Rh(II)-Catalyzed Enantioselective S-Alkylation of Sulfenamides with Acceptor-Acceptor Diazo Compounds Enables the Synthesis of Sulfoximines Displaying Diverse Functionality.

Abstract

The Rh(II)-catalyzed enantioselective S-alkylation of sulfenamides with α-amide diazoacetates at 1 mol % catalyst loading to obtain sulfilimines in high yields and enantiomeric ratios of up to 99:1 is reported. The enantioenriched sulfilimine products incorporate versatile amide functionality poised for further elaboration to diverse sulfoximines with multiple stereogenic centers, including by highly diastereoselective sulfilimine and sulfoximine α-alkylation with alkylating agents and epoxides and by interconversion of the amide to N-tert-butanesulfinyl aldimines, followed by diastereoselective additions.