Palladium-catalyzed remote internal C(sp)-H bond chlorination of alkenes.

C(sp)-Cl bonds are present in numerous biologically active molecules and can also be used as a site for diversification by substitution or cross-coupling reactions. Herein, we report a remote internal site-selective C(sp)-H bond chlorination of alkenes through sequential alkene isomerization and hydrochlorination, enabling the synthesis of both benzylic and tertiary chlorides with excellent site-selectivity. This transformation offers exciting possibilities for the late-stage chlorination of derivatives of natural products and pharmaceuticals. We also demonstrate the regioconvergent synthesis of a single alkyl chloride from unrefined mixtures of isomeric alkenes, which can be extracted directly from petrochemical sources.