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Molecules 2017, 22(8), 1371; doi:10.3390/molecules22081371

BET & ELF Quantum Topological Analysis of Neutral 2-Aza-Cope Rearrangement of γ-Alkenyl Nitrones

1
Instituto de Biocomputación y Física de Sistemas Complejos (BIFI), Universidad de Zaragoza, Zaragoza, 50009 Aragón, Spain
2
Dipartimento di Scienze del Farmaco, Università di Catania, 95124 Catania, Italy
3
Dipartimento di Chimica, Università di Pavia, Via Taramelli 12, 27100 Pavia, Italy
4
Instituto de Síntesis Química y Catalisis Homogénea (ISQCH), Universidad de Zaragoza-CSIC, Zaragoza, 50009 Aragón, Spain
*
Author to whom correspondence should be addressed.
Received: 6 August 2017 / Revised: 15 August 2017 / Accepted: 18 August 2017 / Published: 19 August 2017
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Abstract

The 2-Aza-Cope rearrangement of γ-alkenyl nitrones is a rare example of the neutral thermal 2-aza-Cope process that usually takes place with cationic species. During the rearrangement, a redistribution of bonds and electronic density occurs in one kinetic step. However, the introduction of substituents with different steric requirements and electronic features might alter the activation energies and the synchronicity of the reaction. The electron localization function (ELF) analysis and its application to Bonding Evolution Theory (BET) analysis within the context of Molecular Electron Density Theory (MEDT) is an excellent tool to monitor the electron density along the reaction coordinate and thus investigate in detail bond breaking and formation and the corresponding energy barriers. By analyzing topological ELF calculations of seventeen 2-aza-Cope nitrone rearrangements with selected substituents, the main factors influencing the synchronicity of the process were investigated. This MEDT study results revealed that the rearrangement is a non-polar process mostly influenced by steric factors rather than by electronic ones, and confirms the pseudoradical character of the process rather than any pericyclic electron-reorganization. View Full-Text
Keywords: nitrones; 2-aza-Cope rearrangement; MEDT, ELF analysis; BET analysis nitrones; 2-aza-Cope rearrangement; MEDT, ELF analysis; BET analysis
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Merino, P.; Chiacchio, M.A.; Legnani, L.; Tejero, T. BET & ELF Quantum Topological Analysis of Neutral 2-Aza-Cope Rearrangement of γ-Alkenyl Nitrones. Molecules 2017, 22, 1371.

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