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Updated: Jul 1, 2025
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
High-Valent Copper Catalysis Enables Regioselective Fluoroarylation of Gem-Difluorinated Cyclopropanes
Xiuli Wu1, Xiangyu Song1, Ying Xia1
1West China School of Public Health and West China Fourth Hospital, West China-PUMC C.C. Chen Institute of Health, and State Key Laboratory of Biotherapy, Sichuan University, Chengdu, 610041, China.
Abstract:
Transition-metal (TM) catalyzed reaction of gem-difluorinated cyclopropanes (gem-DFCPs) has drawn much attention recently. The reaction generally occurs via the activation of the distal C─C bond in gem-DFCPs by a low-valent TM through oxidative addition, eventually producing mono-fluoro olefins as the coupling products. However, achieving regioselective activation of the proximal C─C bond in gem-DFCPs that overcomes the intrinsic reactivity via TM catalysis remains elusive. Here, a new reaction mode of gem-DFCPs enabled by high-valent copper catalysis, which allows exclusive activation of the congested proximal C─C bond is presented. The reaction that achieves fluoroarylation of gem-DFCPs uses NFSI (N-fluorobenzenesulfonimide) as electrophilic fluoro reagent and arenes as the C─H nucleophiles, enabling the synthesis of diverse CF3-containing scaffolds. It is proposed that a high-valent copper species plays an important role in the regioselective activation of the proximal C─C bond possibly via a σ-bond metathesis.
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