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Catalytic role of Lewis acids in ArIO-mediated oxidative fluorination reactions revealed by DFT calculations


Farshadfar, K and Abdolalian, P and Ariafard, A, Catalytic role of Lewis acids in ArIO-mediated oxidative fluorination reactions revealed by DFT calculations, European Journal of Organic Chemistry, 2020, (15) pp. 2251-2259. ISSN 1434-193X (2020) [Refereed Article]

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Copyright 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: doi:10.1002/ejoc.202000217


Density functional theory (DFT) at the SMD/M06‐2X/def2‐TZVP//SMD/M06‐2X/SDD,6‐31G(d) level was performed to interrogate the mechanistic details of two oxidative fluorination reactions mediated by hypervalent iodosoarenes (ArIO) in the presence of Lewis acid BF3: (i) formation of a 3‐fluoropyrrolidine from a homoallylic amine and (ii) formation of a fluorinated oxazoline from a benzamide. We found that in both cases, ArIO needs two Lewis acids to be sufficiently activated to mediate the oxidative reactions. When two Lewis acids bind to ArIO, its LUMO mainly centred on the iodine(III) atom becomes energetically more available, resulting in it interacting more strongly with the CC π orbital of the organic substrate and thus the rate‐determining step of the reaction (an intramolecular nucleophilic attack) being accelerated. Finally, one of these Lewis acids serves as the catalyst and the other one supplies a fluorine atom to the organic substrate. A clear understanding of how ArIO reagents are activated in oxidation of organic substrates could be helpful in designing new oxidative reactions mediated by such hypervalent iodine compounds.

Item Details

Item Type:Refereed Article
Keywords:hypervalent compounds, reaction mechanisms, density functional calculations, Lewis bases, oxidative fluorination
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:142022
Year Published:2020
Funding Support:Australian Research Council (DP180100904)
Web of Science® Times Cited:4
Deposited By:Chemistry
Deposited On:2020-12-08
Last Modified:2022-08-19

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