Overlooked potential of N , N -bidentate directing-groups in Ni-catalyzed C-H functionalization of benzamides.

The Ni-catalyzed reactions of benzamides with bicyclic alkenes were explored using DFT calculations. An unprecedented "N-H deprotonation circumvented" catalytic mechanism was proposed, over the more common N-H/C-H activation mechanism, in which (i) the circumvention of N-H deprotonation ensures the presence of N-H⋯O hydrogen bond interaction, thereby stabilizing the critical ortho -C-H functionalization TS; and (ii) the N-H moiety retention results in a weak N⋯Ni σ-coordination, which is flexible to the configurational conversion during the key alkene insertion. These overlooked aspects of the functionalized N , N -bidentate directing groups will aid the design of new related catalytic reactions.