Complexity-Generating Transformations Enabled by Intramolecular Radical Migration: Alkyl–Arylation of Simple Olefins

A free-radical cascade approach has enabled the develop-ment of a synthetically versatile alkyl–arylation of olefins. This transformation engages an excellent range of olefins, from mono- to tetrasubstituted, without requiring directing or electronically activating groups. Further synthetic advantages, such as the facile generation of quaternary cen-ters and the introduction of heteroaryl groups with Lewis basic nitrogen atoms, also complement transition-metal-catalyzed alkyl–arylation. Vicinal stereoarrays were gener-ated with high levels of diastereoselectivity. The synthetic potential of this transformation was demonstrated by serving as the key step in a concise synthesis of oliceridine, a new painkiller that received FDA approval in 2020.