Journal of the American Chemical Society
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(10) Chu, L.; Ohta, C.; Zuo, Z.; MacMillan, D. W. C. J. Am. Chem. Soc. 2014, 136,
Figure 1. Ir[dF(CF3)ppy]2(dtbbpy)PF6 Emission Quenching with
Selectfluor® and Sodium 4-tert-butylcyclohexanecarboxylate.
10886.
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(11) Yin, F.; Wang, Z.; Li, Z.; Li, C. J. Am. Chem. Soc. 2012, 134, 10401.
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(12) (a) Rueda-Becerril, M.; Chatlova-Sazepin, C.; Leung, J. C. T.; Okbinoglu, T.;
Kennepohl, P.; Paquin, J.-F.; Sammis, G. M. J. Am. Chem. Soc. 2012, 134,
4026. (b) Leung, J. C. T.; Chatalova-Sazepin, C.; West, J.; Rueda-Becerril,
M.; Paquin, J.-F.; Sammis, G. M. Angew. Chem. Int. Ed. 2012, 51, 10804. (c)
Rueda-Becerril, M.; Mahe, O.; Drouin, M.; Majewski, M. B.; West, J. G.;
Wolf, M. O.; Sammis, G. M.; Paquin, J.-F. J. Am. Chem. Soc. 2014, 136,
2637.
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(13) Zuo, Z.; MacMillan, D. W. C. J. Am. Chem. Soc. 2014, 136, 5257.
(14) Lowry, M. S.; Goldsmith, J. L.; Slinker, J. D.; Rohl, R.; Pascal, R. A.;
Malliaras, G. G.; Bernhard, S. Chem. Mater. 2005, 17, 5712.
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(15) (a) Stavber, S.; Zupan, M. Acta Chim. Slov. 2005, 52, 13. (b) Girina, G. P.;
Fainzil'berg, A. A.; Feoktistov, L. G. Russ. J. Electrochem. 2000, 36, 162.
(16) Galicia, M.; Gonzalez, F. J. J. Electrochem. Soc. 2002, 149, D46.
(17) Bockman, T. M.; Hubig, S. M.; Kochi, J. K. J. Org. Chem. 1997, 62, 2210.
(18) Fluorides 22, 25 and 29 were also obtained using Ir[dF(CF3)ppy]2(dtbbpy)PF6
photocatalyst in 71%, 89% and 85% yield, respectively. However, we
observed slightly increased efficiency with the ruthenium-based photocatalyst
Ru(bpz)3(PF6)2 in these three cases.
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(19) See Supporting Information for further details about fluorescence quenching
studies.
a diverse collection of valuable fluorinated products. Notably,
under these reaction conditions more activated substrates require
lower amounts of the electrophilic fluorinating reagent and
shorter reaction times. Mechanistic studies have provided
evidence supporting an oxidative quenching pathway, in which
reduction of the N–F bond of Selectfluor® initiates the
photoredox
cycle
prior
to
the
carboxylic
acid
oxidation/decarboxylation sequence.
Acknowledgement. Financial support was provided by the
NIGMS (R01 GM093213-05) and kind gifts from Merck,
Amgen, and AbbVie.
Supporting Information Available. Experimental procedures
and spectral data are provided. This material is available free of
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