The Strategy’s Design On A Bi-sites Modifications For Kinetic Resolution Of Axially Chiral Scaffolds And Related Reaction Studies

Axially chiral compounds that bear rotationally restricted σ bond are finding more and more important role in many disciplines where molecular asymmetry is influential,which akin to the well-represented point-chiral molecules.Axially chiral biaryl frameworks are ubiquitous in biologically active natural products,drugs,and advanced materials.They also constitute the essential chiral element in a variety of privileged chiral ligands and catalysts within asymmetric catalysis.This puts forward a great demand for the atropselective synthesis of various kinds of molecules.However,the main synthesis methods of axial chiral compounds are limited in the range of substrates,especially in the selective construction of complex molecular biaryl analogues.There is still a need to develop more general,gentle,and tolerant synthesis methods of different substituents.Kinetic resolution strategies provides effective stereoscopic control for the synthesis of biaryl compounds,in addition to the advantage of obtaining two single configuration compounds at the same time.This thesis develops a novel two-site reaction kinetic resolution and,based on this,develops a series of methods for obtaining axial chiral skeletons.Using the magnesium catalytic system,it is easier and more efficient to obtain different enantiopure axial chiral compounds,avoiding the use of transition metal catalysts required harsh conditions to react.Notably,The emergence of new chiral pathways is of great significance for the discovery of various enantiotropic biaryl catalysts or ligands,and the development of biologically active axial chiral compounds.This thesis mainly includes five parts.The first part introduces the research progress of the synthesis of axial chiral compounds,as well as summarizing the main synthesis strategies.The second part by the innovative two-site reaction kinetic resolution strategy,which successfully synthesize axial chiral compounds and series of novel cinchonine-derived ligands.The third part using the same strategy synthesis another series axial chiral compounds by propylene esters.Confirmed that the metal magnesium catalytic system is potential in the kinetic resolution of axial chiral compounds.The fourth part using the metal magnesium catalytic system achieved[4+2] cyclization reaction with propylene esters,which preliminary explored the possibility of synthesis of non-aryl axial chiral compounds.The fifth part is a summary of works and prospect about this research field.