Abstract
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.
Original language | English |
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Pages (from-to) | 482-485 |
Number of pages | 4 |
Journal | Chemical Communications |
Volume | 59 |
Issue number | 4 |
Early online date | 19 Dec 2022 |
DOIs | |
Publication status | Published - 19 Dec 2022 |