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.
Saved in:
| Main Authors: | , , |
|---|---|
| Other Authors: | |
| 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 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Summary: | 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. |
|---|