A catalytic enantioselective inverse-electron demand hetero-Diels-Alder reaction of α, β- unsaturated carbonyl compounds with electron-rich alkenes catalyzed by chiral bisoxazolines in combination with Cu (OTf) 2 as the Lewis acid is presented. The reaction of γ-substituted β, γ-unsaturated α-keto esters with vinyl ethers and various types of cis- disubstituted alkenes proceeds in good yield, high diastereoselectivity, and excellent ...