Pd-Catalyzed Asymmetric Arylative Dearomatization Of Indoles

This dissertation mainly focuses on the development of Pd-catalyzed arylative dearomatization reaction.It includes two parts:(1)Dearomatization of bisindole derivatives via arylative reaction was achieved in an intramolecular fashion,providing a facile synthsis of enantioenriched substituted spiroindolenines;(2)An asymmetric arylative dearomatization of simple indoles and pyrroles was realized to expand the substrate scope of the reaction.Pd-catalyzed asymmetric arylative dearomatization of C3-substituted indoles was realized via a desymmetrization strategy.A BINOL-derived chiral phosphoramidite ligand was found to be highly efficient for the stereoselective control in this reaction.This method provided a convenient synthesis of spiroindolenines bearing two stereogenic centers in good yields(up to 98%)with excellent diastereoand enantio-selectivities(up to >20:1 dr and 97% ee).Diverse enantiomerically enriched spiroindolenines bearing a quaternary stereogenic center were obtained in excellent yields with high enantioselectivity by using the simple C3-tethered indoles.This strategy could also be applied in asymmetric arylation of C2-tethered pyrroles,delivering the corresponding pyrrolines in 84-97% yields and 82-91% ee.