How effectively bonding evolution theory retrieves and visualizes curly arrows: The cycloaddition reaction of cyclic nitrones
In the present work, the electron density flows involved throughout the progress of the four reaction pathways associated with the intramolecular [3 + 2] cycloaddition of cyclic nitrones Z‐1 and E‐1 are analyzed using the bonding evolution theory. The present study highlights the nonconcerted nature...
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Published in | International journal of quantum chemistry Vol. 119; no. 19 |
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Main Authors | , , , , , , |
Format | Journal Article |
Language | English |
Published |
Hoboken, USA
John Wiley & Sons, Inc
05.10.2019
Wiley Subscription Services, Inc |
Subjects | |
Online Access | Get full text |
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Summary: | In the present work, the electron density flows involved throughout the progress of the four reaction pathways associated with the intramolecular [3 + 2] cycloaddition of cyclic nitrones Z‐1 and E‐1 are analyzed using the bonding evolution theory. The present study highlights the nonconcerted nature of the processes, which can be described as taking place in several stages. The first stage consists in the depopulation of the initial CN and CC double bonds to render the N lone pair and the corresponding CN and CC single bonds, and these electronic flows initiate the reactions. The CC and CO sigma bond formations take place later on, once the transition states have been overcome. Along the bridged pathways, the CC bond formation process precedes the OC bond formation event, although, along the fused paths, the OC bond formation process occurs first and the formation of the CC bond is the last electronic flow to take place. Finally, curly arrow representations accounting for the timing of the electron flows are obtained from the bonding evolution theory results.
A chemical reaction involves the transformation of the electronic structure of the reactants into that of the products, via the corresponding transition state. The bonding evolution theory is capable of describing this transformation by recovering the curly arrows representation and the timing of the electron density flows along the reaction progress. Here, the intramolecular [3 + 2] cycloadditions of cyclic nitrones are selected as case study. |
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Bibliography: | Funding information Fonds De La Recherche Scientifique ‐ FNRS, Grant/Award Numbers: FRFC Convention 2.4.617.07.F, FRFC Convention 2.5020.11; Ministerio de Economía y Competitividad, Grant/Award Number: CTQ2015‐65207‐P; Universitat Jaume I, Grant/Award Number: UJI‐B2016‐25; Université de Namur, Grant/Award Number: UNamur‐CERUNA Mobility Fellowship |
ISSN: | 0020-7608 1097-461X |
DOI: | 10.1002/qua.25985 |