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Nobakht Y, Arshadi N. DFT study of the dual catalytic role of L-proline in the aldol reaction and the effect of water on it. J Mol Model. 2018;24(12):334doi: 10.1007/s00894-018-3851-0.
Nobakht, Y., & Arshadi, N. (2018). DFT study of the dual catalytic role of L-proline in the aldol reaction and the effect of water on it. Journal of molecular modeling, 24(12), 334. https://doi.org/10.1007/s00894-018-3851-0
Nobakht, Yasaman, and Arshadi, Nematollah. "DFT study of the dual catalytic role of L-proline in the aldol reaction and the effect of water on it." Journal of molecular modeling vol. 24,12 (2018): 334. doi: https://doi.org/10.1007/s00894-018-3851-0
Nobakht Y, Arshadi N. DFT study of the dual catalytic role of L-proline in the aldol reaction and the effect of water on it. J Mol Model. 2018 Nov 06;24(12):334. doi: 10.1007/s00894-018-3851-0. PMID: 30402658.
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J Mol Model. 2018 Nov 06;24(12):334. doi: 10.1007/s00894-018-3851-0.

DFT study of the dual catalytic role of L-proline in the aldol reaction and the effect of water on it.

Journal of molecular modeling

Yasaman Nobakht, Nematollah Arshadi

Affiliations

  1. Department of Chemistry, Faculty of Sciences, University of Zanjan, Zanjan, Iran.
  2. Department of Chemistry, Faculty of Sciences, University of Zanjan, Zanjan, Iran. [email protected].

PMID: 30402658 DOI: 10.1007/s00894-018-3851-0

Abstract

The aldol reaction in the presence of L-proline acting as an organocatalyst is a well-known example of asymmetric synthesis. Many theoretical and experimental studies have been carried out to probe the mechanism of this reaction. In this work, two levels of density functional theory in the gas phase and DMSO were used to elucidate the best pathways for this reaction, with the enamine and enol considered intermediates and L-proline considered either a reactant or a facilitator. The calculations indicated that both intermediates are formed simultaneously in the reaction medium. Interestingly, the formation of the enamine intermediate predominates in DMSO at room temperature, whereas the enol becomes the predominant intermediate upon the addition of water. Graphical Abstract The dual role of L-proline leads to single stereoisomeric aldol product via two completely different pathways.

Keywords: Aldol reaction; DFT calculations; L-Proline; Organocatalysis; Reaction mechanism

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