of Ketones | |
Chen et al. | Thermal induced intramolecular [2+ 2] cycloaddition of allene-ACPs | |
Wang et al. | Synergistic cooperation of bi-active hydrogen atoms in protic carboxyl imidazolium ionic liquids to push cycloaddition of CO2 under benign conditions | |
Wei et al. | Aluminum Alkyl Complexes Supported by Bidentate N, N Ligands: Synthesis, Structure, and Catalytic Activity for Guanylation of Amines | |
Zhu et al. | Synthesis, Characterization, Selective Catalytic Activity, and Reactivity of Rare Earth Metal Amides with Different Metal− Nitrogen Bonds | |
CN106750227B (zh) | 一种活性可控的催化内酯开环聚合的催化体系 | |
Gour et al. | A microwave-assisted SmI2-catalyzed direct N-alkylation of anilines with alcohols | |
CN104607248A (zh) | 芘-4,5,9,10-四亚胺-(芳胺)合氯化钯及其在heck反应中的应用 | |
CN107033179B (zh) | 催化吲哚硅烷化及质子转移氢化的方法 | |
Meyer et al. | CH-activation of methane–Synthesis of an intermediate? | |
Vaughan et al. | Synthesis and characterization of zinc complexes and reactivity with primary phosphines | |
Yuan et al. | Reactions of Boratabenzene Yttrium Complexes with KN (SiMe3) 2: Salt Elimination and π-Ligand Displacement | |
Wei et al. | Synthesis and characterization of rare-earth metallate amido complexes bearing the 2-amidate-functionalized indolyl ligand and their application in the hydroboration of esters with pinacolborane | |
CN105859718A (zh) | 一种铜催化的含氮多杂环化合物的制备方法 | |
Zhao et al. | Nickel-catalyzed cooperative BH bond activation for hydroboration of N‑heteroarenes, ketones and imines |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |