Homologative Radical 1,3‐Dicarbofunctionalization of Unactivated Alkenes Enabled by Sequential Functional Group Migrations

Abstract Despite significant advances in conventional radical‐mediated 1,2‐difunctionalization of alkenes over the past decade, homologative 1,3‐difunctionalization remains largely underdeveloped. Herein, we report a novel photoinduced homologative 1,3‐dicarbofunctionalization of unactivated alkenes via one‐carbon chain elongation, achieved through sequential functional group migrations. By employing strategically designed tertiary alcohols and heteroarylsulfones as versatile coupling partners, this method affords structurally diverse, densely substituted aliphatic ketones and medium‐sized cyclic scaffolds with exclusive chemo‐ and regioselectivity. The transformation accommodates a broad range of migrating groups, including various heteroaryl, phenyl, and alkenyl motifs, and exhibits excellent functional group tolerance.