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可见光光氧化还原催化的α-三氟甲基烯烃与芳基氯化物的自由基脱氟芳基化反应

Visible Light Photoredox-Catalyzed Radical Defluorinative Arylation of α-Trifluoromethyl Alkenes with Aryl Chlorides.

作者信息

Chen Yumeng, Mao Xudong, Li Miao-Miao, Ding Wei

机构信息

Division of Molecular Catalysis and Synthesis, Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou 450001, P. R. China.

出版信息

J Org Chem. 2025 Mar 7;90(9):3391-3403. doi: 10.1021/acs.joc.4c03088. Epub 2025 Feb 26.

Abstract

Photocatalytic defluorinative cross-coupling reactions of α-trifluoromethyl alkenes with diverse radical precursors have emerged as a powerful strategy for the synthesis of -difluoroalkenes. However, the radical defluorinative arylation is relatively rare due to the limitation of aryl radical precursors. Aryl chlorides, as ideal candidates, remain a large challenge in this reaction because of the chemical inertness of the C(sp)-Cl bond and their high negative reduction potential. Herein, we report a radical defluorinative arylation of α-trifluoromethyl alkenes with aryl chlorides as aryl radical precursors through a consecutive photoinduced electron transfer (ConPET) process. This protocol features mild conditions, operational simplicity, wide substrate scope, and functional group tolerance, producing a diverse range of benzylic -difluoroalkenes in moderate to good yields. The scale-up reaction and the valuable transformations of products demonstrate the great potential applications of this approach.

摘要

α-三氟甲基烯烃与多种自由基前体的光催化脱氟交叉偶联反应已成为合成二氟烯烃的有力策略。然而,由于芳基自由基前体的限制,自由基脱氟芳基化反应相对较少。芳基氯化物作为理想的候选物,在该反应中仍然面临巨大挑战,因为C(sp)-Cl键的化学惰性及其高负还原电位。在此,我们报道了通过连续光诱导电子转移(ConPET)过程,以芳基氯化物作为芳基自由基前体,实现α-三氟甲基烯烃的自由基脱氟芳基化反应。该方法具有条件温和、操作简便、底物范围广、官能团耐受性好等特点,能以中等至良好的产率制备多种苄基二氟烯烃。放大反应和产物的有价值转化证明了该方法具有巨大的潜在应用价值。

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Visible Light Mediated Photoredox Catalytic Arylation Reactions.可见光介导的光氧化还原催化芳基化反应。
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