Hypervalent N-sulfonylimino-λ3-bromane: active nitrenoid species at ambient temperature under metal-free conditions

Abstract

The synthesis and reactions of N-triflylimino-λ³-bromane are summarized. The hypervalent iminobromane functions as a highly active nitrenoid species at ambient temperature under transition metal-free conditions, probably because of the increased hypernucleofugality of aryl-λ³-bromanyl groups compared to that of aryl-λ³-iodanyl groups. The imino-λ³-bromane undergoes stereospecific aziridination of olefins and transylidation to aromatic nitrogen heterocycles, trialkylamines and iodobenzenes. Difluoro-λ³-bromane-induced Hofmann rearrangement of primary arylsulfonamides is also discussed.