C-2-symmetric bis(oxazoline)-Cu(II) complexes 1 and 2 catalyze the inverse electron demand hetero Diels-Alder reaction of alpha,beta-unsaturated carbonyl compounds (heterodiene) with electron-rich olefins (heterodienophile) in high diastereo- and enantioselectivity, alpha,beta-Unsaturated acyl phosphonates and beta,gamma-unsaturated a-keto esters and amides are effective heterodienes, while enol ethers and sulfides function as heterodienophiles. A range of substitution patterns is possible on the heterodiene: terminal alkyl, aryl, alkoxy, and thioether substituents are all tolerated. The enantioselective synthesis of dihydropyrans by this method has been shown to be straightforward: cycloadditions may be conducted with as little as 0.2 mol % of the chiral catalyst and are readily run on multigram scale. The reactions exhibit a favorable temperature-enantioselectivity profile, with selectivities exceeding 90% even at room temperature. A simple reaction protocol that employs a solid air-stable catalyst, convenient reaction temperatures, and low catalyst loadings is described. The utility of the derived cycloadducts in the preparation of chiral building blocks is demonstrated. Models for asymmetric induction are discussed considering product stereochemistry, X-ray crystallographic data for the solid catalysts, and mechanistic studies.