Abstract
Cinchonidine, a naturally occurring cinchona alkaloid, was tethered to a high-surface-area silica substrate in order to create a new solid chiral catalyst. Two synthetic routes were explored for this grafting, relying on the use of an intermediate linker and so-called “click” chemistry. Both routes proved viable, but the procedure where cinchonidine is first derivatized with 3-isocyanatopropyltriethoxysilane (ICPTEOS) at the alcohol position and the resulting product then anchored to the silica surface was deemed the most efficient. Bonding to the surface occurs via the formation of Si–O–Si bonds, on average two out of the three possible per cinchonidine, and takes place preferentially at silica surface sites with two geminal hydroxyl groups on the same silicon atom. Approximately 10% of the available OH surface groups are derivatized in this procedure. The resulting catalyst was successfully tested for the addition of aromatic thiols to unsaturated ketones, a reaction promoted by amines (the tertiary quinuclidine nitrogen atom in the case of cinchonidine). The activity of the supported cinchonidine proved comparable to that of the free molecule, but tethering does lead to a significant loss in enantioselectivity.
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Acknowledgements
Funds for this research were provided by a grant from the US Department of Energy. We also thank Dr. Dan Borchardt and the UCR Analytical Chemistry Instrumentation Facility (ACIF) for help with the acquisition of the solid-state NMR data. The NMR spectrometer used for those experiments was purchased with funds from grants from the US National Science Foundation (NSF CHE-0541848) and the US National Institute of Health (NIH S10RR023677).
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Hong, J., Lee, I. & Zaera, F. Cinchona Alkaloids Tethered on Porous Silica as Enantioselective Heterogeneous Catalysts. Top Catal 54, 1340–1347 (2011). https://doi.org/10.1007/s11244-011-9760-4
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DOI: https://doi.org/10.1007/s11244-011-9760-4