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Article

Unveiling the Unexpected Reactivity of Electrophilic Diazoalkanes in [3+2] Cycloaddition Reactions within Molecular Electron Density Theory

1
Department of Organic Chemistry, University of Valencia, Dr. Moliner 50, Burjassot, 46100 Valencia, Spain
2
Department of Chemistry, Durgapur Government College, J. N. Avenue, Durgapur, West Bengal 713214, India
*
Author to whom correspondence should be addressed.
Chemistry 2021, 3(1), 74-93; https://doi.org/10.3390/chemistry3010006
Received: 14 December 2020 / Revised: 31 December 2020 / Accepted: 7 January 2021 / Published: 10 January 2021
(This article belongs to the Special Issue 2020 Profile Papers by Chemistry' Editorial Board Members)
The [3+2] cycloaddition (32CA) reactions of strongly nucleophilic norbornadiene (NBD), with simplest diazoalkane (DAA) and three DAAs of increased electrophilicity, have been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G (d,p) computational level. These pmr-type 32CA reactions follow an asynchronous one-step mechanism with activation enthalpies ranging from 17.7 to 27.9 kcal·mol−1 in acetonitrile. The high exergonic character of these reactions makes them irreversible. The presence of electron-withdrawing (EW) substituents in the DAA increases the activation enthalpies, in complete agreement with the experimental slowing-down of the reactions, but contrary to the Conceptual DFT prediction. Despite the nucleophilic and electrophilic character of the reagents, the global electron density transfer at the TSs indicates rather non-polar 32CA reactions. The present MEDT study establishes the depopulation of the N–N–C core in this series of DAAs with the increase of the EW character of the substituents present at the carbon center is responsible for the experimentally found deceleration. View Full-Text
Keywords: molecular electron density theory; norbornadiene; diazoalkanes; conceptual DFT; electron localization function molecular electron density theory; norbornadiene; diazoalkanes; conceptual DFT; electron localization function
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MDPI and ACS Style

Domingo, L.R.; Ríos-Gutiérrez, M.; Acharjee, N. Unveiling the Unexpected Reactivity of Electrophilic Diazoalkanes in [3+2] Cycloaddition Reactions within Molecular Electron Density Theory. Chemistry 2021, 3, 74-93. https://doi.org/10.3390/chemistry3010006

AMA Style

Domingo LR, Ríos-Gutiérrez M, Acharjee N. Unveiling the Unexpected Reactivity of Electrophilic Diazoalkanes in [3+2] Cycloaddition Reactions within Molecular Electron Density Theory. Chemistry. 2021; 3(1):74-93. https://doi.org/10.3390/chemistry3010006

Chicago/Turabian Style

Domingo, Luis R., Mar Ríos-Gutiérrez, and Nivedita Acharjee. 2021. "Unveiling the Unexpected Reactivity of Electrophilic Diazoalkanes in [3+2] Cycloaddition Reactions within Molecular Electron Density Theory" Chemistry 3, no. 1: 74-93. https://doi.org/10.3390/chemistry3010006

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