Alkene Difunctionalization Triggered by a Stabilized Allenyl Radical: Concomitant Installation of Two Unsaturated C−C Bonds. (28th July 2021)

• Record Type: Journal Article
• Authors: Wei, Yunlong; Zhang, Hong; Wu, Xinxin; Zhu, Chen
• Is Part Of: Angewandte Chemie. Volume 133:Number 37(2021)
• Page Start: 20377
• Page End: 20381
• Publication Date: 2021-07-28
• Subjects: alkene difunctionalization -- alkyne -- allenyl radical -- radical reactions -- rearrangement; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202106145
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Radical‐mediated difunctionalization of alkenes provides a promising approach to introduce one alkenyl or alkynyl group to target compounds. However, simultaneous installation of two unsaturated C−C bonds via alkene difunctionalization remains elusive, attributable to the high instability and transient lifetimes of alkenyl and alkynyl radicals. Herein, we report the photocatalytic 1, 2‐alkynylalkenylation and 1, 2‐enynylalkenylation of alkenes for the first time, triggered by the intermolecular addition of a stabilized allenyl radical to an alkene. A portfolio of strategically designed, easily accessible dual‐function reagents are applied to a radical docking‐migration cascade. The protocol has broad substrate scope and efficiently increases the degree of unsaturation. Abstract : Disclosed herein for the first time is the photocatalytic 1, 2‐alkynylalkenylation and 1, 2‐enynylalkenylation of alkenes, triggered by the intermolecular addition of a stabilized allenyl radical to an alkene. A portfolio of strategically designed, easily accessible dual‐function reagents are applied to a radical docking‐migration cascade. The protocol has broad substrate scope and efficiently increases the degree of unsaturation.