Why do Electron-Deficient Dienes React Rapidly in Diels−Alder Reactions with Electron-Deficient Ethylenes? A Density Functional Theory Analysis
✍ Scribed by Luis R. Domingo
- Publisher
- John Wiley and Sons
- Year
- 2004
- Tongue
- English
- Weight
- 137 KB
- Volume
- 2004
- Category
- Article
- ISSN
- 1434-193X
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✦ Synopsis
Abstract
The Diels−Alder reaction of the electron‐deficient (ED) dimethyl 2,3‐dimethylenesuccinate with two electron‐rich (ER) and two ED ethylenes has been studied at the B3LYP/6‐31G* level of theory. The analysis of the geometry and electronic structure of the transition state of the reaction with the ED dimethyl 2‐methylenemalonate along with the analysis of the global and local electrophilicity indices of the reagents provide an explanation of the participation of this ED diene as nucleophile against powerful electrophiles in polar Diels−Alder reactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)