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Open AccessArticle

Application of β-Phosphorylated Nitroethenes in [3+2] Cycloaddition Reactions Involving Benzonitrile N-Oxide in the Light of a DFT Computational Study

Department of Organic Chemistry and Technology, Cracow University of Technology, Warszawska Street, 24, 31-155 Cracow, Poland
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Academic Editor: Pierluca Galloni
Organics 2021, 2(1), 26-37; https://doi.org/10.3390/org2010003
Received: 12 January 2021 / Revised: 3 February 2021 / Accepted: 4 February 2021 / Published: 16 February 2021
(This article belongs to the Special Issue Cycloaddition Reaction in Organic Synthesis)
The regiochemistry of [3+2] cycloaddition (32CA) processes between benzonitrile N-oxide 1 and β-phosphorylated analogues of nitroethenes 2a–c has been studied using the Density Functional Theory (DFT) at the M062X/6-31+G(d) theory level. The obtained results of reactivity indices show that benzonitrile N-oxide 1 can be classified both as a moderate electrophile and moderate nucleophile, while β-phosphorylated analogues of nitroethenes 2a–c can be classified as strong electrophiles and marginal nucleophiles. Moreover, the analysis of CDFT shows that for [3+2] cycloadditions with the participation of β-phosphorylatednitroethene 2a and β-phosphorylated α-cyanonitroethene 2b, the more favored reaction path forms 4-nitro-substituted Δ2-isoxazolines 3a–b, while for a reaction with β-phosphorylated β-cyanonitroethene 2c, the more favored path forms 5-nitro-substituted Δ2-isoxazoline 4c. This is due to the presence of a cyano group in the alkene. The CDFT study correlates well with the analysis of the kinetic description of the considered reaction channels. Moreover, DFT calculations have proven the clearly polar nature of all analyzed [3+2] cycloaddition reactions according to the polar one-step mechanism. View Full-Text
Keywords: benzonitrile N-oxide; β-phosphorylated nitroethenes; [3+2] cycloaddition reaction; regioselectivity; Density Functional Theory benzonitrile N-oxide; β-phosphorylated nitroethenes; [3+2] cycloaddition reaction; regioselectivity; Density Functional Theory
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MDPI and ACS Style

Zawadzińska, K.; Kula, K. Application of β-Phosphorylated Nitroethenes in [3+2] Cycloaddition Reactions Involving Benzonitrile N-Oxide in the Light of a DFT Computational Study. Organics 2021, 2, 26-37. https://doi.org/10.3390/org2010003

AMA Style

Zawadzińska K, Kula K. Application of β-Phosphorylated Nitroethenes in [3+2] Cycloaddition Reactions Involving Benzonitrile N-Oxide in the Light of a DFT Computational Study. Organics. 2021; 2(1):26-37. https://doi.org/10.3390/org2010003

Chicago/Turabian Style

Zawadzińska, Karolina; Kula, Karolina. 2021. "Application of β-Phosphorylated Nitroethenes in [3+2] Cycloaddition Reactions Involving Benzonitrile N-Oxide in the Light of a DFT Computational Study" Organics 2, no. 1: 26-37. https://doi.org/10.3390/org2010003

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