H. Y. Fu, H. Doucet
FULL PAPER
(d, J = 3.5 Hz, 1 H), 6.86 (d, J = 3.5 Hz, 1 H), 1.42 (s, 9 H) ppm. H), 7.97–7.80 (m, 4 H), 7.74 (t, J = 7.2 Hz, 1 H), 7.70–7.42 (m, 4
13C NMR (75 MHz, CDCl3): δ = 154.1, 152.7, 150.6, 134.1, 130.3, H), 7.09 (d, J = 3.5 Hz, 1 H), 6.92 (d, J = 3.5 Hz, 1 H) ppm. 13C
128.6, 128.5, 128.2, 126.6, 126.0, 125.7, 125.6, 125.4, 123.7, 111.4,
106.4, 34.7, 31.3 ppm. C24H22O (326.43): calcd. C 88.31, H 6.79;
found C 88.40, H 6.61.
NMR (75 MHz, CDCl3): δ = 154.2, 151.2, 147.1, 134.0, 130.3,
129.4, 129.3, 129.0, 128.9, 128.7, 128.1, 128.0, 127.3, 126.8, 126.3,
126.1, 125.4, 125.3, 124.0, 111.7, 108.7 ppm. C23H15NO (321.37):
calcd. C 85.96, H 4.70; found C 85.89, H 4.87.
3-[5-(4-tert-Butylphenyl)furan-2-yl]pyridine (36): 3-Bromopyridine
(0.158 g, 1 mmol) and methyl 5-(4-tert-butylphenyl)furan-2-carb-
oxylate 9 (0.322 g, 1.25 mmol) afforded 36 (0.194 g) in 70% yield.
1H NMR (300 MHz, CDCl3): δ = 9.01 (s, 1 H), 8.51 (d, J = 4.5 Hz,
1 H), 8.01 (d, J = 8.0 Hz, 1 H), 7.70 (d, J = 8.4 Hz, 2 H), 7.46 (d,
J = 8.4 Hz, 2 H), 7.34 (dd, J = 8.0, 4.5 Hz, 1 H), 6.84 (d, J =
3.5 Hz, 1 H), 6.74 (d, J = 3.5 Hz, 1 H), 1.37 (s, 9 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 154.6, 151.0, 150.0, 148.0, 145.3,
130.5, 127.7, 126.9, 125.7, 123.7, 123.5, 108.6, 106.7, 34.7,
31.3 ppm. C19H19NO (277.36): calcd. C 82.28, H 6.90; found C
82.42, H 6.78.
4-[5-(4-tert-Butylphenyl)furan-2-yl]benzaldehyde (42): 4-Bromo-
benzaldehyde (0.185 g, 1 mmol) and methyl 5-(4-tert-butylphenyl)-
furan-2-carboxylate
9 (0.322 g, 1.25 mmol), KOAc (0.392 g,
4 mmol), K2CO3 (0.276 g, 2 mmol) and Pd(OAc)2 (2.2 mg,
0.01 mmol) were dissolved in DMAc (4 mL) under argon. The re-
action mixture was stirred at 150 °C for 20 h. The solvent was then
evaporated, and the product was purified by silica gel column
chromatography to afford 42 (0.125 g) in 41% yield. 1H NMR
(300 MHz, CDCl3): δ = 10.01 (s, 1 H), 7.93 (d, J = 8.4 Hz, 2 H),
7.88 (d, J = 8.4 Hz, 2 H), 7.72 (d, J = 8.3 Hz, 2 H), 7.48 (d, J =
8.3 Hz, 2 H), 6.95 (d, J = 3.5 Hz, 1 H), 6.76 (d, J = 3.5 Hz, 1 H),
1.38 (s, 9 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 191.5, 155.3,
151.6, 151.3, 136.1, 134.7, 130.4, 127.5, 125.7, 123.9, 123.7, 110.5,
107.1, 34.7, 31.2 ppm. C21H20O2 (304.38): calcd. C 82.86, H 6.62;
found C 82.74, H 6.47.
