Enantioselective Redox‐Divergent Chiral Phosphoric Acid Catalyzed Quinone Diels–Alder Reactions

An efficient enantioselective construction of tetrahydronaphthalene‐1,4‐diones as well as dihydronaphthalene‐1,4‐diols by a chiral phosphoric acid catalyzed quinone Diels–Alder reaction with dienecarbamates is reported. The nature of the protecting group on the diene is key to the success of achieving high enantioselectivity. The divergent “redox” selectivity is controlled by using an adequate amount of quinones. Reversible redox switching without erosion of enantioselectivity was possible from individual redox isomers.