Stereoconvergent Approach to the Enantioselective Construction of <i>α</i>‐Quaternary Alcohols by Radical Epoxide Allylation
Sebastian Höthker, Annika Plato, Stefan Grimme, Zheng‐Wang Qu, Andreas Gansäuer
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.
Topics & Concepts
Enantioselective synthesisEpoxideQuaternaryChemistryOrganic chemistryCatalysisGeologyPaleontologyAsymmetric Synthesis and CatalysisRadical Photochemical ReactionsOxidative Organic Chemistry Reactions