The Design And Synthesis Of Chiral (R)-BINOL Diphosphoric Acids Catalysts And CatalyticAsymmetric Reaction

Chiral BINOL-based phosphoric acids are an array of privileged and powerful organocatalysts, which have been successfully demonstrated in varieties of organic transformations, such as catalytic enantioselective Mannich, Friedel-Crafts reactions, hydrogen-transferation, and etc. The prominent feature of the BINOL-phosphoric acid is a bifunctional catalyst, in which the hydroxyl group serves as a Bronsted acid whereas the O-atom in the unsaturated P=O acts as a Bronsted base. Thus the chiral phosphoric acid behaves as a acid-base bifunctional and metal-free chiral catalysts. Based upon these findings, two cases of bisphosphoric acids were developed by research groups of Terada and Gong, respectively, and these are bisphosphoric acids and also showed highly enantioselective catalytic activity in the investigated reactions. In addition, biscarbonyl acids and bissulfonic acids were successfully developed by Maruoka’s group to catalyze a series of asymmetric transformations in high enantioselectivity. Although some Bronsted diacids were successfully demonstrated in some asymmetric reactions, chiral BINOL-based bisphosphoric acids are highly undeveloped. Furthermore, current chiral phosphoric acids and bisphosphoric acids are all based on diester phosphate, no phosphoric acids including phosphamide. This undeveloped feature stirred us to explore some new bisphosphoric acids with phosphamide coined in.In this dissertation, we designed and synthesized five new chiral BINOL-based bisphosphoric acids for the first time, the phosphoric acid contain the phosphamide and ester phosphonate motifs. These bisphosphoric acids were primarily used as chiral organocatalysts to catalyze the enantioselective hydrogen transformation of a series of quinolones. The results indicated that the chiral bisphosphoric acids are active to catalyze the hydrogen transformation in high yield but low enantioselectivity. Therefore, further works on the optimization of the bisphosphoric acids and investigation other reactions are needed in this laboratory.