二价钌催化的金属卡宾经由的硫叶立德[2,3]-σ重排反应研究详解.PDFVIP

2007 年第 65 卷 化 学 学 报 Vol. 65, 2007 第 16 期, 1733～1735 ACTA CHIMICA SINICA No. 16, 1733～1735 ·研究简报· 二价钌催化的金属卡宾经由的硫叶立德[2,3]-σ 重排反应研究 肖 卿 王剑波* (北京分子科学国家实验室 生物有机与分子工程教育部重点实验室 北京大学化学学院 北京 100871) 摘要 报道烯(炔)基硫醚与 α-重氮羰基化合物, 在[RuCl2(p -cymene)]2 催化下, 经由金属卡宾发生硫叶立德[2,3]-σ 重排 反应(Doyle-Kirmse 反应). 在 Ru(II)作用下, α-重氮羰基化合物与烯丙基硫醚的反应以较好收率生成相应的[2,3]-σ 重排 产物高烯丙基硫醚. 同样条件下与炔丙基硫醚的反应则生成[2,3]-σ 重排产物联烯和呋喃衍生物, 后者是联烯进一步在 Ru(II)作用下重排的产物. 关键词 二价钌催化剂; α-重氮羰基化合物; 硫叶立德[2,3]-σ 重排 Investigation on Ru(II)-Catalyzed Reaction of [2,3]-Sigmatropic Rearrangement of Sulfur Ylide Generated from Metal Carbene XIAO, Qing WANG, Jian-Bo* (Beijing National Laboratory of Molecular Sciences (BNLMS), and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871) Abstract The Doyle-Kirmse reaction, namely the [2,3]-sigmatropic rearrangement of sulfonium ylides generated from α-diazo carbonyl compounds and sulfides has been for the first time catalyzed by [RuCl2- (p -cymene)]2 . The reaction with allyl sulfides afforded the corresponding [2,3]-sigmatropic rearrangement products in moderate to good yields. The reaction with propargyl sulfide gave a mixture of allenic sulfide and furan. The former is the [2,3]-sigmatropic rearrangement product, while the latter is derived from the further rearrangement of the allene product under Ru(II) catalysis. Keywords ruthenium(II) catalyst; α-diazo carbonyl compound; [2,3]-sigmatropic rearrangement of sulfo- nium ylide