Origin of the Bürgi-Dunitz Angle

Humberto A. Rodríguez; F. Matthias Bickelhaupt; Israel Fernández

doi:10.1002/cphc.202300379

Origin of the Bürgi-Dunitz Angle

Humberto A. Rodríguez, F. Matthias Bickelhaupt, Israel Fernández^*

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

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.

Original language	English
Article number	e202300379
Pages (from-to)	1-6
Number of pages	6
Journal	ChemPhysChem
Volume	24
Issue number	17
Early online date	12 Jun 2023
DOIs	https://doi.org/10.1002/cphc.202300379
Publication status	Published - 1 Sept 2023

Bibliographical note

Funding Information:
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).

Publisher Copyright:
© 2023 The Authors. ChemPhysChem published by Wiley-VCH GmbH.

Keywords

Bürgi-Dunitz angle
carbonyl
density functional calculations
nucleophilic addition
Pauli repulsion

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AU - Fernández, Israel

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Origin of the Bürgi-Dunitz Angle

Abstract

Bibliographical note

Keywords

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