Study On Catalytic Asymmetric Synthesis And Recognition Of Atropisomeric Arylquinolines

Axial chirality reprents an important type of chirality which has been found widely.It has become a shining pearl in asymmetry synthesis field after fast development for several decades.On the other hand,chiral phosphoric acids were proved to be outstanding organocatalyst which are wildly used in catalytic asymmetric synthesis in the last two decades.Quinolines are important synthetic targets which have been found in numerous natural products,bioactive compounds,chiral catalysts,and ligands.However,there were limited examples exist for the catalytic asymmetric synthesis of axial chiral 4-arylquinolines.The classical Friedl(?)nder reaction is a powerful strategy for constructing quinoline scaffolds,but never used for the construction of axial chiral ones before we carry out our research.In this thesis,we developed a catalytic asymmetric synthesis of atropisomeric quinolines via the Friedl(?)nder reaction by employing 2-aminobenzophenones and acetylacetone as reactants..giving a variety of electron-withdrawing and donating axial chiral 4-arylquinolines.This method takes advantage of easy operation and structural diversity;beisides,a gram-scale reaction was also achieved.Mechanism study revealed this reaction may undergo enamine formationintramolecular nucleophilic attack process.Besides,we studied the chiral recognition of atropisomeric arylquinolines by employing chiral phosphoric acid as sensor.In recent years various types of chiral solvating agent(CSA)have been used as chiral sentors to enable the analysis of the optical purity of chiral compounds via NMR spectroscopy.In our research,chiral phosphoric acid was successfully applied in chiral recognition of various arylquinolines.Our method is simple to operate and has a wide range of substrate applications.The linear relationship shows that optical purity of non-racemic arylquinolines guest can be measured rapidly with high-precision.