Organic Syntheses Utilizing Trimethylsilyldiazomethane

本文主要研究了三甲基硅基重氮甲烷（TMSCHN_2）作为一种稳定、安全的有害重氮甲烷替代品的合成利用。氯化亚铜催化α -三甲基硅基重氮烷烃的分解得到高产的(E)-1-三甲基硅基-1-烯烃。2. 三甲基硅基重氮甲烷锂与酮胺顺利反应生成1,2,3-三唑，收率高。3. 在金属盐催化剂存在或不存在的情况下，TMSCHN_2与各种烯烃反应生成硅基环丙烷。4. 铑（II）私人催化分解-三甲基硅基重氮烷烃立体选择性地得到(Z)-1-三甲基硅基-1-烯，收率高。5. 根据底物的不同，TMSCHN_2与不同的醌类化合物反应得到吲哚、硅基环丙烷、2-取代的3-三甲基硅基甲基、4-醌和三甲基硅基二氧基衍生物。

Synthetic utilizations of trimethylsilyldiazomethane (TMSCHN_2), as a stable and safe substitute for hazardous diazomethane, were investigated as follows: 1. The cuprous chloride-catalyzed decomposition of alpha-trimethylsilyldiazoalkanes gives (E)-1-trimethylsilyl-1-alkenes in high yields. 2. Lithium trimethylsilyldiazomethane smoothly reacts with ketenimines to give 1,2,3-triazoles in good yields. 3. Most of the reactions of TMSCHN_2 with various olefins in the presence or absence of metal salt catalysts give silylcyclopropanes. 4. The rhodium(II) pivalate-catalyzed decomposition of alpha-trimethylsilyldiazoalkanes stereoselectively affords (Z)-1-trimethylsilyl-1-alkenes,in,good yields. 5. Reaction of TMSCHN_2 with various quinones affords indazoles, silylcyclopropanes, 2-substituted 3-trimethylsilylmethylml,4-quinones, and trimethylsilylmethylenedioxy derivatives,depending upon substrates.