Synthesis Of Chiral Monodentate Phosphorous And Phosphino-Oxazoline Ligands With Spirobiindane Scaffold And Their Applications In Asymmetric Catalytic Reactions

The design and synthesis of effective chiral ligands play important roles in transition-metal catalyzed asymmetric reactions. In this dissertation, series of chiral monodentate phospholane (SITCP), and phosphino-oxazoline (SIPHOX) ligands were designed and synthesized based on the optically pure 1,1′-spirobiindane-7,7′-diol (SPINOL).SITCP ligand has been proven to be efficient for Pd-catalyzed enantioselective allylation of aldehydes with allylic alcohols and their derivatives in good enantioselectivties (83% ee) and excellent anti diastereoselectivities (up to 99:1 dr).SIPHOX are effective ligands in Ir-catalyzed asymmetric hydrogenation of N-arylimines, providing chiral amine with excellent enantioselectivities (up to 93% ee) under ambient pressure. This work again proved the spirobiindane scaffold was an excellent chiral ligands'backbone.Furthermore, electronic effects of chiral monophosphoramidites ligands 4,4′-DiR-SIPHOS were also studied in asymmetric hydrogenation of olefins.