Theoretical Study on the Copper-Catalyzed ortho -Selective C-H Functionalization of Naphthols with α -Phenyl- α -Diazoesters.

The aromatic C(sp 2 )-H functionalization of unprotected naphthols with α -phenyl- α -diazoesters under mild conditions catalyzed by CuCl and CuCl 2 exhibits high efficiency and unique ortho -selectivity. In this study, the combination of density functional theory (DFT) calculations and experiments is employed to investigate the mechanism of C-H functionalization, which reveals the fundamental origin of the site-selectivity. It explains that CuCl-catalyzed ortho -selective C-H functionlization is due to the bimetallic carbene, which differs from the reaction catalyzed by CuCl 2 via monometallic carbene. The results demonstrate the function of favourable H-bond interactions on the site- and chemo-selectivity of reaction through stabilizing the rate-determining transition states in proton (1,3)-migration.