On the Mechanism of the Synthesis of Nitrofunctionalised Δ<sup>2</sup>-Pyrazolines via [3+2] Cycloaddition Reactions between α-EWG-Activated Nitroethenes and Nitrylimine TAC Systems

Agnieszka Fryźlewicz; Aleksandra Olszewska; Karolina Zawadzińska; Przemysław Woliński; Karolina Kula; Agnieszka Kącka-Zych; Agnieszka Łapczuk-Krygier; Radomir Jasiński

doi:10.3390/org3010004

Organics (Mar 2022)

On the Mechanism of the Synthesis of Nitrofunctionalised Δ<sup>2</sup>-Pyrazolines via [3+2] Cycloaddition Reactions between α-EWG-Activated Nitroethenes and Nitrylimine TAC Systems

Agnieszka Fryźlewicz,
Aleksandra Olszewska,
Karolina Zawadzińska,
Przemysław Woliński,
Karolina Kula,
Agnieszka Kącka-Zych,
Agnieszka Łapczuk-Krygier,
Radomir Jasiński

Affiliations

Agnieszka Fryźlewicz: Department of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, Poland
Aleksandra Olszewska: Department of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, Poland
Karolina Zawadzińska: Department of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, Poland
Przemysław Woliński: Department of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, Poland
Karolina Kula: Department of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, Poland
Agnieszka Kącka-Zych: Department of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, Poland
Agnieszka Łapczuk-Krygier: Department of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, Poland
Radomir Jasiński: Department of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, Poland

DOI: https://doi.org/10.3390/org3010004
Journal volume & issue: Vol. 3, no. 1
pp. 59 – 76

Abstract

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We investigated the reactivity of different substituted nitrylimine-type three atom components (TACs) in [3+2] cycloaddition (32CAs) reactions with electrophilically activated nitroethenes within molecular electron density theory (MEDT). In parallel research, the molecular mechanism of the considered transformation was examined through analysis of all possible reaction channels and full optimization of all critical structures. In particular, the existence of zwitterionic intermediates on reaction paths was verified. On the basis of the bonding evolution theory (BET), the mechanism of the 32CA reaction between C,N-diphenylnitrylimine and (E)-2-phenyl-1-cyano-1-nitroethene should be treated as a one-step two-stage mechanism.

Published in Organics

ISSN: 2673-401X (Online)
Publisher: MDPI AG
Country of publisher: Switzerland
LCC subjects: Science: Chemistry: Organic chemistry
Website: https://www.mdpi.com/journal/organics

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