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

作者：Wu, Weirong; Zhao, Xufang; Chen, Guang; Liu, Lingjun; Li, Yulin; Chen, Tao; James, Tony D.^*; Liu, Yuxia^*

来源：Chemical Communications, 2023, 59(4): 482-485.

DOI：10.1039/d2cc06177e

• INDANONE DERIVATIVES
• BOND ACTIVATION
• AROMATIC AMIDES
• ANNULATION
• MECHANISM
• ARYLATION
• IODINATION
• DISCOVERY
• CLEAVAGE
• LIGANDS

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.

• 单位
  中国科学院; 陕西科技大学