Comparison of Nitroaldol Reaction Mechanisms Using Accurate Ab Initio Calculations

TitleComparison of Nitroaldol Reaction Mechanisms Using Accurate Ab Initio Calculations
Publication TypeJournal Article
Year of Publication2008
AuthorsZorn D, Lin VSY, Pruski M, Gordon MS
Journal TitleJournal of Physical Chemistry A
Volume112
Pages10635-10649
Date Published10/01
Type of ArticleArticle
ISBN Number1089-5639
Accession NumberISI:000260100800025
Keywordsalgorithms, BASIS-SETS, PATHS, silica, system
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.

DOI10.1021/jp805135p
Alternate JournalJ. Phys. Chem. A