Application of β-Phosphorylated nitroethenes in [3+2] cycloaddition reactions involving benzonitrile N-Oxide in the light of a DFT computational study
Authors:
- Karolina Zawadzińska,
- Karolina Kula
Abstract
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.
- Record ID
- CUT990f9f1cd1684efb83fb826679e579f1
- Publication categories
- ;
- Author
- Journal series
- Organics , ISSN , e-ISSN 2673-401X, Annual
- Issue year
- 2021
- Vol
- 2
- No
- 1
- Pages
- 26-37
- Other elements of collation
- schem.; tab.; wykr.; Bibliografia (na s.) - 35-37; Bibliografia (liczba pozycji) - 55; Oznaczenie streszczenia - Abstr.; Numeracja w czasopiśmie - Vol. 2, Iss. 1, Spec. Iss.
- Substantive notes
- Special Issue: Cycloaddition Reaction in Organic Synthesis
- Keywords in English
- benzonitrile N-oxide, β-phosphorylated nitroethenes, [3+2] cycloaddition reaction, regioselectivity, Density Functional Theory
- DOI
- DOI:10.3390/org2010003 Opening in a new tab
- URL
- https://www.mdpi.com/2673-401X/2/1/3/htm Opening in a new tab
- Language
- eng (en) English
- License
- Score (nominal)
- 5
- Uniform Resource Identifier
- https://cris.pk.edu.pl/info/article/CUT990f9f1cd1684efb83fb826679e579f1/
- URN
urn:pkr-prod:CUT990f9f1cd1684efb83fb826679e579f1
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