eCite Digital Repository
DFT mechanistic investigation into phenol dearomatization mediated by an iodine(III) reagent
Citation
Ganji, B and Ariafard, A, DFT mechanistic investigation into phenol dearomatization mediated by an iodine(III) reagent, Organic & Biomolecular Chemistry, 17 pp. 3521-3528. ISSN 1477-0520 (2019) [Refereed Article]
Copyright Statement
© The Royal Society of Chemistry 2019
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 Details
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: | 19 |
Deposited By: | Chemistry |
Deposited On: | 2019-08-13 |
Last Modified: | 2019-12-09 |
Downloads: | 0 |
Repository Staff Only: item control page