Asymmetric Synthesis Of Indolyl-heterocycles Via C-O/S Bonds Functionalization

In this thesis, the research focused on the asymmetric synthesis ofindolyl-heterocycles based on functionalization of C-O/S bonds. There are three parts inthis thesis which were described as follows:Part I: we have reported an efficient way for a useful Friedel-Crafts reaction ofindoles with tert-enamides. The reaction proceeded smoothly in AcOH without catalystparticipation. By employing this method, a series of analogues of pharmaceuticals bearing2-oxo-1-pyrrolidine skeletons were facilely synthesized. The protocol has advantages suchas wider substrate scope, mild reaction conditions.Part II: we have developed an efficient MacMillan imidazolidinone-catalyzedasymmetric α-alkylation of aldehydes with3-hydroxy-3-indolylox-indoles. The reactionsproceeded smoothly in aqueous media (H2O/CH3CN) to afford3-indolyl-oxindoles in goodto excellent yields (up to98%) with moderate diastereoselectivities (up to70:30dr) andexcellent enantioselectivities (up to99%ee). Especially noteworthy is that the feasibilityof performing the reaction in water makes the protocol attractive for organic synthesisfrom both economic and environmental standpoints.Part III: we have demonstrated an enantioselective Michael addition of2-naphthols tovinylogous imine intermediates catalyzed by cinchona-alkaloid derived thioureaorganocatalyst. The vinylogous imine intermediates were generated fromarenesulfonyloxindoles. The protocol provides an efficient and convenient access to3-indolyl-oxindoles containing phenolic hydroxyl groups with high yields (up to86%) andenantioselectivities (up to90%ee) under mild conditions.