Zhang Weigang, Zou Zhenlei, Wang Yuanheng, Wang Yi, Liang Yong, Wu Zhengguang, Zheng Youxuan, Pan Yi
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
Angew Chem Int Ed Engl. 2019 Jan 8;58(2):624-627. doi: 10.1002/anie.201812192. Epub 2018 Dec 5.
Redox-active esters (RAEs) as alkyl radical precursors have been extensively developed for C-C bond formations. However, the analogous transformations of fluoroalkyl radicals from the corresponding acid or ester precursors remain challenging because of the high oxidation potential of the fluoroalkyl carboxylate anions. The newly developed N-hydroxybenzimidoylchloride (NHBC) ester provides a general leaving group assisted strategy to generate a portfolio of fluoroalkyl radicals, and can be successfully applied in photoinduced decarboxylative hydrofluoroalkylation and heteroarylation of unactivated olefins. In addition, DFT calculations revealed that the NHBC ester proceeds by the fluorocarbon radical pathway, whereas other well-known RAEs proceed by the nitrogen radical pathway.
氧化还原活性酯（RAEs）作为烷基自由基前体已被广泛用于碳-碳键的形成。然而，从相应的酸或酯前体生成氟烷基自由基的类似转化仍然具有挑战性，因为氟烷基羧酸根阴离子具有较高的氧化电位。新开发的N-羟基苯甲亚胺酰氯（NHBC）酯提供了一种通用的离去基团辅助策略，以生成一系列氟烷基自由基，并可成功应用于未活化烯烃的光诱导脱羧氢氟烷基化和杂芳基化反应。此外，密度泛函理论（DFT）计算表明，NHBC酯通过碳氟自由基途径进行反应，而其他著名的RAEs则通过氮自由基途径进行反应。
