Polarity Umpolung Strategy for the Radical Alkylation of Alkenes. (11th March 2020)

• Record Type: Journal Article
• Authors: Liu, Jige; Wu, Shuo; Yu, Jiajia; Lu, Chenxi; Wu, Zhen; Wu, Xinxin; Xue, Xiao‐Song; Zhu, Chen
• Is Part Of: Angewandte Chemie. Volume 132:Number 21(2020)
• Page Start: 8272
• Page End: 8279
• Publication Date: 2020-03-11
• Subjects: Alkene -- Heterocyclen -- Photochemie -- Radikale -- Umpolung; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201915837
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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. Abstract : Ein einfaches Protokoll für die radikalische Alkylierung von Alkenen wurde basierend auf einer Strategie der Polaritätsumpolung entwickelt. Sowohl aktivierte als auch schwierige unaktivierte Alkene können umgesetzt werden. Die Methode bietet sich für späte Modifizierungen von Natur‐ und Wirkstoffmolekülen mit Alkengruppen an.