Stereoconvergent Approach to the Enantioselective Construction of α‐Quaternary Alcohols by Radical Epoxide Allylation

Abstract We describe a highly stereoconvergent radical epoxide allylation towards diastereomerically and enantiomerically enriched α ‐quaternary alcohols in two steps from olefins. Our approach combines the stereospecifity and enantioselectivity of the Shi epoxidation with the unprecedented Ti(III)‐promoted intramolecular radical group transfer allylation of epoxides. A directional isomerization step via configurationally labile radical intermediates enables the selective preparation of all‐carbon quaternary stereocenters in a unique fashion.