Polarity Umpolung Strategy for the Radical Alkylation of Alkenes
Jige Liua,+, Shuo Wua,+, Jiajia Yua, Chenxi Lub, Zhen Wua, Xinxin Wua, Xiao-Song Xueb, and Chen Zhua,*（朱晨）
aKey Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu 215123 (China)
bState Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071 (China)
+These authors contributed equally to this work.
Angew. Chem. Int. Ed. 2020, 59, 8195--8202
Free radical mediated alkylation of alkenes is a challenging and largely unmet goal. Disclosed here is a conceptually novel “polarity umpolung” strategy for radical alkylation of alkenes using a portfolio of easily accessed, difunctional alkylating reagents. This strategy is achieved by substituting inherently nucleophilic alkyl radicals with electrophilic sulfone‐bearing surrogates, thus inverting the usual mode of reactivity. Along with alkylation, either an heteroaryl or oximino group is concurrently incorporated into the alkenes by a consecutive docking and migration process, leading to valuable products. The reaction displays a broad functional‐group tolerance under mild reaction conditions. The protocol opens new vistas for the late‐stage modification of complex natural products and drug molecules containing alkene moieties.