2,5-Bis(3-trifluoromethylphenyl)furan (37): 1-Bromo-3-(trifluoro-
methyl)benzene (0.225 g, 1 mmol) and methyl 5-(3-trifluoromethyl-
phenyl)furan-2-carboxylate 14 (0.337 g, 1.25 mmol) afforded 37
1
(0.139 g) in 39% yield. H NMR (300 MHz, CDCl3): δ = 7.98 (s,
2 H), 7.93 (t, J = 7.7 Hz, 2 H), 7.58 (d, J = 7.7 Hz, 2 H), 7.53 (d,
J = 7.7 Hz, 2 H), 6.88 (s, 2 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 152.6, 131.3 (q, J = 32.4 Hz), 131.1, 129.3, 126.8 (q, J =
1.2 Hz), 124.0 (q, J = 272.4 Hz), 124.1 (q, J = 3.8 Hz), 120.5 (q, J
= 3.9 Hz), 108.7 ppm. C18H10F6O (356.26): calcd. C 60.68, H 2.83;
found C 60.81, H 2.97.
4-[5-(3-Trifluoromethylphenyl)furan-2-yl]benzonitrile (43): 4-Bromo-
benzonitrile (0.182 g, 1 mmol), methyl 5-(3-trifluoromethylphenyl)-
furan-2-carboxylate 14 (0.337 g, 1.25 mmol), KOAc (0.392 g,
4 mmol), K2CO3 (0.276 g, 2 mmol) and Pd(OAc)2 (2.2 mg,
0.01 mmol) were dissolved in DMAc (4 mL) under argon. The re-
action mixture was stirred at 150 °C for 80 h. The solvent was evap-
orated, and the product was purified by silica gel column
chromatography to afford 43 (0.162 g) in 52% yield. 1H NMR
(300 MHz, CDCl3): δ = 7.98 (s, 1 H), 7.93 (t, J = 7.7 Hz, 1 H),
7.85 (d, J = 8.4 Hz, 2 H), 7.72 (d, J = 8.4 Hz, 2 H), 7.60–7.50 (m,
2 H), 6.94 (d, J = 3.5 Hz, 1 H), 6.89 (d, J = 3.5 Hz, 1 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 153.4, 152.0, 134.1, 132.7, 131.4 (q,
J = 32.2 Hz), 130.8, 129.4, 127.0, 124.4 (q, J = 4.0 Hz), 124.0, 123.9
(q, J = 272.9 Hz), 120.7 (q, J = 4.0 Hz), 118.9, 110.6, 110.5,
108.9 ppm. C18H10F3NO (313.27): calcd. C 69.01, H 3.22; found C
69.07, H 3.47.
2-Naphthalen-1-yl-5-(4-nitrophenyl)furan (38): 4-Bromonitrobenz-
ene (0.202 g, 1 mmol) and methyl 5-(naphthalen-1-yl)furan-2-carb-
oxylate 23 (0.315 g, 1.25 mmol) afforded 38 (0.161 g) in 51% yield.
1H NMR (300 MHz, CDCl3): δ = 8.47 (d, J = 8.1 Hz, 1 H), 8.28
(d, J = 8.1 Hz, 2 H), 7.98–7.62 (m, 5 H), 7.68–7.51 (m, 3 H), 7.08
(d, J = 3.5 Hz, 1 H), 6.91 (d, J = 3.5 Hz, 1 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 155.3, 151.4, 146.0, 136.3, 134.0, 130.2,
129.4, 128.8, 127.7, 127.0, 126.5, 126.2, 125.3, 125.2, 124.5, 123.8,
112.1, 111.0 ppm. C20H13NO3 (315.32): calcd. C 76.18, H 4.16;
found C 76.25, H 4.07.
2-(4-Fluorophenyl)-5-naphthalen-1-ylfuran (39): 4-Bromofluoro-
benzene (0.175 g, 1 mmol) and methyl 5-(naphthalen-1-yl)furan-2-
carboxylate 23 (0.315 g, 1.25 mmol) afforded 39 (0.225 g) in 78%
Acknowledgments
1
yield. H NMR (300 MHz, CDCl3): δ = 8.52 (d, J = 8.1 Hz, 1 H),
H. Y. F. is grateful to the Chinese Scholarship Council for a grant.
We thank Centre National de la Recherche Scientifique (CNRS)
and Rennes Metropole for providing financial support.
