Organocatalytic Asymmetric Reaction Of Phosphorus Ylides

In recent years, asymmetric organocatalysis is a rapidly growing field and now has been as the third general approach to the catalytic production of enantiomerically pure organic compounds between the extremes of enzymatic transformations and transition metal catalysis. Particularly, cinchona alkaloid derivatives has been widely used in asymmetric organocatalysis. In additonal, phosphorus ylides as good nucleophiles have previously been shown in organic synthesis to construct the carbon carbon bond skeleton, but the application of phosphorus ylides in asymmetric synthesis is currently limited. This dissertation mainly focuses on asymmetric reaction of phosphorus ylides under the catalysis of cinchona alkaloid derivatives.In the first chapter, we introduce the research of phosphorus ylides and cinchona alkaloid derivatives in asymmetric organocatalysis.In the second chapter, we have provided an organocatalytic Michael-Type addition of phosphorus ylides and α,β-unsaturated ketones using a chiral ion pair catalyst. And the catalyst was easily prepared by mixing9-amino-(9-deoxy)-epi-quinine with L-N-Boc-Proline.At-15℃, the δ-ketoesters were obtained in good yields with excellent enantioselectivities (up to95%ee) in dichloroethane. The absolute configuration of the product was determined to be S by means of an X-ray crystallographic analysis. We also infered the activation mode according to the results of reaction. In the third chapter, we have provided a highly efficient asymmetric allylic substitution of Morita-Baylis-Hillman (MBH) carbonates with phosphorus ylides under the catalysis of a cinchona alkaloid derivative chiral tertiary amine. At room temperature, The chiral3-substituted2,4-functionalized1,4-pentadienes could be obtained with excellent enantioselectivities (up to98%ee) and good yields in dichloromethane. The absolute configuration of the product was determined to be R by means of an X-ray crystallographic analysis. The broad scope and simple operation makes this methodology very practical.