Cobalt-Catalyzed Radical Ligand Transfer (RLT) Enables Remote-Markovnikov Hydroamination of Alkenes

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_N2 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.