5
reaction mixture was stirred and irradiated for 1 to 6 hours. Upon
Acknowledgment
ACCEPTED MANUSCRIPT
completion, the reaction mixture was diluted with Et2O or ethyl
acetate (for less soluble substrates) and washed successively with
water and brine. The combined aqueous washings were extracted
with the appropriate organic solvent (2 x 25mL). The combined
organic extracts were dried (MgSO4), filtered and concentrated in
vacuo. Purification by flash column chromatography over silica
gel afforded the pure product.
This paper is dedicated to Professors Stephen L. Buchwald
and John F. Hartwig on the occasion of being the 2018 recipients
of the Tetrahedron Prize for creativity in organic chemistry.
Financial support was provided by NIH NIGMS R01
GM09321301 and kind gifts from Merck, BMS, Janssen, and Eli
Lilly, Pfizer and AbbVie. J.L.J. is grateful for a NIH postdoctoral
fellowship (F32GM109536). J.M. thanks University of Valencia
for a predoctoral fellowship. Jack Twilton, Chi Le, and Dr. Chun
Liu are thanked for their help in preparing this paper.
4.1. Synthesis of 2-fluorodecane (10).
Following the general deoxyfluorination procedure, 2-(decan-
2-yloxy)-2-oxoacetic acid (207 mg, 0.9 mmol, 1.0 equiv),
Na2HPO4 (256 mg, 1.8 mmol, 2.0 equiv), Selectfluor® (638 mg,
1.8 mmol, 2.0 equiv), Ir[dF(OMe)ppy]2(dtbbpy)PF6 (9.4 mg, 9.0
ꢀmol, 1 mol%) and 4:1 acetone/H2O (9.0 mL, 0.1 M) provided
after 1.5 h the desired product (111 mg, 77% yield) as a
colourless liquid. Purification was accomplished via flash column
chromatography over silica gel (hexanes). IR (film): νmax 2926,
Notes
‡These authors contributed equally. The authors declare no
competing financial interest.
References
1
2856, 1463, 1383, 1341, 1130, 1079 cm–1. H NMR (300 MHz,
CDCl3): δ 4.80-4.47 (m, 1H), 1.80-1.15 (m, 17H), 0.94-0.80 (m,
3H) ppm. 13C NMR (125 MHz, CDCl3): δ 91.7, 90.4, 37.0, 36.9,
31.9, 29.5, 29.2, 25.1, 22.7, 21.1, 20.9, 14.1 ppm. 19F NMR (282
MHz, CDCl3): δ -171.8 – -172.4 (m, 1F). HRMS (EI) m/z calcd.
for C10H20 [(M-F)*+] 140.1560, found 140.1561.
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1030, 734, 696 cm–1. H NMR (300 MHz, CDCl3): δ 7.38-7.33
(m, 2H), 7.26 (d, J = 7.3 Hz, 3H), 2.82-2.76 (m, 2H), 2.05-1.93
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((8-phenyloctyl)oxy)acetic acid (278 mg, 1.0 mmol, 1.0 equiv),
Na2HPO4 (284 mg, 2.0 mmol, 2.0 equiv), Selectfluor® (1.6 g, 4.5
mmol, 4.5 equiv), Ir[dF(CF3)ppy]2(dtbbpy)PF6 (11.2 mg, 10.0
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7.30-7.27 (m, 2H), 7.19-7.17 (m, 3H), 4.44 (dt, J = 47.4, 6.2 Hz,
2H), 2.61 (t, J = 7.5 Hz, 2H), 1.74-1.59 (m, 4H), 1.42-1.33 (m,
8H) ppm. 13C NMR (125 MHz, CDCl3): δ 142.8, 128.4, 128.2,
125.6, 84.2 (d, JC,F = 162.8 Hz), 35.9, 31.5, 30.4 (d, JC,F = 19.1
Hz), 29.4, 29.2, 29.2, 25.1 (d, JC,F = 5.5 Hz) ppm. 19F NMR (282
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