Chiral Sulfinamide Phosphine Ligands:Application In Palladium-Catalyzed Asymmetric Reactions

Palladium-catalyzed asymmetric coupling reaction is a classical method for the efficient synthesis of chiral organic compounds,in which the chiral ligands play a crucial role in this field.This dissertation focuses on palladium-catalyzed asymmetric processes for the formation of C-S and C-O bonds.1.Palladium/PC-Phos catalyzed enantioselective arylation of general sulfenate anions to synthesize chiral sulfoxidesThe palladium/PC-Phos catalyzed system is a kind of robust system for the enantioselective arylation of aryl sulfenate anions and alkyl sulfenate anions to deliver chiral diaryl or aryl alkyl sulfoxides in good yields with high enantioselectivity.The method has been applied to the synthesis of the marketed medicine Sulindac.Besides,it is noteworthy that the chiral sulfinamide monophosphine and palladium can form a rarely observed 11-membered ring via coordination of the phosphine and the O-atom of the sulfonamide moiety.Based on the further exploration of this related reaction,an efficient arylation of general sulfenate anions with diaryliodonium salts under transition metal-free conditions was founded.2.Palladium/Xiang-Phos catalyzed enantioselective carboetherification of alkenyl oximes We developed a Palladium/Xiang-Phos catalyzed alkene carboalkoxylation reactions between alkenyl oximes and aryl/alkenyl halides for the construction of isoxazolines,which successfully realized the formation of C-C and C-O bonds through the carboalkoxylation reactions with high enantioselectivity.The salient features of this transformation include mild reaction conditions,general substrate scope,well functional group tolerance,good yields and high enantioselectivity.