Mechanism of coenzyme-B12-dependent molecular rearrangements. Evidence for a radical-like process in a model reaction for methylmalonyl–CoA mutase

Abstract

Mechanistic probes of a model system for the coenzyme-B₁₂-dependent methylmalonyl–CoA mutase reaction have suggested (i) that the C–Co bond in the alkylcobalamin intermediate is capable of both carbanionic and homolytic cleavage, and (ii) that the skeletal rearrangement most probably takes place at the radical stage.