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Mechanistic investigations of Cu-catalyzed fluorination of diaryliodonium salts: elaborating the CuI/CuII manifold in copper catalysis

Citation

Ichiishi, N and Canty, AJ and Yates, BF and Sanford, MS, Mechanistic investigations of Cu-catalyzed fluorination of diaryliodonium salts: elaborating the CuI/CuII manifold in copper catalysis, Organometallics, 33, (19) pp. 5525-5534. ISSN 0276-7333 (2014) [Refereed Article]

Copyright Statement

Copyright 2014 American Chemical Society

DOI: doi:10.1021/om5007903

Abstract

A combination of experimental and density functional theory (DFT) investigations suggests that the Cu-catalyzed fluorination of unsymmetrical diaryliodonium salts with general structure [Mes(Ar)I]+ in N,N′-dimethylformamide proceeds through a CuI/CuIII catalytic cycle. A low concentration of fluoride relative to combined iodonium reagent plus copper ensures that [Mes(Ar)I]+ is available as the reactive species for oxidative "Ar+" transfer to a CuI center containing one or two fluoride ligands. A series of different possible CuI active catalysts (containing fluoride, triflate, and DMF ligands) have been evaluated computationally, and all show low-energy pathways to fluorinated products. The oxidation of these CuI species by [Mes(Ar)I]+ to form cis-Ar(F)CuIII intermediates is proposed to be rate-limiting in all cases. ArF bond-forming reductive elimination from CuIII is computed to be very facile in all of the systems examined. The conclusions of the DFT experiments are supported by several experimental studies, including tests showing that CuI is formed rapidly under the reaction conditions and that the fluoride concentration strongly impacts the reaction yields/selectivities.

Item Details

Item Type:Refereed Article
Keywords:copper catalysis, iodonium
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Organometallic Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Canty, AJ (Professor Allan Canty)
Author:Yates, BF (Professor Brian Yates)
ID Code:97173
Year Published:2014
Web of Science® Times Cited:25
Deposited By:Chemistry
Deposited On:2014-12-05
Last Modified:2015-04-28
Downloads:0

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