Catalytic Asymmetric [4+2] Cycloadditions and Hosomi-Sakurai Reactions of α-Alkylidene β-Keto Imides

Highly enantioselective catalytic asymmetric reactions of rationally designed alpha-alkylidene beta-keto Imides are described. The [4 + 2] cycloadditions and Hosomi-Sakurai reactions of alpha-alkylidene beta-keto imides proceed with high enantioselectivity and yield. The [4 + 2] cycloadditions of the imides with various dienes afford products bearing an all-carbon quaternary stereogenic center at the ring junction. alpha-Alkylidene beta-keto imides should be useful for the enantioselective total synthesis of natural products and other catalytic asymmetric applications.