Asymmetric Inverse-Electron-Demand Oxa-Diels–Alder Reaction of Allylic Ketones through Dienamine Catalysis

A remote
β,γ-regioselective asymmetric inverse-electron-demand
oxa-Diels–Alder reaction between allylic ketones and α-cyano-α,β-unsaturated
ketones has been developed through induced extended dienamine catalysis
of a cinchona-derived primary amine. A spectrum of densely substituted
dihydropyran frameworks were efficiently produced with excellent enantioselectivity
and fair to exclusive diastereoselectivity.