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Issue 48, 2014
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Understanding the mechanism of the Povarov reaction. A DFT study

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Abstract

The molecular mechanism of the Povarov reaction in acetonitrile has been studied at the MPWB1K/6-311G** level of theory. This reaction follows a domino process that comprises two sequential reactions: (i) a Lewis acid catalysed aza-Diels–Alder (A-DA) reaction between a N-aryl imine and a nucleophilic ethylene yielding a formal [4 + 2] cycloadduct; (ii) a stepwise 1,3-hydrogen shift at this intermediate affording the final tetrahydroquinoline. At this computational level, the Lewis acid catalysed A-DA reaction presents a two-step mechanism as a consequence of the large stabilisation of the corresponding zwitterionic intermediate. Our study allows establishing that the N-aryl substituent has no remarkable incidence in the activation energy, but the presence of a second C-aryl substituent has a relevant role in the reaction rate. Analysis of the DFT-based reactivity indices of the reagents provides further explanation of the behaviours of the mechanism of the A-DA reaction involved in the Povarov reaction.

Graphical abstract: Understanding the mechanism of the Povarov reaction. A DFT study

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Publication details

The article was received on 02 Apr 2014, accepted on 28 May 2014 and first published on 29 May 2014


Article type: Paper
DOI: 10.1039/C4RA02916J
Citation: RSC Adv., 2014,4, 25268-25278
  • Open access: Creative Commons BY license
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    Understanding the mechanism of the Povarov reaction. A DFT study

    L. R. Domingo, M. J. Aurell, J. A. Sáez and S. M. Mekelleche, RSC Adv., 2014, 4, 25268
    DOI: 10.1039/C4RA02916J

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