Application Of Chiral Phosphonium Salts Ion Pairs Derived From ?-amino Acids In Asymmetric Michael Addition

Asymmetric Michael reaction and double Michael reaction cascade cyclization catalyzed by amino acids or dipeptide-derived chiral organophosphinium ion pairs have been achieved.And,the combination of dipeptide-derived chiral quaternary phosphonium salt phase transfer catalyst and silver catalyst for a "one pot" Michael addition and cyclization reaction also have been realized.This dissertation consists of four chapters as below:(1)The concept,classification,development and applications in asymmetric catalysis of asymmetric ion-pairing catalysis were briefly reviewed.And chiral quaternary ammonium,phosphonium and tertiary sulfonium cation-directed catalysis and chiral anion-directed catalysis were elaborately introduced.(2)Double Michael addition cascade cyclization reactions of 2-substituted malonates and double Michael receptors catalyzed by dipeptide-derived chiral multiple functional quaternary phosphonium salt were developed,which provided chiral cyclopentane,cyclohexane and tetrahydropyran derivatives with three trans,cis contiguous stereo genic centers in moderate to excellent yields(up to 98%),diastereoselectivities(up to>20:1)and enantioselectivities(up to 94%ee).And the reaction mechanism was preliminarily explored by the control experiments.(3)A catalytic system of combination of chiral phase transfer catalyst and the transition metal catalyst have been developed.Asymmetric sequential cyclizations via intermolecular Michael addition/intramolecular Conia-ene reaction by combining dipeptide-derived multifunctional quaternary phosphonium salt and silver catalysis have been realized successfully under mild reaction condition,which synthesized a series of chiral methylenecyclopentane derivatives in moderate to excellent yields(up to 97%)and enantioselectivities(up to 93%ee).(4)Asymmetric Michael addition of malonates to ?,?-unsaturated N-acylpyrroles,N-acyl indoles,N-acyl carbazoles and N-acylpyrazoles catalyzed by amino acids and dipeptide-derived chiral quaternary phosphonium salts were developed.An enantioselectivity switch could be realized by adjusting the framework of the catalyst to change the chiral environment and the synergistic effect of multiple hydrogen bonds and substrate,and two enantiomers of the product were obtained with moderate to excellent yields(up to 99%)and good to excellent enantioselectivity(up to 99%ee).Further,a catalytic amount of potassium tert-butoxide was found to highly efficiently promote the above reaction using a simple amino acid-derived chiral quaternary phosphonium salt as a catalyst.finally,the reaction mechanism was preliminarily explored...