Direct Enantioselective Synthesis of Bicyclic Diels–Alder Products

The direct amine‐catalyzed enantioselective Diels–Alder reaction between α,β‐unsaturated cyclic ketones and nitroolefins is presented. A simple diamine catalyzes the asymmetric Diels–Alder reaction with high stereoselectivity and furnishes the corresponding Diels–Alder adducts in good to high yields with >25:1 dr and up to 86 % ee. The study demonstrates a convenient entry to functionalized bicyclic molecules contaning four stereocenters that are formed with excellent diastreoselectivity and good to high enantioselectivity.