Phosphine Catalyzed Enantioselective Cascade Reaction Initiated by Intermolecular Cross Rauhut‐Currier Reaction of Electron‐Deficient ortho‐Formyl Styrenes

The Rauhut-Currier reaction generally employs alpha,beta-unsaturated carbonyl compounds and nitroalkenes as the substrates. Here we develop an enantioselective formal [4+2] annulation reaction, which is initiated by an intermolecular cross Rauhut-Currier reaction between electron-deficient-ortho-formyl-styrenes and 2-benzoyl-acrylonitriles catalyzed by an L-phenylglycine-derived phosphine, followed by a cascade aldol/acyl transfer/elimination process. A series of enantioenriched dialin frameworks with an unusualexo-double bond are furnished in fair to good yields with moderate to excellent enantioselectivity, and the architectures with higher molecular complexity can be constructed via simple transformations.