Recent advances in the chemistry and synthetic uses of magnesium carbenoids

Abstract

Carbenes and carbenoids have long been recognized to be a highly reactive species and are frequently used as intermediates in organic synthesis. However, most of the carbenes and carbenoids are relatively short-lived and are too reactive to control. Recently, the author's group found that the treatment of aryl α-chloroalkyl sulfoxides and α-chlorovinyl p-tolyl sulfoxides with a Grignard reagent at low temperature gave magnesium carbenoids via the sulfoxide-magnesium exchange reaction. Magnesium carbenoids, cyclopropylmagnesium carbenoids, cyclobutylmagnesium carbenoids, magnesium alkylidene carbenoids, and magnesium α-oxido carbenoids were generated from the corresponding α-chloro sulfoxides with a Grignard reagent at low temperature. The generated magnesium carbenoids were proved to be relatively stable and they showed very interesting reactivity with several nucleophiles to afford many unprecedented new reactions. The present review is written for the purpose of reflecting recent achievements in the areas of chemistry and synthetic application of above-mentioned magnesium carbenoids. This review mainly covers literature from 2006 to late 2011. © 2012 The Japan Institute of Heterocyclic Chemistry.