Campus Units

Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Published Version

Publication Date

9-2008

Journal or Book Title

Journal of Physical Chemistry A

Volume

112

Issue

42

First Page

10635

Last Page

10649

DOI

10.1021/jp805135p

Abstract

In the nitroaldol reaction, condensation between a nitroalkane and an aldehyde yields a nitroalcohol that can undergo dehydration to yield a nitroalkene. Amine-functionalized, MCM-41-type mesoporous silica nanosphere (MSN) materials have been shown to selectively catalyze this reaction. Gas-phase reaction paths for the several competing mechanisms for the nitroaldol reaction have been mapped out using second-order perturbation theory (MP2). Improved relative energies were determined using singles and doubles coupled cluster theory with perturbative triples, CCSD(T). The mechanism in the absence of a catalyst was used to provide a baseline against which to assess the impact of the catalyst on both the mechanism and the related energetics. Catalyzed mechanisms can either pass through a nitroalcohol intermediate as in the classical mechanism or an imine intermediate.

Comments

Reprinted (adapted) with permission from Journal of the American Chemical Society 136 (2014): 16951, doi:10.1021/ja508477e. Copyright 2014 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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