CO insertion enabled γ-C(sp3)-H heteroarylative carbonylation of tertiary alcohols via heteroaryl migration.

The direct functionalization of remote C(sp3)-H is valuable but challenging, and is even more difficult to achieve than the γ-C(sp3)-H functionalization of alcohols. Among the strategies, hydrogen atom transfer (HAT) is one of the solutions for such transformations. Herein, we designed a migration reaction involving carbon monoxide, forming an alkoxy radical by photocatalysis, and used carbon monoxide to extend the carbon chain to provide a site for the migration of heteroaryl groups, which makes 1,4-HAT more advantageous, and we relied on this strategy to successfully achieve the synthesis of 1,4-dicarbonyl compounds by γ-C(sp3) functionalization of alcohols.