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A bonding evolution analysis for the thermal Claisen rearrangement: an experimental and theoretical exercise for testing the electron density flow

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Abstract

A comprehensive theoretical investigation of the thermal Claisen rearrangement of allyl vinyl ether (AVE) to allylacetaldehyde has been carried out. We present the use of the electron localization function (ELF) to monitor the bonding evolution aspects in the course of this thermal rearrangement and the results are compared with a photo-impulsive process where instantaneous vibration frequencies are monitored [I. Iwakura, Phys. Chem. Chem. Phys., 2011, 12, 5546–5555]. Our results reveal an asynchronous electron density rearrangement inasmuch that the breaking of the C3–O bond and the formation of C1–C5 do not take place simultaneously. We also demonstrate how the bonding evolution brings about the natural appearance of the curly arrows representing the electronic flow in molecular rearrangements. This holds the key to gaining an unprecedented insight into the mapping of the electron density flow while the bonds change throughout the reaction progress.

Graphical abstract: A bonding evolution analysis for the thermal Claisen rearrangement: an experimental and theoretical exercise for testing the electron density flow

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Publication details

The article was received on 08 Nov 2017, accepted on 30 Nov 2017 and first published on 30 Nov 2017


Article type: Paper
DOI: 10.1039/C7CP07557J
Citation: Phys. Chem. Chem. Phys., 2018, Advance Article
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    A bonding evolution analysis for the thermal Claisen rearrangement: an experimental and theoretical exercise for testing the electron density flow

    P. González-Navarrete, J. Andrés and V. S. Safont, Phys. Chem. Chem. Phys., 2018, Advance Article , DOI: 10.1039/C7CP07557J

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