Yang Xin-Jun, Lin Jin-Hong, Xiao Ji-Chang
Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 200032, Shanghai, China.
Department of Chemistry, Innovative Drug Research Center, Shanghai University, 200444, Shanghai, China.
Nat Commun. 2025 Jan 7;16(1):445. doi: 10.1038/s41467-024-55797-4.
Considering the unique electronic properties of the CF and the CN groups, the CFCN group has significant potential in drug and agrochemical development, as well as material sciences. However, incorporating a CFCN group remains a considerable challenge. In this work, we disclose a use of bromodifluoroacetonitrile (BrCFCN), a cost-effective and readily available reagent, as a radical source for cyanodifluoromethylation of alkyl alkenes, aryl alkenes, alkynes, and (hetero)arenes under photocatalytic conditions. This protocol demonstrates an exceptionally broad substrate scope and remarkable tolerance to various functional groups. Notably, the cyanodifluoromethylation of alkynes predominantly provides sterically hindered alkenes, a thermodynamically unfavorable outcome, and (hetero)arene C-H bonds are directly amenable to cyanodifluoromethylation without pre-functionalization.
考虑到CF和CN基团独特的电子性质，CFCN基团在药物和农用化学品开发以及材料科学方面具有巨大潜力。然而，引入CFCN基团仍然是一个相当大的挑战。在这项工作中，我们公开了使用溴二氟乙腈（BrCFCN），一种经济高效且易于获得的试剂，作为光催化条件下烷基烯烃、芳基烯烃、炔烃和（杂）芳烃氰基二氟甲基化的自由基源。该方案展示了异常广泛的底物范围以及对各种官能团的显著耐受性。值得注意的是，炔烃的氰基二氟甲基化主要生成空间位阻烯烃，这是一种热力学上不利的结果，并且（杂）芳烃的C-H键无需预官能化即可直接进行氰基二氟甲基化。
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