Enantioselective One‐Pot Reaction: Organocatalyzed Synthesis of Fully Functionalized Oxabicyclo[2.2.2]octanes with Seven Contiguous Stereocenters

An enantioselective one‐pot Michael/Michael/Henry/hemiacetalization reaction between α,β‐unsaturated aldehydes, α‐ketoamides, and nitroalkenes under mild conditions catalyzed by a diarylprolinol silyl ether has been developed. The sequential methodology provides a direct approach to a wide range of fully substituted chiral oxabicyclo[2.2.2]octanes with seven contiguous stereocenters in moderate to excellent yields (up to 99%), high to excellent diastereoselectivities (up to >25:1 dr), and high to excellent enantioselectivities (up to 99% ee).