Inverting polarity in a cobalt MHAT reaction <i>via</i> reductive catalytic turnover.

ABSTRACT: Metal hydride hydrogen-atom-transfer (MHAT) catalysis proceeds via selective hydrogen atom transfer to olefins and is a key strategy in modern organic synthesis. The resulting carbon-centred radicals can engage in classical one-electron, radical transformations. Alternatively, following cage-collapse with the metalloradical and oxidation, an electrophilic alkyl-metal intermediate is formed which reacts as a carbocation equivalent. While this oxidative pathway is well-established, strategies to reverse the inherent polarity of the olefin, such that the internal carbon atom is nucleophilic, remain unexplored. The scarcity of this approach arises from challenges in integrating the classic oxidative MHAT catalytic cycle with single electron reduction of a radical reaction intermediate.

SUBMITTER: Jana S 

PROVIDER: S-EPMC12628006 | biostudies-literature | 2026 Jan

REPOSITORIES: biostudies-literature