Two steps, one catalyst: A vanadium(V)–oxo complex with a tridentate Schiff base as an additional ligand catalyzes the title reaction which transforms racemic bishomoallylic α-hydroxyesters into trans-tetrahydropyrans (THPs) and cis-tetrahydrofurans (THFs). This synthetic method provides an efficient asymmetric synthesis of cyclic ethers as demonstrated by the first enantioselective synthesis of (−)-pantofuranoid E. TBHP=tert-butylhydroperoxide.
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