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Mechanism of Iodine(III)‐Promoted Oxidative Dearomatizing Hydroxylation of Phenols: Evidence for a Radical‐Chain Pathway
- Source :
- Chemistry – A European Journal. 26:11584-11592
- Publication Year :
- 2020
- Publisher :
- Wiley, 2020.
-
Abstract
- The oxidative dearomatization of phenols with the addition of nucleophiles to the aromatic ring induced by hypervalent iodine(III) reagents and catalysts has emerged as a highly useful synthetic approach. However, experimental mechanistic studies of this important process have been extremely scarce. In this report, we describe systematic investigations of the dearomatizing hydroxylation of phenols using an array of experimental techniques. Kinetics, EPR spectroscopy, and reactions with radical probes demonstrate that the transformation proceeds by a radical-chain mechanism, with a phenoxyl radical being the key chain-carrying intermediate. Moreover, UV and NMR spectroscopy, high-resolution mass spectrometry, and cyclic voltammetry show that before reacting with the phenoxyl radical, the water molecule becomes activated by the interaction with the iodine(III) center, causing the Umpolung of this formally nucleophilic substrate. The radical-chain mechanism allows the rationalization of all existing observations regarding the iodine(III)-promoted oxidative dearomatization of phenols.
- Subjects :
- 010405 organic chemistry
Chemistry
Organic Chemistry
Hypervalent molecule
General Chemistry
Nuclear magnetic resonance spectroscopy
010402 general chemistry
01 natural sciences
Combinatorial chemistry
Catalysis
0104 chemical sciences
Umpolung
Hydroxylation
chemistry.chemical_compound
Nucleophile
Reagent
Phenols
Subjects
Details
- ISSN :
- 15213765 and 09476539
- Volume :
- 26
- Database :
- OpenAIRE
- Journal :
- Chemistry – A European Journal
- Accession number :
- edsair.doi.dedup.....9b88f57fc954ecd3ba4f4310e271b547