Origin of the Bürgi-Dunitz Angle

Origin of the Bürgi-Dunitz Angle

The Bürgi-Dunitz (BD) angle plays a pivotal role in organic chemistry to rationalize the nucleophilic addition to carbonyl groups. Yet, the origin of the obtuse trajectory of the nucleophile remains incompletely understood. Herein, we quantify the importance of the underlying physical factors quantum chemically. The obtuse BD angle appears to originate from the concerted action of a reduced Pauli repulsion between the nucleophile HOMO and carbonyl π bond, a more stabilizing HOMO-π*-LUMO(C=O) interaction, as well as a more favorable electrostatic attraction.

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Bibliographic Details
Main Authors: Rodríguez, Humberto A., Bickelhaupt, F. Matthias, Fernández, Israel
Other Authors: Ministerio de Ciencia e Innovación (España)
Format: artículo biblioteca
Language:English
Published: John Wiley & Sons 2023-06-12
Subjects:Bürgi-Dunitz angle, nucleophilic addition, carbonyl, Pauli repulsion, density functional calculations, Protect, restore and promote sustainable use of terrestrial ecosystems, sustainably manage forests, combat desertification, and halt and reverse land degradation and halt biodiversity loss,
Online Access:http://hdl.handle.net/10261/341977
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spelling dig-ipna-es-10261-3419772024-01-09T14:13:49Z Origin of the Bürgi-Dunitz Angle Rodríguez, Humberto A. Bickelhaupt, F. Matthias Fernández, Israel Ministerio de Ciencia e Innovación (España) Agencia Estatal de Investigación (España) Dutch Research Council Bürgi-Dunitz angle nucleophilic addition carbonyl Pauli repulsion density functional calculations Protect, restore and promote sustainable use of terrestrial ecosystems, sustainably manage forests, combat desertification, and halt and reverse land degradation and halt biodiversity loss The Bürgi-Dunitz (BD) angle plays a pivotal role in organic chemistry to rationalize the nucleophilic addition to carbonyl groups. Yet, the origin of the obtuse trajectory of the nucleophile remains incompletely understood. Herein, we quantify the importance of the underlying physical factors quantum chemically. The obtuse BD angle appears to originate from the concerted action of a reduced Pauli repulsion between the nucleophile HOMO and carbonyl π bond, a more stabilizing HOMO-π*-LUMO(C=O) interaction, as well as a more favorable electrostatic attraction. This work was supported by the Spanish MCIN/AEI/10.13039/501100011033 (Grants PID2019-106184GB-I00 and RED2018-102387-T) and the Dutch Research Council (NWO). Peer reviewed 2024-01-09T14:11:56Z 2024-01-09T14:11:56Z 2023-06-12 artículo ChemPhysChem, 24(17), e202300379: 1-6 (2023) 1439-4235 http://hdl.handle.net/10261/341977 10.1002/cphc.202300379 1439-7641 en #PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-106184GB-I00/ES/UNA APROXIMACION DIFERENTE PARA ENTENDER Y CONTROLAR LA CATALISIS/ info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013 -2016/RED2018-102387-T Publisher's version https://doi.org/10.1002/cphc.202300379 Sí open John Wiley & Sons
institution IPNA ES
collection DSpace
country España
countrycode ES
component Bibliográfico
access En linea
databasecode dig-ipna-es
tag biblioteca
region Europa del Sur
libraryname Biblioteca del IPNA España
language English
topic Bürgi-Dunitz angle
nucleophilic addition
carbonyl
Pauli repulsion
density functional calculations
Protect, restore and promote sustainable use of terrestrial ecosystems, sustainably manage forests, combat desertification, and halt and reverse land degradation and halt biodiversity loss
Bürgi-Dunitz angle
nucleophilic addition
carbonyl
Pauli repulsion
density functional calculations
Protect, restore and promote sustainable use of terrestrial ecosystems, sustainably manage forests, combat desertification, and halt and reverse land degradation and halt biodiversity loss
spellingShingle Bürgi-Dunitz angle
nucleophilic addition
carbonyl
Pauli repulsion
density functional calculations
Protect, restore and promote sustainable use of terrestrial ecosystems, sustainably manage forests, combat desertification, and halt and reverse land degradation and halt biodiversity loss
Bürgi-Dunitz angle
nucleophilic addition
carbonyl
Pauli repulsion
density functional calculations
Protect, restore and promote sustainable use of terrestrial ecosystems, sustainably manage forests, combat desertification, and halt and reverse land degradation and halt biodiversity loss
Rodríguez, Humberto A.
Bickelhaupt, F. Matthias
Fernández, Israel
Origin of the Bürgi-Dunitz Angle
description The Bürgi-Dunitz (BD) angle plays a pivotal role in organic chemistry to rationalize the nucleophilic addition to carbonyl groups. Yet, the origin of the obtuse trajectory of the nucleophile remains incompletely understood. Herein, we quantify the importance of the underlying physical factors quantum chemically. The obtuse BD angle appears to originate from the concerted action of a reduced Pauli repulsion between the nucleophile HOMO and carbonyl π bond, a more stabilizing HOMO-π*-LUMO(C=O) interaction, as well as a more favorable electrostatic attraction.
author2 Ministerio de Ciencia e Innovación (España)
author_facet Ministerio de Ciencia e Innovación (España)
Rodríguez, Humberto A.
Bickelhaupt, F. Matthias
Fernández, Israel
format artículo
topic_facet Bürgi-Dunitz angle
nucleophilic addition
carbonyl
Pauli repulsion
density functional calculations
Protect, restore and promote sustainable use of terrestrial ecosystems, sustainably manage forests, combat desertification, and halt and reverse land degradation and halt biodiversity loss
author Rodríguez, Humberto A.
Bickelhaupt, F. Matthias
Fernández, Israel
author_sort Rodríguez, Humberto A.
title Origin of the Bürgi-Dunitz Angle
title_short Origin of the Bürgi-Dunitz Angle
title_full Origin of the Bürgi-Dunitz Angle
title_fullStr Origin of the Bürgi-Dunitz Angle
title_full_unstemmed Origin of the Bürgi-Dunitz Angle
title_sort origin of the bürgi-dunitz angle
publisher John Wiley & Sons
publishDate 2023-06-12
url http://hdl.handle.net/10261/341977
work_keys_str_mv AT rodriguezhumbertoa originoftheburgidunitzangle
AT bickelhauptfmatthias originoftheburgidunitzangle
AT fernandezisrael originoftheburgidunitzangle
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