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Catalyst Design

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Our group is interested in the design and utilization of new catalyst types.  In one area, we have developed the first general conditions for Rh-catalyzed intermolecular reactions of alkyldiazo compounds.  Ordinarily, intermolecular chemistry of carbenoids from alkyldiazo compounds is precluded by beta-hydride elimination.  Current interests include the development of new classes of Rh-catalysts for enantioselective transformations of alkyldiazo compounds. 

Our group is actively investigation the origin of asymmetric induction in salen-based catalysis.  To this end, we have designed a novel class of metallofoldamers.  We have shown how these macromolecules can provide unusual insight into the conformation of salen-metal complexes and the mechanisms by which they induce asymmetry.

   



Some recent publications in this area

Panne, P.; DeAngelis, A.; Fox, J. M. “Rh-Catalyzed Intermolecular Cyclopropanation with α-Alkyl-α-diazoesters: Catalyst-Dependent Chemo- and Diastereoselectivity” Org Lett. 2008, 10 , 29872989.

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30) DeAngelis, A.; Panne, P.; Yap, G. P. A.; Fox, J. M. “Rh-Catalyzed Formation of Dioxolanes from α-Alkyl Diazoesters: Diastereoselective Cycloadditions of Carbonyl Ylides with Selectivity over β-Hydride Elimination” J. Org. Chem. 2008, 73, 1435-1439.

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Dong, Z.; Yap, G. P. A.; Fox, J. M. “trans-Cyclohexane-1,2-diamine Is a Weak Director of Absolute Helicity in Chiral Nickel-Salen Complexes” J. Am. Chem. Soc. 2007, 129, 11850-11853.

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Panne, P.; Fox, J. M. “Rh-catalyzed Intermolecular Reactions of Alkynes with α-Diazoesters that Possess β-hydrogens: Ligand-based Control over Divergent Pathways” J. Am. Chem. Soc. 2007, 129, 22-23.

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