859
S. R. Dubbaka et al.
Paper
Synthesis
1-Fluoro-4-isopropylbenzene (2k) and 1-Fluoro-2-isopropylben-
1,4-Difluorobenzene (2q) (Table 4, Entry 17)36
zene (3k) (Table 4, Entry 11)35
The reaction was performed using potassium trifluoro(4-fluorophe-
The reaction was performed using potassium trifluoro(3-isopropyl-
phenyl)borate (1k, 56.5 mg, 0.25 mmol, 1 equiv) to give 2k/3k
(29:36); yield: 65% (19F NMR analysis of the crude reaction mixture).
19F NMR (376 MHz, DMSO-d6): δ = –119.05 (s, F) (2k), –121.79 (s, F)
(3k).
nyl)borate (1q, 50.5 mg, 0.25 mmol, 1 equiv) to give 2q; yield: 60%
(
19F NMR (CDCl3, 376 M Hz): δ = –120.16 (s, F).
GC-MS: m/z = 114 (M+).
19F NMR analysis of the crude reaction mixture).
GC-MS: m/z = 226 (M+).
4-Fluorobenzonitrile (2r) (Table 4, Entry 18)
The reaction was performed using potassium (4-cyanophenyl)trifluo-
roborate (1r, 52.3 mg, 0.25 mmol, 1 equiv) to give 2r; yield: 10% (19
F
1-Fluoro-4-methoxybenzene (2a) and 1-Fluoro-2-methoxyben-
zene (3a) (Table 4, Entry 12)31
NMR analysis of the crude reaction mixture with 3-fluorotoluene as
an internal standard). The 19F NMR spectral data for 2r matched that
of an authentic sample (δ = –104.01, s).
19F NMR (376 MHz, CDCl3): δ = –104.13 (s, F).
GC-MS: m/z = 121 (M+).
The reaction was performed using potassium trifluoro(2-methoxy-
phenyl)borate (1l, 53.5 mg, 0.25 mmol, 1 equiv) to give 2a/3a (2:40);
yield: 42% (19F NMR analysis of the crude reaction mixture).
19F NMR (376 MHz, DMSO-d6): δ = –125.41 (s, F) (2a), –136.35 (s, F)
(3a).
GC-MS: m/z = 126 (M+).
Acknowledgment
1-Fluoro-2-methylbenzene (3m) (Table 4, Entry 13)24c
We thank Dr. Anjan Charkrabarti and Dr. Sergei Belyakov for their
support of this manuscript. We also thank Dr. Thresen Mathew and
Dr. Isherwood Matthew for their careful and valuable correction of
this manuscript.
The reaction was performed using potassium trifluoro(2-methylphe-
nyl)borate (1m, 49.5 mg, 0.25 mmol, 1 equiv) to give 3m; yield: 60%
(
19F NMR analysis of the crude reaction mixture); isolated yield: 13.7
mg (50%).
19F NMR (376 MHz, DMSO-d6): δ = –119.07 (s, F).
GC-MS: m/z = 110 (M+).
Supporting Information
Supporting information for this article is available online at
Fluorobenzene (2n) (Table 4, Entry 14)
S
u
p
p
ortiInfogrmoaitn
S
u
p
p
o
nrtogI
f
rmoaitn
The reaction was performed using potassium trifluoro(phenyl)borate
(1n, 46.0 mg, 0.25 mmol, 1 equiv) to give 2n; yield: 40% (19F NMR
analysis of the crude reaction mixture). 19F NMR spectral data for 2n
matched that of an authentic sample (δ = –114.01, s).
References
19F NMR (376 MHz, CDCl3): δ = –113.53 (s, F).
GC-MS: m/z = 96 (M+).
(1) These authors contributed equally.
(2) (a) Müller, K.; Faeh, C.; Diederich, F. Science (Washington, D.C.)
2007, 317, 1881. (b) Hagmann, W. K. J. Med. Chem. 2008, 51,
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ences therein.
1-Fluoronaphthalene (2o) (Table 4, Entry 15)31
The reaction was performed using potassium trifluoro(1-naphth-
yl)borate (1o, 58.5 mg, 0.25 mmol, 1 equiv) to give 2o; yield: 75% (19
F
NMR analysis of the crude reaction mixture); isolated yield: 25.5 mg
(70%).
1H NMR (300 MHz, CDCl3): δ = 8.14–8.09 (m, 1 H), 7.89–7.84 (m, 1 H),
7.63 (d, J = 8.0 Hz, 1 H), 7.58–7.52 (m, 2 H), 7.40 (ddd, J = 8.8, 8.8, 4.8
Hz, 1 H), 7.15 (dd, J = 11.2, 8.0 Hz, 1 H).
19F NMR (282 MHz, CDCl3): δ = –123.96 (s, F).
GC-MS: m/z = 146 (M+).
(4) (a) Mu, X.; Liu, G. Org. Chem. Front. 2014, 1, 430. (b) Lin, A.;
Huehls, B.; Yang, J. Org. Chem. Front. 2014, 1, 434. (c) Liang, T.;
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(d) Fier, P. S.; Hartwig, J. F. Science (Washington, D.C.) 2013, 342,
956. (e) Chen, P.; Liu, G. Synthesis 2013, 45, 2919.
1-Fluoronaphthalene (2o) and 2-Fluoronaphthalene (2p) (Table 4,
Entry 16)24
The reaction was performed using potassium trifluoro(2-naphth-
yl)borate (1p, 58.5 mg, 0.25 mmol, 1 equiv) to give 2o/2p (50:10);
yield: 60% (19F NMR analysis of the crude reaction mixture).
(5) (a) Sandford, G. J. Fluorine Chem. 2007, 128, 90. (b) Adams, D. J.;
Clark, J. H. Chem. Soc. Rev. 1999, 225.
(6) Balz, G.; Schiemann, G. Ber. Dtsch. Chem. Ges. 1927, 60, 1186.
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H.; DiMagno, S. G. Angew. Chem. Int. Ed. 2006, 45, 2720. (c) Sun,
H.; DiMagno, S. G. J. Am. Chem. Soc. 2005, 127, 2050.
19F NMR (376 MHz, CDCl3): δ = –124.09 (s, F) (2o), –115.51 (s, F) (2p).
GC-MS: m/z = 146 (M+).
(9) Grushin, V. V. US 7202388, 2007.
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 854–860