Super silyl ester directed stereoselective reactions

A series of super silyl esters were synthesized in high yields. The super silyl group is a strong and robust protecting group even against highly reactive anionic species. By treating with alkyllithium reagents, organolithium compounds bearing super silyl ester group were generated and reacted with a variety of electrophiles to give the desired products. Moreover, alpha-alkylation/arylation of super silyl chloroacetate was achieved by the Matteson rearrangement. We also developed the aldol reactions of super silyl haloacetates to give beta-hydroxy-alpha-haloacetates in good yields with high syn-diastereoselectivities. Moreover, Darzens reaction of super silyl bromoacetate provided a concise synthetic route for cis-glycidic esters.;Finally, we developed super silyl ester directed Z-selective Peterson olefination. The reaction of alpha-silyl super silyl acetate derived lithium enolates with a wide range of aldehydes gave unsaturated esters in good yields with excellent Z selectivities. The starting materials can be easily prepared by the selective C-silylation of super silyl ester. We believed this method shed light on an effective synthesis of the less stable Z-unsaturated esters.