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Understanding the Regioselectivity and the Molecular Mechanism of [3 + 2] Cycloaddition Reactions between Nitrous

Ewa Dresler¹, Aneta Wróblewska², Radomir Jasiński³

¹Łukasiewicz Research Network, Institute of Heavy Organic Synthesis "Blachownia", Energetyków 9, 47-225 Kędzierzyn-Koźle, Poland.

Molecules (Basel, Switzerland)

|December 11, 2022

Abstract:

Regiochemical aspects and the molecular mechanism of the [3 + 2] cycloaddition between nitrous oxide and conjugated nitroalkenes were evaluated on the basis of the wb97xd/6-311 + G(d) (PCM) computational study. It was found that, independently of the nature of the nitroalkene, all considered processes are realized via polar, single-step mechanisms. All attempts at the localization of hypothetical zwitterionic intermediates were unsuccessful. Additionally, the DFT computational study suggested that, in the course of the reaction, the formation of respective Δ²-4-nitro-4-R₁-5-R₂-1-oxa-2,3-diazolines was preferred from the kinetic point of view.

Keywords:

[3 + 2] cycloaddition conceptual density functional theory molecular electron density theory molecular mechanism nitroalkenes nitrous oxide

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