Asymmetric Addition Reactions Catalyzed Chiral Br(?)nsted Acids

This thesis mainly focused on the development of novel asymmetric addition reactions by chiral Bronsted acids (or chiral sliver phosphate) and sequential reactions by Ru complex\chiral phosphoric acid (Hoveyda-Grubbs II, Zhan-1B and chiral phosphoric acid), which further expanded the application of these catalytic systems. chiral tetrahydropyrano[3,4-b]indoles (THPIs),1,2-dihydroisoquinolines, dihydrobenzofuran and3,4-dihydro-2H-benzo[b][1,4]oxazine derivatives and tetrahydro-1H-indoles were constructed in a concise manner.In the first part, chiral N-triflyl phosphoramide-catalyzed intramolecular Friedel-Crafts alkylation reaction has been realized to afford various tetrahydropyrano[3,4-b] indoles (THPIs) with excellent yields and up to98%ee. Moreover, the catalyst loading could be reduced to1mol%without erosion of yield and enantiomeric excess. The transformation of the ketone moiety to ester functionality with preserved ee was also successfully demonstrated through the Beckman rearrangement followed by hydrolysis and esterification.In the second part, the reaction of ortho-alkynylaryl aldimines and indoles catalyzed by a silver BINOL-derived phosphate was realized to afford a series of enantioenriched1,2-dihydroisoquinolines in moderate to good yields and ee. An interesting phenomenon that highly enantioenriched products could be obtained from their lower ee form by silica gel column chromatography was observed, providing an easy access to the enantiopure form of the product.In the third part, chiral phosphoric acid and Hoveyda-Grubbs II were found to catalyze an olefin cross-metathesis/intramolecular oxo-Michael cascade reaction of the ortho-allylphenols and enones to provide a variety of dihydrobenzofuran and3,4-dihydro-2H-benzo[b][1,4]oxazine derivatives in good yields and enantioselectivity.In the fourth part, with catalytic amount of Ru complex (Zhan-1B) and chiral phosphoric acid, the cross-metathesis/asymmetric intramolecular Friedel-Crafts type Michael cascade reaction of pyrrole linked olefins and enones was achieved to provide a variety of tetrahydro-1H-indole derivatives in good yields and up to93%ee. This study provides a novel route to construct these highly enantiomeric tetrahydro-1H-indole derivatives, which are valuable intermediates in the synthesis of natural products and pharmaceticals.