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Understanding the Reactivity of Trimethylsilyldiazoalkanes Participating in [3+2] Cycloaddition Reactions towards Diethylfumarate with a Molecular Electron Density Theory Perspective

1
Department of Organic Chemistry, University of Valencia, Dr. Moliner 50, Burjassot, E-46100 Valencia, Spain
2
Department of Chemistry, Durgapur Government College, Durgapur 713214, West Bengal, India
3
Department of Chemistry, University of Zakho, Duhok 42001, Iraq
*
Authors to whom correspondence should be addressed.
Received: 29 August 2020 / Revised: 22 September 2020 / Accepted: 4 October 2020 / Published: 16 October 2020
(This article belongs to the Special Issue Cycloaddition Reaction in Organic Synthesis)
A Molecular Electron Density Theory (MEDT) study is presented here for [3+2] cycloaddition (32CA) reactions of three trimethylsilyldiazoalkanes with diethyl fumarate. The presence of silicon bonded to the carbon of these silyldiazoalkanes changes its structure and reactivity from a pseudomonoradical to that of a zwitterionic one. A one-step mechanism is predicted for these polar zw-type 32CA reactions with activation enthalpies in CCl4 between 8.0 and 19.7 kcal·mol−1 at the MPWB1K (PCM)/6-311G(d,p) level of theory. The negative reaction Gibbs energies between −3.1 and −13.2 kcal·mole−1 in CCl4 suggests exergonic character, making the reactions irreversible. Analysis of the sequential changes in the bonding pattern along the reaction paths characterizes these zw-type 32CA reactions. The increase in nucleophilic character of the trimethylsilyldiazoalkanes makes these 32CA reactions more polar. Consequently, the activation enthalpies are decreased and the TSs require less energy cost. Non-covalent interactions at the TSs account for the stereoselectivity found in these 32CA reactions involving the bulky trimethylsilyl group. View Full-Text
Keywords: molecular electron density theory; trimethylsilyldiazoalkanes; [3+2] cycloaddition reactions; electron localization function molecular electron density theory; trimethylsilyldiazoalkanes; [3+2] cycloaddition reactions; electron localization function
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MDPI and ACS Style

Domingo, L.R.; Acharjee, N.; Mohammad-Salim, H.A. Understanding the Reactivity of Trimethylsilyldiazoalkanes Participating in [3+2] Cycloaddition Reactions towards Diethylfumarate with a Molecular Electron Density Theory Perspective. Organics 2020, 1, 3-18. https://0-doi-org.brum.beds.ac.uk/10.3390/org1010002

AMA Style

Domingo LR, Acharjee N, Mohammad-Salim HA. Understanding the Reactivity of Trimethylsilyldiazoalkanes Participating in [3+2] Cycloaddition Reactions towards Diethylfumarate with a Molecular Electron Density Theory Perspective. Organics. 2020; 1(1):3-18. https://0-doi-org.brum.beds.ac.uk/10.3390/org1010002

Chicago/Turabian Style

Domingo, Luis R., Nivedita Acharjee, and Haydar A. Mohammad-Salim 2020. "Understanding the Reactivity of Trimethylsilyldiazoalkanes Participating in [3+2] Cycloaddition Reactions towards Diethylfumarate with a Molecular Electron Density Theory Perspective" Organics 1, no. 1: 3-18. https://0-doi-org.brum.beds.ac.uk/10.3390/org1010002

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