Platinum Complex-Catalyzed Hydrosilylation and Isomerization of Methylenecyclopropane Derivatives. Effect of Structures of the Substrate and Catalyst
作者:Masumi Itazaki、Yasushi Nishihara、Kohtaro Osakada
DOI:10.1021/jo020293+
日期:2002.10.1
the silyl compounds with a (2,2-diphenylcyclopropyl)methyl substituent in moderate to high yields without ring-opening of the substrate. PtI(2)(PPh(3))(2) is converted by the reaction into PtH(I)(PPh(3))(2), which also catalyzes the hydrosilylation of the methylenecyclopropanes. The reaction of 2-phenyl-1-methylenecyclopropane, 2-methyl-2-phenyl-1-methylenecyclopropane, 2,2-diphenethyl-1-methylenecyclopropane
PtI(2)(PPh(3))(2)催化2,2-二苯基-1-亚甲基环丙烷与HSiEt(3),HSiPh(3),HSiEt(2)Ph,HSiPhCl(2)和HSiCl( 3)在140℃的无溶剂条件下以中等至高的产率生产具有(2,2-二苯基环丙基)甲基取代基的甲硅烷基化合物,而没有底物开环。通过反应将PtI(2)(PPh(3))(2)转化为PtH(I)(PPh(3))(2),该催化剂还催化亚甲基环丙烷的氢化硅烷化。PtI(2)(PPh(3)催化的HSiEt(3)与2-苯基-1-亚甲基环丙烷,2-甲基-2-苯基-1-亚甲基环丙烷,2,2-二苯乙基-1-亚甲基环丙烷和亚烷基亚环丙烷的反应))(2)导致将氢硅烷添加到基材上并伴随开环。2,2-二苯基-1-亚甲基环丙烷在HSi(OEt)Me(2)和Pt(PEt(3))(3)催化剂存在下经历开环异构化反应,得到1,1-二苯基-1,3-丁二烯。讨论了氢化硅烷化和异构化的途径。