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“Cyclopropylidene Effect” in the 1,3-Dipolar Cycloaddition of Nitrones to Alkylidene Cyclopropanes: A Computational Rationalization
[Image: see text] The regioselectivity in the 1,3-dipolar cycloaddition (1,3-DC) between five-membered cyclic nitrone and methylenecyclopropane (MCP) has been studied through density functional theory (DFT) calculations. The computational study of 1,3-DC with different 1-alkyl- (or 1,1-dialkyl)-subs...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2021
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8279640/ https://www.ncbi.nlm.nih.gov/pubmed/33929857 http://dx.doi.org/10.1021/acs.jpca.1c02204 |
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author | Briccolani-Bandini, Lorenzo Pagliai, Marco Cordero, Franca M. Brandi, Alberto Cardini, Gianni |
author_facet | Briccolani-Bandini, Lorenzo Pagliai, Marco Cordero, Franca M. Brandi, Alberto Cardini, Gianni |
author_sort | Briccolani-Bandini, Lorenzo |
collection | PubMed |
description | [Image: see text] The regioselectivity in the 1,3-dipolar cycloaddition (1,3-DC) between five-membered cyclic nitrone and methylenecyclopropane (MCP) has been studied through density functional theory (DFT) calculations. The computational study of 1,3-DC with different 1-alkyl- (or 1,1-dialkyl)-substituted alkenes and the comparison with MCP have evidenced that the electrostatic interaction has a central role in the regioselectivity of the reactions. It has been observed that the electronic effect of the substituent (donor or attractor groups) determines the polarization of the alkene double bond and the reaction mechanism, consequently determining the interaction with nitrones and favoring an orientation between this moiety and the dipolarophile. |
format | Online Article Text |
id | pubmed-8279640 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-82796402021-07-15 “Cyclopropylidene Effect” in the 1,3-Dipolar Cycloaddition of Nitrones to Alkylidene Cyclopropanes: A Computational Rationalization Briccolani-Bandini, Lorenzo Pagliai, Marco Cordero, Franca M. Brandi, Alberto Cardini, Gianni J Phys Chem A [Image: see text] The regioselectivity in the 1,3-dipolar cycloaddition (1,3-DC) between five-membered cyclic nitrone and methylenecyclopropane (MCP) has been studied through density functional theory (DFT) calculations. The computational study of 1,3-DC with different 1-alkyl- (or 1,1-dialkyl)-substituted alkenes and the comparison with MCP have evidenced that the electrostatic interaction has a central role in the regioselectivity of the reactions. It has been observed that the electronic effect of the substituent (donor or attractor groups) determines the polarization of the alkene double bond and the reaction mechanism, consequently determining the interaction with nitrones and favoring an orientation between this moiety and the dipolarophile. American Chemical Society 2021-04-30 2021-05-13 /pmc/articles/PMC8279640/ /pubmed/33929857 http://dx.doi.org/10.1021/acs.jpca.1c02204 Text en © 2021 The Authors. Published by American Chemical Society Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Briccolani-Bandini, Lorenzo Pagliai, Marco Cordero, Franca M. Brandi, Alberto Cardini, Gianni “Cyclopropylidene Effect” in the 1,3-Dipolar Cycloaddition of Nitrones to Alkylidene Cyclopropanes: A Computational Rationalization |
title | “Cyclopropylidene Effect” in the 1,3-Dipolar
Cycloaddition of Nitrones to Alkylidene Cyclopropanes: A Computational
Rationalization |
title_full | “Cyclopropylidene Effect” in the 1,3-Dipolar
Cycloaddition of Nitrones to Alkylidene Cyclopropanes: A Computational
Rationalization |
title_fullStr | “Cyclopropylidene Effect” in the 1,3-Dipolar
Cycloaddition of Nitrones to Alkylidene Cyclopropanes: A Computational
Rationalization |
title_full_unstemmed | “Cyclopropylidene Effect” in the 1,3-Dipolar
Cycloaddition of Nitrones to Alkylidene Cyclopropanes: A Computational
Rationalization |
title_short | “Cyclopropylidene Effect” in the 1,3-Dipolar
Cycloaddition of Nitrones to Alkylidene Cyclopropanes: A Computational
Rationalization |
title_sort | “cyclopropylidene effect” in the 1,3-dipolar
cycloaddition of nitrones to alkylidene cyclopropanes: a computational
rationalization |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8279640/ https://www.ncbi.nlm.nih.gov/pubmed/33929857 http://dx.doi.org/10.1021/acs.jpca.1c02204 |
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