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Organic & Biomolecular Chemistry
Page 4 of 4
COMMUNICATION
Journal Name
2016, 45, 4638.
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Scheme 2 Fluorination of 3h with Selectfluor
Cortés and K. J. Szabó, ACS Catal., 2016,
6, 447; (c) N. O.
(3JHH = 7.5 Hz). This provided good evidence for the formation of a
hydrogen-bonded adduct between the HFIP and fluoroiodane.
In conclusion, we have demonstrated that HFIP is an excellent
solvent for promoting fluorinations with the hypervalent fluoro-
iodane reagent 1 and crucially, it removes the need for transition
metals or TREAT-HF activators. NMR data revealed the formation of
a hydrogen-bonded adduct between the solvent and fluoroiodane,
showing that the fluoroiodane reagent 1 is activated by hydrogen
bonding to HFIP. 1,3-Ketoesters and a 1,3-ketoamide were mono-
fluorinated in excellent yields in HFIP in 1-4 hours compared to 24
hours in dichloromethane using TREAT-HF. The metal-free fluoro-
cyclisations of unsaturated carboxylic acids also proceeded well in
HFIP to deliver the fluorinated lactones in excellent yields.
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We would like to thank Vanessa Timmermann for assistance with
the NMR experiments and Kuldip Singh for X-ray crystallography.
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Conflicts of Interest
There are no conflicts to declare.
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13 G. C. Geary, PhD Thesis, University of Leicester, 2015.
14 E. E. Gray, M. K. Nielsen, K. A. Choquette, J. A. Kalow, T. J. A.
Graham and A. G. Doyle, J. Am. Chem. Soc., 2016, 138
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10802.
15 The -lactone 5e is unstable and decomposed to 5-oxo-6-
Figure 1. 1H NMR spectra of (a) fluoroiodane 1, (b) HFIP and (c) a 1:1 mixture of
fluoroiodane:HFIP, showing a plausible structure of an adduct. The red star indicates the
position of the deshielded OH signal of interest.
phenylhexanoic acid over 2-3 hours in CDCl3.
Notes and references
1
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