We have developed a catalytic system for MPV reduction based on calix[4]arene ligands and an Al(III) Lewis-acid active site. Solution and solid-state 27Al NMR spectroscopy of the homogeneous catalyst confirms that the calix[4]arene scaffold is effective at rigorously enforcing site-isolation. Molecular insight into the homogeneous catalytic mechanism is achieved by careful and systematic variations in the ligand and substrate structure, kinetic isotope effect, and data from X-ray crystallography and DFT-modeling. Building on these results, we develop a heterogeneous variant of the homogeneous active site, which is shown to be single site in nature. Finally, recent progress in ligand design is demonstrated to enable homogenous and heterogeneous asymmetric MPV reduction catalysts, and these results will also be presented.

Homogeneous and heterogeneous MPV reduction catalysis using Al(III)- Calix[4]arene complexes

243rd National Meeting (2012)

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