Development of highly efficient asymmetric synthesis process directed for "racemic switch" of the racemic medicines

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The aim of this research is to establish the methodology for i) simple preparation of tricyclic "roofed" 2-oxazolidinones, 2-imidazolidinones and 2-thiazolidinones with conformational rigidity and steric congestion as extremely powerful chiral auxiliaries by catalytic resolution, and ii) excellent asymmetric reactions with bicyclic 2-amino alcohols, 1,2-diamines and 2-aminothiols derived from the above tricyclic compounds and their derivatives, directed for "racemic switch" of the racemic medicines.1.Easy access to highly efficient chiral auxiliaries by kinetic resolutionThe optically active "roofed" 2-oxazolidinones, 2-imidazolidinones and 2-thiazolidinones were readily obtained from kinetic resolution with oxazaborolidine catalysts.2.Application of highly efficient chiral "roofed" ligandsBicyclic "roofed" 2-amino alcohols, 1,2-diamines and 2-aminothiols derived from the corresponding tricyclic compounds have been proven to be good to excellent chiral ligands for following metal-catalyzed asymmetric reactions :(1)Asymmetric borane reduction of ketones with oxazaborolidine-borane system ("2-Aminoalcohol" ligands).(2)Practical synthesis of versatile chiral synthons, 4,5-dialkoxy-2-imidazolidinone ("2-Aminoalcohol" ligands).(3)Ruthenium (II)-catalyzed asymmetric transfer hydrogenation of ketones ("cis-1,2-Diamine" ligands).(4)Pd (II)-catalyzed asymmetric alkylation of allylacetates ("2-Aminothiol" ligands).(5)Cu (II)-catalyzed asymmetric Diels-Alder reaction ("2-Aminothiol" ligands).