Cinchona Alkaloid Catalyzed Asymmetric Allylic Amination Of MBH Carbonates With Isatins And Synthesis Of Novel Bifunctional Chiral Phosphines

This thesis mainly focused on the cinchona alkaloid catalyzed asymmetric allylic amination of MBH carbonates with iastins; synthesis of novel bifunctional chiral phosphines combining chiral binaphthalene scaffold and amino acid containing phosphine and their initial applications in organocatalytic asymmetric reactions.A series of cinchona alkaloid organocatalysts were employed in asymmetric allylic amination of MBH carbonates with isatins. (DHQD)2PHAL was found to be the best organocatalyst, and the corresponding amination products were obtained in moderate to good yields (46-85% yield) and moderate to good enantioselectivities (50-89% ee). The electronic and steric properties of the substituents on the isatins and the aromatic rings of MBH carbonates were examined. To further illustrate the synthetic utility of this reaction, the amination product was selectively hydrogenation, affording the desired reduction product in good yield, diastereoselectivity and enantioselectivity. Moreover, the absolute configuration of product was determined by X-ray diffraction as-S-configuration, and possible mechanism and transition state model were proposed.Novel bifunctional chiral phosphines, which combined chiral dinaphthalene scaffold and amino acid-derived phophine, have been synthesized from N-Boc protected serine ester and their initial applications in the organocatalytic asymmetric reaction have been explored. These chiral phosphine catalysts have shown some catalytic activity in aza-Morita-Baylis-Hillman reaction of MVK and imines, affording the aza-MBH product in excellent yield and moderate enantioselectivity.