Synthesis Of Titanium Phosphonate-Supported Primary-Amine Catalysts Derived From Cinchona Alkaloid And Their Application In Asymmetric Aldol Reaction

In this thesis, a series of organic phosphonates were synthesized by using cinchonidine as starting material by several steps:Mistunobu, free radical addition and hydrolysis reaction. By the precipitation reaction of various organic phosphonates with Ti(O/Pr)4, titanium phosphonate-supported9-amino-9-deoxy-epi-cinchonidine catalysts were prepared.The chemical compositions and structures of titanium phosphonate-supported primary amine catalysts were characterized by NMR, TG, IR, XPRD,TEM, SEM and N2adsorption-desorption analysis.These titanium phosphonate-supported primary amine catalysts6a-c were applied in model asymmetric Aldol reaction of nitrobenzaldehyde with cyclohexanone. The catalytic conditions such as amount of catalyst, solvent, temperature and reaction time were screened out in details. Under the optimal catalytic conditions, the result of the reaction of cyclohexanone with aromatic aldehyde in15-98%yield,76-98%ee anti and74/26-98/2Dr(anti/syn) were obtained at20℃for72h in water (1mL) by using7.5wt%catalyst6b1(S/C=13.3) and TfOH (15mol%). The supported catalyst was recycled for at least five times without the sharp loss of the catalytic activities.The fresh titanium phosphonate-supported primary amine could be reconstructed by terms of reassembly after using six times. Catalytic performance has not been satisfactory results.