7.98–7.70 (m, 5 H), 7.65–7.51 (m, 3 H), 7.12 (t, J = 8.2 Hz, 2 H),
6.84 (d, J = 3.5 Hz, 1 H), 6.81 (d, J = 3.5 Hz, 1 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 162.2 (d, J = 241.7 Hz), 153.0, 134.1, 130.3,
128.6, 128.4, 127.2 (d, J = 3.4 Hz), 126.7, 126.0 (d, J = 4.6 Hz),
125.6, 125.5, 125.4, 115.7 (d, J = 22.0 Hz), 111.5, 106.6 ppm.
C20H13FO (288.32): calcd. C 83.32, H 4.54; found C 83.47, H 4.41.
[1] a) J. J. Li, G. W. Gribble, Palladium in Heterocyclic Chemistry,
Pergamon, Amsterdam, 2000; b) E. Negishi (Ed.), Handbook
of Organopalladium Chemistry for Organic Synthesis, Wiley-In-
terscience, New York, 2002, part III, p. 213; c) J. Hassan, M.
Sévignon, C. Gozzi, E. Schultz, M. Lemaire, Chem. Rev. 2002,
102, 1359; d) I. Kondolff, H. Doucet, M. Santelli, Synlett 2005,
2057.
[2] For selected examples of synthesis of 2-arylfurans using Stille,
Suzuki, or Negishi couplings, see: a) A. Pelter, M. Rowlands,
G. Clements, Synthesis 1987, 51; b) M. Larhed, M. Hoshino,
S. Hadida, D. P. Curran, A. Hallberg, J. Org. Chem. 1997, 62,
5583; c) T. Osswald, S. Schneider, S. Wang, W. Bannwarth, Tet-
rahedron Lett. 2001, 42, 2965; d) S. Kotha, A. K. Ghosh, K. D.
Deodhar, Synthesis 2004, 549; e) J. R. Naber, S. L. Buchwald,
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turk, L. E. Kennedy, J. Org. Chem. 2009, 74, 973; g) Y. Yabe,
T. Maegawa, Y. Monguchi, H. Sajiki, Tetrahedron 2010, 66,
8654.
4-(5-Naphthalen-1-ylfuran-2-yl)pyridine (40): 4-Bromopyridine hy-
drochloride (0.195 g, 1 mmol) and methyl 5-(naphthalen-1-yl)-
furan-2-carboxylate 23 (0.315 g, 1.25 mmol) afforded 40 (0.171 g)
in 63% yield. 1H NMR (300 MHz, CDCl3): δ = 8.65 (d, J = 5.9 Hz,
2 H), 8.47 (d, J = 8.1 Hz, 1 H), 7.97–7.89 (m, 2 H), 7.84 (d, J =
7.2 Hz, 1 H), 7.66–7.45 (m, 5 H), 7.09 (d, J = 3.5 Hz, 1 H), 6.88
(d, J = 3.5 Hz, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 154.9,
150.9, 150.3, 137.4, 134.0, 130.2, 129.3, 128.7, 127.9, 126.9, 126.5,
126.1, 125.3, 125.2, 117.6, 111.7, 110.7 ppm. C19H13NO (271.31):
calcd. C 84.11, H 4.83; found C 84.02, H 4.69.
3-(5-Naphthalen-1-ylfuran-2-yl)quinoline (41): 3-Bromoquinoline
(0.208 g, 1 mmol) and methyl 5-(naphthalen-1-yl)furan-2-carboxyl-
1
ate 23 (0.315 g, 1.25 mmol) afforded 41 (0.186 g) in 58% yield. H
NMR (300 MHz, CDCl3): δ = 9.35 (d, J = 1.6 Hz, 1 H), 8.51 (d,
J = 8.1 Hz, 1 H), 8.47 (d, J = 1.6 Hz, 1 H), 8.14 (d, J = 8.4 Hz, 1
[3] a) Y. Akita, A. Inoue, K. Yamamoto, A. Ohta, T. Kurihara,
M. Shimizu, Heterocycles 1985, 23, 2327; b) A. Ohta, Y. Akita,
7172
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Eur. J. Org. Chem. 2011, 7163–7173