Theoretical Study on the Copper-Catalyzed ortho-Selective C-H Functionalization of Naphthols with α-Phenyl-α-Diazoesters-Reference-Cited by-同舟云学术

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

Published:2023-02-13 Issue:4 Volume:28 Page:1767
ISSN:1420-3049
Container-title:Molecules
language:en
Short-container-title:Molecules

Author:

Zhu Xiaoli¹,Liu Xunshen¹²,Xia Fei¹³,Liu Lu¹²^ORCID

Affiliation:

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.

Funder

the National Natural Science Foundation of China

the Science and Technology Commission of Shanghai Municipality

Publisher

MDPI AG

Subject

Chemistry (miscellaneous),Analytical Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Molecular Medicine,Drug Discovery,Pharmaceutical Science

Link

https://www.mdpi.com/1420-3049/28/4/1767/pdf

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