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

Xiaoli Zhu; Xunshen Liu; Fei Xia; Lu Liu

doi:10.3390/molecules28041767

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

Molecules. 2023 Feb 13;28(4):1767. doi: 10.3390/molecules28041767.

Authors

Xiaoli Zhu¹, Xunshen Liu^{1

2}, Fei Xia^{1

3}, Lu Liu^{1

2}

Affiliations

¹ School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai 200241, China.
² Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, East China Normal University, Shanghai 200062, China.
³ NYU-ECNU Center for Computational Chemistry at New York University, East China Normal University, 3663 Zhongshan Road, Shanghai 200062, China.

Abstract

The aromatic C(sp²)-H functionalization of unprotected naphthols with α-phenyl-α-diazoesters under mild conditions catalyzed by CuCl and CuCl₂ 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 CuCl₂ 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.

Keywords: copper catalysis; density functional theory (DFT) calculations; diazo compounds; metal carbene; naphthols; ortho-C(sp2)-H bond functionalization.

MeSH terms

Catalysis
Copper
Models, Theoretical
Naphthols*
Protons*

Substances

Naphthols
Protons
Copper
carbene

Abstract

MeSH terms

Substances

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