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Participation of Phosphorylated Analogues of Nitroethene in Diels–Alder Reactions with Anthracene: A Molecular Electron Density Theory Study and Mechanistic Aspect

Institute of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, Poland
Received: 30 October 2020 / Revised: 16 November 2020 / Accepted: 20 November 2020 / Published: 23 November 2020
(This article belongs to the Special Issue Cycloaddition Reaction in Organic Synthesis)
The structure and the contribution of the bis(2-chloroethyl) 2-nitro 1a and 2-bromo-2-nitroethenylphosphonates 1b with anthracene 2 in the Diels–Alder (DA) reactions have been studied within the Molecular Electron Density Theory (MEDT) at the B3LYP functional together with 6-31G(d), 6-31+G(d) and 6-31+G(d,p) basic sets. Analysis of the Conceptual Density Functional Theory (CDFT) reactivity indices indicates that 1a and 1b can be classified as a strong electrophile and marginal nucleophile, while 2 is classified as a strong electrophile and strong nucleophile. The studied DA reactions take place through a one-step mechanism. A Bonding Evolution Theory (BET) of the one path associated with the DA reaction of 1a with 2 indicates that it is associated with non-concerted two-stage one-step mechanism. BET analysis shows that the first C2-C3 single bond is formed in Phase VI, while the second C1-C6 single bond is formed in the Phase VIII. The formation of both single bonds occurs through the merging of two C2 and C3, C1 and C6 pseudoradical centers, respectively. View Full-Text
Keywords: Diels–Alder reaction; anthracene; molecular mechanism; bonding evolution theory; molecular electron density theory Diels–Alder reaction; anthracene; molecular mechanism; bonding evolution theory; molecular electron density theory
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MDPI and ACS Style

Kącka-Zych, A. Participation of Phosphorylated Analogues of Nitroethene in Diels–Alder Reactions with Anthracene: A Molecular Electron Density Theory Study and Mechanistic Aspect. Organics 2020, 1, 36-48. https://0-doi-org.brum.beds.ac.uk/10.3390/org1010004

AMA Style

Kącka-Zych A. Participation of Phosphorylated Analogues of Nitroethene in Diels–Alder Reactions with Anthracene: A Molecular Electron Density Theory Study and Mechanistic Aspect. Organics. 2020; 1(1):36-48. https://0-doi-org.brum.beds.ac.uk/10.3390/org1010004

Chicago/Turabian Style

Kącka-Zych, Agnieszka. 2020. "Participation of Phosphorylated Analogues of Nitroethene in Diels–Alder Reactions with Anthracene: A Molecular Electron Density Theory Study and Mechanistic Aspect" Organics 1, no. 1: 36-48. https://0-doi-org.brum.beds.ac.uk/10.3390/org1010004

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