Rh(II)-Catalyzed [2,3]-Sigmatropic Rearrangement of Sulfur Ylides Derived from Cyclopropenes and Sulfides

A new
type of Rh2(OAc)4-catalyzed [2,3]-sigmatropic
rearrangement of sulfur ylides is reported. A series of cyclopropenes
were successfully employed for [2,3]-sigmatropic rearrangement by
a reaction with either allylic or propargylic sulfides. Under the
optimized conditions, the reaction afforded the products in moderate
to excellent yields. In these transformations, the vinyl metal carbenes
generated in situ from the cyclopropenes were effectively trapped
by sulfides, resulting in the formation of corresponding products
upon [2,3]-sigmatropic rearrangements.

本研究报道了一种新型四乙酸二铑（Rh₂(OAc)₄）催化的硫叶立德[2,3]-σ迁移重排反应。一系列环丙烯可分别与烯丙基硫醚或炔丙基硫醚发生[2,3]-σ迁移重排反应。在优化后的反应条件下，该反应可获得中等至优异的产物收率。在此类转化过程中，由环丙烯原位生成的乙烯基金属卡宾可被硫醚有效捕获，随后经[2,3]-σ迁移重排得到相应产物。