Catalytic Enantioselective Inverse Electron Demand Hetero-Diels-Alder Reaction with Allylsilanes

The first diastereo- and enantioselective inverse electron demand hetero-Diels-Alder reaction of beta,gamma-unsaturated alpha-ketoesters with allylsilanes is described. Chiral copper( II) catalysts successfully activate the beta,gamma-unsaturated alpha-ketoesters and promote the reaction with allylsilanes with excellent enantioselectivities. This process represents a new entry to chiral oxanes.