The combination of TsNH₂ and NCS as nitrogen and chlorine sources for direct diamination of enones

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 TsNH₂ 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.