Substrate inhibition in the heterogeneous catalyzed aldol condensation: A mechanistic study of supported organocatalysts

Date
2012-01-01
Authors
Kandel, Kapil
Althaus, Stacey
Peeraphatdit, Chorthip
Slowing, Igor
Kobayashi, Takeshi
Trewyn, Brian
Pruski, Marek
Slowing, Igor
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Ames Laboratory
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Chemistry
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Ames LaboratoryChemistry
Abstract

In this study, we demonstrate how materials science can be combined with the established methods of organic chemistry to find mechanistic bottlenecks and redesign heterogeneous catalysts for improved performance. By using solid-state NMR, infrared spectroscopy, surface and kinetic analysis, we prove the existence of a substrate inhibition in the aldol condensation catalyzed by heterogeneous amines. We show that modifying the structure of the supported amines according to the proposed mechanism dramatically enhances the activity of the heterogeneous catalyst. We also provide evidence that the reaction benefits significantly from the surface chemistry of the silica support, which plays the role of a co-catalyst, giving activities up to two orders of magnitude larger than those of homogeneous amines. This study confirms that the optimization of a heterogeneous catalyst depends as much on obtaining organic mechanistic information as it does on controlling the structure of the support.

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NOTICE: this is the author’s version of a work that was accepted for publication in Journal of Catalysis. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Journal of Catalysis, [291, (2012)] DOI 10.1016/j.jcat.2012.04.005

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