ABSTRACT CTS-9708227, Seton Hall University Prof. Augustine is being funded by the Chemical Reactions Program (Kinetics and Catalysis) to continue his prior work on enantioselective heterogeneous catalysis (NSF grant 9312533) in two directions: develop more general chiral modifiers for supported metal catalysts, and support chiral homogeneous complex catalysts. The modifier to be developed is based on amine derivatives of naphthyl binaphtol acetal, and so provide binding groups and molecular orientation to favor enantiomeric resolution for the hydrogenation of alpha-methyl butenoic acid. For the second part of the project, phosphotungstic heteropolyacid anions will be loaded on a modified support (clay), or included during sol-gel synthesis of another oxide. Support modifiers will be vanadyl alkoxide, titanium tetraethoxide or aluminum isopropoxide. The oxide-heteropolyacid combination will be used as support for a chiral metal complex such as RhDIPAMP. Preparative variables will be studied in detail. The hydrogenation of prochiral acrylates will be used as test reaction for activity and enantioselectivity. The expectation is that the electronic effects introduced by heteropolyacids can be used to fine-tune the activity and selectivity of the chiral modifier. Spectroscopy (UV, VIS, IR, XPS, 31P, 13C, and 1H MAS NMR) will be used for catalysts characterization. The research will have major significance in the pharmaceutical and agrochemical industries.
