We disclose a catalytic method for the enantio- and diastereoselective union of alkyl ethers and heterodienes. We demonstrate that a chiral Cu-BOX complex catalyzes the efficient oxidation of ethers into enol ethers in the presence of trityl acetate. Then, the organocopper promotes stereoselective hetero Diels-Alder reaction between the generated enol ethers and β,γ-unsaturated ketoesters, allowing for rapid access to an array of dihydropyran derivatives possessing three vicinal stereogenic centers.
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