Ma Zhigang, Wu Xinxin, Zhu Chen
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, 215123, Jiangsu, China.
Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, 800 Dongchuan Road, 200240, Shanghai, China.
Chem Rec. 2023 Sep;23(9):e202200221. doi: 10.1002/tcr.202200221. Epub 2022 Nov 11.
Fluorine incorporation by concomitant fluoroalkyl radical addition to alkene or alkyne and functional group migration (FGM) represents an ingenious and robust strategy for the synthesis of structurally diverse fluorinated compounds. This account gives an overview of related studies in our group, in which three main reaction modes are discussed: 1) radical fluoroalkylative difunctionalization of unactivated alkenes via intramolecular FGM; 2) alkene difunctionalization by docking-migration process using fluoroalkyl-containing bifunctional reagents; 3) incorporation of fluoroalkyl group into C(sp )-H bond via consecutive hydrogen atom transfer (HAT) and FGM. Relying on these methods, a variety of trifluoromethylation and di-/mono-fluoroalkylation reactions along with the migration of cyano, heteroaryl, oximino, formyl, alkynyl, and alkenyl groups have been accomplished under mild conditions.
通过将氟烷基自由基加成到烯烃或炔烃上并伴随官能团迁移（FGM）来引入氟，是合成结构多样的氟化化合物的一种巧妙且稳健的策略。本综述概述了我们小组的相关研究，其中讨论了三种主要反应模式：1）通过分子内FGM对未活化烯烃进行自由基氟烷基化双官能化；2）使用含氟烷基的双官能试剂通过对接-迁移过程进行烯烃双官能化；3）通过连续氢原子转移（HAT）和FGM将氟烷基引入C(sp) -H键。依靠这些方法，在温和条件下实现了各种三氟甲基化以及二氟/单氟烷基化反应，同时还实现了氰基、杂芳基、肟基、甲酰基、炔基和烯基的迁移。
