The Combination of TsNH₂ and NCS as Nitrogen and Chlorine Sources for Direct Diamination of Enones

Abstract

Abstract The regio‐, stereo‐, and chemoselective diamination of enones has been achieved without the observation of any haloamines. The reaction employs the readily available inexpensive combination of NCS and TsNH 2 as an electrophilic nitrogen source, and three nitriles as nucleophilic nitrogen sources. A novel mechanism involving the formation of aziridinium intermediates from the reaction of TsNHCl with olefins and a new [2+3] cyclic addition for aziridinim ring opening has been proposed for the electrophilic diamination of olefins. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)