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

摘要

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-HMIDLINE HORIZONTAL ELLIPSISO hydrogen bond interaction, thereby stabilizing the critical ortho-C-H functionalization TS; and (ii) the N-H moiety retention results in a weak NMIDLINE HORIZONTAL ELLIPSISNi sigma-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.

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