Issue 48, 2014

Understanding the mechanism of the Povarov reaction. A DFT study

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

Supplementary files

Article information

Article type
Paper
Submitted
02 Apr 2014
Accepted
28 May 2014
First published
29 May 2014
This article is Open Access
Creative Commons BY license

RSC Adv., 2014,4, 25268-25278

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

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements