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:	Refereed Article
Keywords:	density functional theory, activation energy, DFT mechanistic investigation, BF3‑Catalyzed Reactions, phenol dearomatization
Research Division:	Chemical Sciences
Research Group:	Organic chemistry
Research Field:	Physical organic chemistry
Objective Division:	Expanding Knowledge
Objective Group:	Expanding knowledge
Objective Field:	Expanding knowledge in the chemical sciences
UTAS Author:	Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:	134445
Year Published:	2019
Funding Support:	Australian Research Council (DP180100904)
Web of Science® Times Cited:	27
Deposited By:	Chemistry
Deposited On:	2019-08-13
Last Modified:	2022-08-18
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