Phosphine-catalyzed Asymmetric ?-Addition Reactions And Design, Synthesis Of A Novel Chiral Phosphine Ligands

Allenoate is one of the most commonly employed electron-deficient substrates in asymmetric phosphine-catalyzed reactions.This dissertation mainly focuses on enantioselective ?-addition reactions of N-centered nucleophiles to allenoates.Besides,the development of new ligands is very important in transition-metal catalysis.We have been focusing on the design and synthesis of new chiral sulfinamide monophosphine ligands,such as MingPhos and PC-Phos which performed well in asymmetric transition-metal catalysis.In order to further advance new catalyst design,we designed and synthesized a new type of chiral phosphine ligands.The detailed contents of dissertation including the following two parts:The first part was based on enantioselective ?-addition reactions of N-centered nucleophiles to allenoates using a noval class of cyclic phosphine catalyst LePhos.In this part,we successfully acquired a series of ?-addition adducts in high yields with up to 98% ees and excellent regioselectivity under mild conditions.Furthermore,different types of N-centered nucleophiles were also compatible by changing the substituents of LePhos.In the second part,inspiring by the successful skeleton of MingPhos,we designed two routes and synthesed a new class of chiral sulfonamide phosphine ligands,so called CF-Phos.