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.
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Höthker et al. (2024) studied this question.
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