A New Method for generation of Magnesium Carbnoids and Magnesium Carbanions, and its Application to Organic Synthesis

摘要

On treatment of alkyl aryl sulfoxides with alkylmetals (alkyllithium or Grignard reagent) sulfuralkyl or sulfur-aryl bond-cleavage takes place to give new alkylmetals or arylmetals. This reaction is called sulfoxide-metal exchange reaction. In this paper, the author mainly reviews the new methods for the generation of magnesium carbenoids and alkylmagnesiums having a heteroatom on their #alpha#-position by the sufoxide-magnesium exchange reaction.When the alkyl aryl sulfoxides have a heteroatom (such as Cl, O, N) on the #alpha#position in the alkyl group, the reaction with alkylmetals results in the sulfur-alkyl bond cleavage to give a carbenoids and/or #alpha#-heteroatom-substituted carbanions at low temperature in high yields. Especially, magnesium carbenoids are quite interesting compounds and some novel synthetic reactions have been developed via the carbenoids. The sulfoxide-magnesium exchange reaction of sulfinylaziridines gave the stable aziridinylmagnesiums, from which a new synthesis of both enantiomers of the optically active amines having a quaternary ciral center was realized. a new synthesis of olefins and allenes, including optically active form, from sulfoxides and alkenyl sulfoxides, and carbonyl compounds by the sulfoxide-magnesium exchange reaction is also reviewed.