Asymmetric inverse-electron-demand hetero-Diels-Alder reaction of six-membered cyclic ketones: An enamine/metal lewis acid bifunctional approach

On demand: The first example of the title reaction involving cyclic ketones and β,γ-unsaturated α-ketoesters has been achieved using the novel enamine/metal Lewis acid bifunctional catalysis (see scheme; Tf=trifluoromethanesulfonyl). Enones with both electron-withdrawing and electron-donating groups at the γ position reacted smoothly with cyclohexanone affording the products in excellent chemo- and enantioselectivity.