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

Chemical Sciences

Complutense University
Consejo Superior de Investigaciones Científicas (CSIC)
Vrije Universiteit Amsterdam
Radboud University Nijmegen

Research output: Contribution to journal › Article › peer-review

25 Citations (Scopus)

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
Journal	ChemPhysChem
Volume	24
Issue number	17
DOIs	https://doi.org/10.1002/cphc.202300379
Publication status	Published - 1 Sept 2023

Keywords

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

ASJC Scopus subject areas

Atomic and Molecular Physics, and Optics
Physical and Theoretical Chemistry

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10.1002/cphc.202300379

Cite this

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abstract = "The B{\"u}rgi-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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AU - Bickelhaupt, F. Matthias

AU - Fernández, Israel

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AB - 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.

KW - Bürgi-Dunitz angle

KW - Pauli repulsion

KW - carbonyl

KW - density functional calculations

KW - nucleophilic addition

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ER -

Origin of the Bürgi-Dunitz Angle

Abstract

Keywords

ASJC Scopus subject areas

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