Remote Catalytic C(sp)-H Alkylation via Relayed Carbenoid Transfer upon Olefin Chain Walking.

Transition metal carbenes have emerged as versatile intermediates for various types of alkylations. While reactions of metal carbene species with alkenes have been extensively studied, most examples focus on cyclopropanation and allylic C-H insertion. Herein, we present the first example of a catalytic strategy for the carbene-involved regioselective remote C-H alkylation of internal olefins by synergistically combining two iridium-mediated reactivities of olefin chain walking and carbenoid migratory insertion. The present method, utilizing sulfoxonium ylides as a bench-stable robust carbene precursor, was found to be effective for a series of olefins tethered with alkyl chains, heteroatom substituents, and complex biorelevant moieties. Combined experimental and computational studies revealed that reversible iridium hydride-mediated olefin chain walking proceeds to lead to a terminal alkyl-Ir intermediate, which then forms a carbenoid species for the final migratory insertion, resulting in regioselective terminal-alkylated products.