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DFT mechanistic investigation into phenol dearomatization mediated by an iodine(III) reagent

Ganji, B and Ariafard, A ORCID: 0000-0003-2383-6380 2019 , 'DFT mechanistic investigation into phenol dearomatization mediated by an iodine(III) reagent' , Organic & Biomolecular Chemistry, vol. 17 , 3521–3528 , doi: 10.1039/c9ob00028c.

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Abstract

Density functional theory (DFT) was utilized to investigate the mechanistic aspects of the oxidative dearomatization of phenols mediated by an iodine(III) reagent. In this article, we will show that the conventional mechanism in which an iodine(III) phenolate is proposed as the key intermediate is not operative, and the process is promoted if the phenolate ligand is dearomatized on the iodine(III) center. The dearomatized phenolate is calculated to be a more potent reductant than phenolate itself. In such a case, the reaction is capable of proceeding via two competitive mechanisms (dissociative and associative). Consistent with the experimental findings, we found that while the less polar solvents considerably disfavor the dissociative mechanism, they have an insignificant effect on the associative one. The energetic order of these two mechanisms is calculated to be influenced by the nature of the counter anion coordinated to the iodine(III) center.

Item Type: Article
Authors/Creators:Ganji, B and Ariafard, A
Keywords: density functional theory, activation energy, DFT mechanistic investigation, BF3‑Catalyzed Reactions, phenol dearomatization
Journal or Publication Title: Organic & Biomolecular Chemistry
Publisher: Royal Soc Chemistry
ISSN: 1477-0520
DOI / ID Number: 10.1039/c9ob00028c
Copyright Information:

© The Royal Society of Chemistry 2019

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