Research Of Asymmetric Reactions Catalyzed By Chiral Bisphosphorylimides

Chiral bisphosphorylimides is one of novel Br?nsted acid catalysts, can be used to catalyze a variety of reactions, for example, asymmetric oxidation reaction,Friedel-Crafts reaction, Mannich reaction, Michael addition reaction, etc..Chiral Phosphorus Imide can reduce the reaction time and even the dosage of it. The field of chiral bisphosphorylimides catalysts is relatively new but full of potential. In this paper we studied Friedel-Crafts reaction of indole with isatin and Kabachnik-Fields reaction catalyzed by biaxial chiral phosphorus imides, and good results have been achieved. The specific content of the experiment and the experimental results are as follows:In this paper, we introduce the Friedel-Crafts reaction of indole with isatin,generated by which asymmetric products can be applied to the field of biology and medicine. Under this background, we apply four different phosphoric acids and four different chiral bisphosphorylimides to the asymmetric Friedel-Crafts reaction of indoles with isatins, and screen out the most excellent catalyst, then the reaction conditions is optimized, Finally, the optimal reaction condition was obtained, at ambient temperature under 20 o C, with 1,4-dioxane as solvent,3,3’-3,5-bitrifluoromethylphenyl-substituted H8-BINOL bisphosphorylimides as catalyst. Under the optimal condition, we extended 19 different structures of reaction examples. The yield of products is to 92%, and the enantioselectivity is up to 99%.That shows that chiral bisphosphorylimides can be an effective catalyst of catalytic asymmetric Friedel- Crafts reaction of Indole with isatin.To more fully studing on the results of chiral bisphosphorylimides catalyst application in different reactions, we apply six different chiral bisphosphorylimidesto Kabachnik-Fields reaction, benzaldehyde, p-methoxyaniline and diethyl phosphite as substrate. After the catalyst, solvent, additive and temperature screened we get the catalytic product. The best results have been obtained, when we use3,3’-3,5-bitrifluoromethylphenyl-substituted H8-BINOL bisphosphorylimides as catalyst, m-xylene as solvent, anhydrous magnesium sulfate as the additive in 50 o C,the yield in 96%,ee is up to 83%. The study shows that the catalysts in catalytic kabachnik- fields reaction also has high research value.In short, chiral bisphosphorylimides is relatively new but full of potential,performance out better chirality control effect, limited loadings, higher activity and higher yield characteristics, both in Friedel-Crafts reaction of indoles with isatins and Kabachnik-Fields reaction have shown excellent results,...