Pd-Catalyzed Asymmetric Intramolecular Arylative Dearomatization of para-Aminophenols†

The Summary of main observation and conclusion Asymmetric arylative dearomatization reactions of para-aminophenols are realized by a Pd-catalyst consisting of a TADDOL (alpha,alpha,alpha',alpha'-tetraaryl-2,2-disubstituted 1,3-dioxolane-4,5-dimethanol)-derived chiral phosphoramidite ligand. The tetracyclic products bearing the key skeleton of Erythrina alkaloids are afforded in reasonable yields (up to 73%) with good to excellent enantioselectivity (up to 97% ee). Concise total synthesis of (-)-3-demethoxyerythratidinone is achieved by employing this method as the key step.