An enantioselective method for the intramolecular sulfenoamination of unactivated alkenes has been developed using a chiral BINAM-based selenophosphoramide Lewis base catalyst (LB*). Generation of an active chiral aryl sulfide species by coordination of the chiral selenophosphoramide catalyst to an aryl sulfur electrophile enables enantioselective formation of a thiiranium intermediate. Cyclization through the stereospecific capture of this enantio-enriched thiiranium intermediate by the pendant arylsulfonyl-protected amine nucleophile affords pyrrolidines, piperidines, and azepanes in high yields and up to 97:3 enantiomeric ratio.

Lewis base catalyzed, enantioselective, intramolecular sulfenoamination of olefins

249th National Meeting (2015)

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