Unexpected copper-catalyzed aminohalogenation reaction of olefins using N-halo-N-metallo-sulfonamide as the nitrogen and halogen sources

N-Chloro-N-sodium-sulfonamide was found to react with olefins in the presence of copper catalyst to give vicinal haloamine derivatives instead of aziridines. The resulting regio and stereochemistry indicates that this unexpected reaction could proceed through the formation of unprecedented N-chloro-N-copper-2-nitrobenzenesulfonyl aziridinium intermediates, which can increase the successful chance to render the asymmetric version of the aminohalogenation reaction. In addition, this finding provides a more convenient protocol by the use of solely pure NsNClNa for the aminohalogenation reaction as compared to the mixed nitrogen and chlorine sources consisting of NsNCl2 and NsNHNa as previously reported by us. Two new simple olefin substrates, trans-stilbene and styrene, were also found to be effective for this new reaction system.