Exploitation of the Chemistry of Magnesium Carbenoids and Their Use in New Synthetic Method for Organic Synthesis

点击翻译按钮获取中文摘要

Carbenes and carbenoids have long been known to be highly reactive carbon species that show a variety of unique reactivities. However, those reactive species are not fully used in organic synthesis. The reasons are as follows : one is the precursors for the generation of carbenes and carbenoids are quite limited and the other is that the reactivity of the species is too high to control. In order to solve the problem mentioned above, we used α-haloalkyl (or alkenyl) aryl sulfoxides as the precursors and used sulfoxide-magnesium exchange reaction for generation of much mild magnesium carbenoids. α-Haloalkyl (or alkenyl) aryl sulfoxides are quite easily synthesized in high overall yields. Magnesium carbenoids, cyclopropylmagnesium carbenoids, cyclobutylmagnesium carbenoids, magnesium β-oxido carbenoids, and magnesium alkylidene carbenoids are generated at low temperature from the corresponding sulfoxides with a Grignard reagent in quantitative yields. They were found to be stable usually at below -60℃ for at least 30 min. The each magnesium carbenoids have their own unique reactivities and we could found many unprecedented reactions from these reactive species.