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

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
• Public URL: https://durham-repository.worktribe.com/output/1217060