Cobalt‐Catalyzed Radical Ligand Transfer (RLT) Enables <i>Remote</i> ‐Markovnikov Hydroamination of Alkenes

Abstract

ABSTRACT Amino alcohols are prevalent in pharmaceuticals, agrochemicals, and functional materials, yet regioselective remote C─N bond formation from simple alkenes remains limited. We report a remote ‐Markovnikov formal 1,3‐hydroamination of allyl carboxylates enabled by cooperative photoredox, cobalt, and Brønsted acid catalysis. The reaction proceeds via metal–hydride hydrogen atom transfer (MHAT) followed by 1,2‐radical acyloxy migration (1,2‐RAM) to generate a tertiary carbon‐centered radical at a site remote from the original alkene, affording protected tertiary alkyl amino alcohols across a broad substrate scope, with secondary variants also accessible. Experimental and computational studies support a C─N bond‐forming step best described as radical ligand transfer (RLT) at a Co(III)─N intermediate, rather than Co(IV)/S N 2 or carbocationic pathways. This rare nitrogen‐transfer manifold accounts for the observed regioselectivity and catalyst‐influenced stereochemical outcomes. By enabling migration‐controlled 1,3‐hydroamination, this strategy complements conventional 1,2‐hydroamination and expands accessible amino alcohol chemical space.