Cu@CuCl-visible light co-catalysed chlorination of C(sp3)–H bonds with MCln solution and photocatalytic serial reactor-based synthesis of benzyl chloride

Zhang, Qi; Liu, Shouxin; Tian, Xia; Liu, Yidong; Fan, Shiming; Huang, Baibiao; Whiting, Andrew

doi:10.1039/d1gc03092b

Cu@CuCl-visible light co-catalysed chlorination of C(sp3)–H bonds with MCln solution and photocatalytic serial reactor-based synthesis of benzyl chloride

Zhang, Qi; Liu, Shouxin; Tian, Xia; Liu, Yidong; Fan, Shiming; Huang, Baibiao; Whiting, Andrew

Authors

Qi Zhang

Shouxin Liu

Xia Tian

Yidong Liu

Shiming Fan

Baibiao Huang

Professor Andrew Whiting andy.whiting@durham.ac.uk
Emeritus Professor

Abstract

A highly selective, green and sustainable chlorination of aliphatic C–H bonds is reported using MCln under the co-catalysis of visible light and nano-Cu@CuCl, which was synthesised via a one-step, hydrothermal strategy using copper(II) sulfate and D-glucose as the reducing agent in a KCl solution. A novel cascade method of producing Cl2 occurs in situ chlorinating C(sp3)–Hs, achieved through nano-Cu@CuCl catalysis using inorganic chloride MCln as a chlorine source under visible light and without the need for a strong oxidant. The reaction was applied to the chlorination of different alkylarene α-Hs and cyclic hydrocarbons C–HS and was developed for use in a photocatalytic serial reactor system which accomplished the chlorination of toluene α-Hs to give 92% conversion, 90% yield and 98% selectivity. Electron spin resonance (ESR) studies of DMPO-Cl. revealed that the reaction mechanism belonged to a free radical process.

Citation

Zhang, Q., Liu, S., Tian, X., Liu, Y., Fan, S., Huang, B., & Whiting, A. (2022). Cu@CuCl-visible light co-catalysed chlorination of C(sp3)–H bonds with MCln solution and photocatalytic serial reactor-based synthesis of benzyl chloride. Green Chemistry, 24(1), 384-393. https://doi.org/10.1039/d1gc03092b

Journal Article Type	Article
Acceptance Date	Dec 6, 2021
Online Publication Date	Dec 6, 2021
Publication Date	Jan 7, 2022
Deposit Date	Jan 26, 2022
Publicly Available Date	Dec 6, 2022
Journal	Green Chemistry
Print ISSN	1463-9262
Electronic ISSN	1463-9270
Publisher	Royal Society of Chemistry
Peer Reviewed	Peer Reviewed
Volume	24
Issue	1
Pages	384-393
DOI	https://doi.org/10.1039/d1gc03092b