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

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. [ABSTRACT FROM AUTHOR]