Sterically Demanding Oxidative Amidation of α-Substituted Malononitriles with Amines Using O2

An efficient amidation method between readily available 1,1-dicyanoalkanes and either chiral or nonchiral amines was realized simply with molecular oxygen and a carbonate base. This oxidative protocol can be applied to both sterically and electronically challenging substrates in a highly chemoselective, practical, and rapid manner. The use of cyclopropyl and thioether substrates support the radical formation of alpha-peroxy malononitrile species, which can cyclize to dioxiranes that can monooxygenate malononitrile alpha-carbanions to afford activated acyl cyanides capable of reacting with amine nucleophiles.