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Origin of asynchronicity in Diels–Alder reactions

Asynchronicity in Diels–Alder reactions plays a crucial role in determining the height of the reaction barrier. Currently, the origin of asynchronicity is ascribed to the stronger orbital interaction between the diene and the terminal carbon of an asymmetric dienophile, which shortens the correspond...

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Autores principales: Vermeeren, Pascal, Hamlin, Trevor A., Bickelhaupt, F. Matthias
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8457343/
https://www.ncbi.nlm.nih.gov/pubmed/34499069
http://dx.doi.org/10.1039/d1cp02456f
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author Vermeeren, Pascal
Hamlin, Trevor A.
Bickelhaupt, F. Matthias
author_facet Vermeeren, Pascal
Hamlin, Trevor A.
Bickelhaupt, F. Matthias
author_sort Vermeeren, Pascal
collection PubMed
description Asynchronicity in Diels–Alder reactions plays a crucial role in determining the height of the reaction barrier. Currently, the origin of asynchronicity is ascribed to the stronger orbital interaction between the diene and the terminal carbon of an asymmetric dienophile, which shortens the corresponding newly formed C–C bond and hence induces asynchronicity in the reaction. Here, we show, using the activation strain model and Kohn–Sham molecular orbital theory at ZORA-BP86/TZ2P, that this rationale behind asynchronicity is incorrect. We, in fact, found that following a more asynchronous reaction mode costs favorable HOMO–LUMO orbital overlap and, therefore, weakens (not strengthens) these orbital interactions. Instead, it is the Pauli repulsion that induces asynchronicity in Diels–Alder reactions. An asynchronous reaction pathway also lowers repulsive occupied–occupied orbital overlap which, therefore, reduces the unfavorable Pauli repulsion. As soon as this mechanism of reducing Pauli repulsion dominates, the reaction begins to deviate from synchronicity and adopts an asynchronous mode. The eventual degree of asynchronicity, as observed in the transition state of a Diels–Alder reaction, is ultimately achieved when the gain in stability, as a response to the reduced Pauli repulsion, balances with the loss of favorable orbital interactions.
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spelling pubmed-84573432021-10-18 Origin of asynchronicity in Diels–Alder reactions Vermeeren, Pascal Hamlin, Trevor A. Bickelhaupt, F. Matthias Phys Chem Chem Phys Chemistry Asynchronicity in Diels–Alder reactions plays a crucial role in determining the height of the reaction barrier. Currently, the origin of asynchronicity is ascribed to the stronger orbital interaction between the diene and the terminal carbon of an asymmetric dienophile, which shortens the corresponding newly formed C–C bond and hence induces asynchronicity in the reaction. Here, we show, using the activation strain model and Kohn–Sham molecular orbital theory at ZORA-BP86/TZ2P, that this rationale behind asynchronicity is incorrect. We, in fact, found that following a more asynchronous reaction mode costs favorable HOMO–LUMO orbital overlap and, therefore, weakens (not strengthens) these orbital interactions. Instead, it is the Pauli repulsion that induces asynchronicity in Diels–Alder reactions. An asynchronous reaction pathway also lowers repulsive occupied–occupied orbital overlap which, therefore, reduces the unfavorable Pauli repulsion. As soon as this mechanism of reducing Pauli repulsion dominates, the reaction begins to deviate from synchronicity and adopts an asynchronous mode. The eventual degree of asynchronicity, as observed in the transition state of a Diels–Alder reaction, is ultimately achieved when the gain in stability, as a response to the reduced Pauli repulsion, balances with the loss of favorable orbital interactions. The Royal Society of Chemistry 2021-09-03 /pmc/articles/PMC8457343/ /pubmed/34499069 http://dx.doi.org/10.1039/d1cp02456f Text en This journal is © the Owner Societies https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Vermeeren, Pascal
Hamlin, Trevor A.
Bickelhaupt, F. Matthias
Origin of asynchronicity in Diels–Alder reactions
title Origin of asynchronicity in Diels–Alder reactions
title_full Origin of asynchronicity in Diels–Alder reactions
title_fullStr Origin of asynchronicity in Diels–Alder reactions
title_full_unstemmed Origin of asynchronicity in Diels–Alder reactions
title_short Origin of asynchronicity in Diels–Alder reactions
title_sort origin of asynchronicity in diels–alder reactions
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8457343/
https://www.ncbi.nlm.nih.gov/pubmed/34499069
http://dx.doi.org/10.1039/d1cp02456f
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