Control of meta -selectivity in the Ir-catalyzed aromatic C-H borylation directed by hydrogen bond interaction: A combined computational and experimental study

The origin of regioselectivity in meta-selective C-H borylation of benzamides directed by hydrogen bond interaction between ligand and substrate is elucidated through combined computational and experimen-tal studies. We discover that a non-directed pathway, in which the urea moiety in ligand recognizes the O atom in Bpin instead of substrate, competes with the directed pathway and erodes the meta-selectivity. The non-directed pathway is sensitive to steric repulsion between Bpin and urea, and thus can be im-peded by introducing a bulky substituent into the urea moiety. Accordingly, we optimize the ligand and improve the meta-selectivity in the Ir-catalyzed C-H borylation of some previously reported unsuccessful arenes.(c) 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.