| Summary: | The aromatic C(sp<sup>2</sup>)-H functionalization of unprotected naphthols with <i>α</i>-phenyl-<i>α</i>-diazoesters under mild conditions catalyzed by CuCl and CuCl<sub>2</sub> exhibits high efficiency and unique <i>ortho</i>-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 <i>ortho</i>-selective C-H functionlization is due to the bimetallic carbene, which differs from the reaction catalyzed by CuCl<sub>2</sub> 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.
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