Understanding the Origin of the Regioselectivity in Non-Polar [3+2] Cycloaddition Reactions through the Molecular Electron Density Theory

Domingo, Luis R.; Ríos Gutiérrez, Mar; Castellanos Soriano, Jorge

doi:10.3390/org1010003

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Understanding the Origin of the Regioselectivity in Non-Polar [3+2] Cycloaddition Reactions through the Molecular Electron Density Theory

Luis R. Domingo

^1,*

Mar Ríos Gutiérrez

^1,2,*

and

Jorge Castellanos Soriano

Department of Organic Chemistry, University of Valencia, Dr. Moliner 50, Burjassot, 46100 Valencia, Spain

Department of Chemistry and Chemical Biology, McMaster University, 1280 Main Street West, Hamilton, ON L8S 4L8, Canada

Department of Chemistry, Polytechnic University of Valencia, Camí de Vera, s/n, 46022 Valencia, Spain

Authors to whom correspondence should be addressed.

Organics 2020, 1(1), 19-35; https://doi.org/10.3390/org1010003

Received: 5 September 2020 / Revised: 10 November 2020 / Accepted: 10 November 2020 / Published: 13 November 2020

(This article belongs to the Special Issue Cycloaddition Reaction in Organic Synthesis)

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Abstract

The regioselectivity in non-polar [3+2] cycloaddition (32CA) reactions has been studied within the Molecular Electron Density Theory (MEDT) at the B3LYP/6-311G(d,p) level. To this end, the 32CA reactions of nine simplest three-atom-components (TACs) with 2-methylpropene were selected. The electronic structure of the reagents has been characterized through the Electron Localisation Function (ELF) and the Conceptual DFT. The energy profiles of the two regioisomeric reaction paths and ELF topology of the transition state structures are studied to understand the origin of the regioselectivity in these 32CA reactions. This MEDT study permits to conclude that the least electronegative X1 end atom of these TACs controls the asynchronicity in the C−X (X=C, N, O) single bond formation, and consequently, the regioselectivity. This behaviour is a consequence of the fact that the creation of the non-bonding electron density required for the formation of the new single bonds has a lower energy demand at the least electronegative X1 atom than at the Z3 one. View Full-Text

Keywords: non-polar [3+2] cycloaddition reactions; regioselectivity; molecular electron density theory; electronegativity; molecular mechanism

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Domingo, L.R.; Ríos Gutiérrez, M.; Castellanos Soriano, J. Understanding the Origin of the Regioselectivity in Non-Polar [3+2] Cycloaddition Reactions through the Molecular Electron Density Theory. Organics 2020, 1, 19-35. https://doi.org/10.3390/org1010003

AMA Style

Domingo LR, Ríos Gutiérrez M, Castellanos Soriano J. Understanding the Origin of the Regioselectivity in Non-Polar [3+2] Cycloaddition Reactions through the Molecular Electron Density Theory. Organics. 2020; 1(1):19-35. https://doi.org/10.3390/org1010003

Chicago/Turabian Style

Domingo, Luis R., Mar Ríos Gutiérrez, and Jorge Castellanos Soriano. 2020. "Understanding the Origin of the Regioselectivity in Non-Polar [3+2] Cycloaddition Reactions through the Molecular Electron Density Theory" Organics 1, no. 1: 19-35. https://doi.org/10.3390/org1010003

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Understanding the Origin of the Regioselectivity in Non-Polar [3+2] Cycloaddition Reactions through the Molecular Electron Density Theory

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