Synthesis Of QUINAP-Type P-N Ligands Catalyzed By Lewis Acid

Because of their special framework structure and chiral recognition function,biaryl compounds with axial chirality,such as BINAP,QUINAP and other ligands play a unique regulatory role in asymmetric catalysis and other fields,so they have attracted people's attention widely,and it is very important for the improvement and modification of its structure.Quinoline is a common and widely used nitrogen-containing heterocyclic molecule.Applications of the phosphorus-containing quinoline molecular structure,a potential chiral P-N ligand similar to QUINAP can be designed.In addition to the traditional methods for preparing quinoline,many new methods using transition metal,Lewis acid or metal-free catalysis have been developed in recent years,but many of these methods have the disadvantages of high cost,difficulty in removing catalyst residues,and poor functional group tolerance.Therefore,its application has limitations.Recently a new mothod of A~3 reaction was developed,it is the amine,alkyne and aldehyde three-molecule in one-pot for preparing quinoline,has the characteristics of strong functional group tolerance,low cost,and suitable for a variety of systems,so it has become one of the research hotspots in the recent years to prepare quinoline.based on this,a mild and convenient method for preparing QUINAP-type P-N ligands by A~3 reaction was developed in this paper.The content of this paper includes the following two parts:In the first chapter,a systematic review of the synthetic quinoline methods developed in recent years is given.These include traditional methods of synthesizing quinoline,and synthesis of quinoline catalyzed by transition metals,Lewis acids or metal-free.It focuses on the preparation of quinoline by parorov reaction and A~3reaction.The second chapter introduces the preparation of QUINAP-type P-N ligand and its application in asymmetric synthesis.On this basis,a method for preparing new QUINAP ligands containing quinoline ring by A~3 reaction was developed.In this method,phosphorus-containing benzaldehyde derivatives are used as phosphorus sources to react with amines to form imines,and then to cyclize with alkynes to form a series of QUINAP molecules containing quinoline structures.