Palladium-catalyzed,Sulfoxide-directed Asymmetric Activation Of C-H Bonds

Chiral sulfoxides structural existed in many drugs and biologically active molecules.And as chiral ligand and auxiliaries,chiral sulfoxide has very important applications in asymmetric synthesis.However,the method of synthesis chiral sulfoxides is very difficult,regularly requiring multiple steps and rigorous conditions,especially for the chiral diaryl sulfoxide.Therefore,it is necessary and urgent to develop an efficient method for synthesis chiral diaryl sulfoxide.In recent years,transition metal-catalyzed carbon-hydrogen activation has developed rapidly due to significant atom economy and step economy,and it is widely used in natural products and asymmetric synthesis as an efficient and convenient synthesis method.In this dissertation,we reported Pd(?)-catalyzed enantioselective carbon-hydrogen olefination of diaryl sulfoxides via desymmetrization and parallel kinetic resolution.And the palladium-catalyzed a-C-H arylation of carboxamides using sulfoxide-amide bidentate auxiliaries.The dissertation includes 5 chapters:Chapter 1:IntroductionIn this chapter firstly introduced many drugs and biologically active molecules that containing sulfoxide.Second,reviewed the development of chiral sulfoxide ligands and the important application of sulfoxides as directing group in organic synthesis.Finally,several methods for synthesis of chiral sulfoxides were introduced.Chapter 2:Pd(?)-catalyzed enantioselective carbon(sp2)-hydrogen olefination of diaryl sulfoxides through desymmetrizationThe main contents of this chapter introduced that our group developed sulfoxide-directed Pd(?)-catalyzed enantioselective carbon(sp2)-hydrogen olefination via desymmetrization.And the highest ee of product was 99%.Chapter 3:Palladium-catalyzed enantioselective carbon-hydrogen olefination of diaryl sulfoxides through parallel kinetic resolution.In order to further develop the method for synthesis chiral diaryl sulfoxide,our group continued research carbon(sp2)-hydrogen bond activation of the racemic asymmetric diary]sulfoxides to constructed chiral diaryl sulfoxides.We have unexpectedly found that such diaryl sulfoxides can undergo parallel kinetic resolution procedure to give two separable chiral diaryl sulfoxides.Chapter 4:Palladium-catalyzed a-C-H arylation of carboxamides using sulfoxide-amides bidentate auxiliariesAccording to our research about sulfoxides,sulfoxide-amides can also be used as bidentate auxiliaries to directed a-C-H arylation of carboxamides.Chapter 5:Summary of the Full TextSummarizing the three parts of the work of this dissertation.