SHORT PAPER
A Novel and Efficient Coupling Reaction
945
Reaction of Sodium Tetraphenylborate with Iodonium Salts;
General Procedure
References
(1) For recent reviews, see: (a) Hassen, J.; Sevignon, M.; Gozzi,
C.; Schulz, E.; Lemaire, M. Chem. Rev. 2002, 102, 1359.
(b) Kotha, S.; Lahiri, K.; Kashinath, D. Tetrahedron 2002,
58, 9633. (c) Suzuki, A. J. Organomet. Chem. 1999, 576,
147. (d) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
(2) (a) Leadbeater, N. E.; Marco, M. Angew. Chem. Int. Ed.
2003, 42, 1407. (b) Leadbeater, N. E.; Marco, M. J. Org.
Chem. 2003, 68, 5660.
Ph4BNa (1; 137 mg, 0.4 mmol, 4 equiv), iodonium salt (2; 0.1
mmol, 1 equiv), and p-TsOH (38 mg, 0.2 mmol, 2 equiv) in H2O (5
mL) were stirred at 50 °C until the reaction was complete (Table 1).
After cooling to r.t., the mixture was extracted with Et2O (3 × 20
mL), the organic layer was dried over anhyd MgSO4, and the sol-
vent was evaporated in vacuo. The crude product was purified by
preparative thin-layer chromatography (silica gel, hexane) to afford
pure products 3 in good yields.
(3) (a) Varvoglis, A. Hypervalent Iodine in Organic Synthesis;
Academic Press: London, 1997. (b) Varvoglis, A.
Tetrahedron 1997, 53, 1179. (c) Stang, P. J.; Zhdankin, V.
V. Chem. Rev. 1996, 96, 1123. (d) Zhdankin, V. V.; Stang,
P. J. Chem. Rev. 2002, 102, 2523. (e) Wirth, T.; Hirt, U. H.
Synthesis 1999, 1271. (f) Kirschning, A. Eur. J. Org. Chem.
1998, 2267. (g) Kitamura, T.; Fujiwara, Y. Org. Prep.
Proced. Int. 1997, 29, 409. (h) Moriarty, R. M.; Prakasa, O.
Org. React. (N.Y.) 1999, 54, 273. (i) Ochiai, M. In
Chemistry of Hypervalent Compounds; Akibe, K., Ed.; VCH
Publishers: New York, 1999, Chap. 13, 359–387.
Biphenyl (3a)
Mp 68–69 °C (Lit.9 69–72 °C).
IR (KBr): 3035, 1569, 1481, 730 cm–1.
1H NMR (CDCl3): d = 7.32–7.36 (m, 2 H), 7.42–7.46 (m, 4 H),
7.58–7.61 (m, 4 H).
MS (70 eV, EI): m/z (%) = 154 (M+, 100).
p-Methylbiphenyl (3b)
Mp 43–46 °C (Lit.10 44–47°C).
(j) Ochiai, M. J. Organomet. Chem. 2000, 611, 494.
(k) Okuyama, T. Acc. Chem. Res. 2000, 35, 12.
IR (KBr): 3067, 3033, 1488, 1007, 823, 766, 690 cm–1.
1H NMR (CDCl3): d = 2.39 (s, 3 H), 7.23–7.26 (m, 2 H), 7.30–7.34
(m, 1 H), 7.40–7.44 (m, 2 H), 7.48–7.51 (m, 2 H), 7.56–7.59 (m, 2
H).
MS (70 eV, EI): m/z (%) = 168 (M+, 100).
(l) Zhdankin, V. V.; Stang, P. J. Tetrahedron 1998, 54,
10927. (m) Grushin, V. V. Chem. Soc. Rev. 2000, 29, 315.
(4) (a) Kang, S.-K.; Lee, H.-W.; Jang, S.-B.; Ho, P.-S. J. Org.
Chem. 1996, 61, 4720. (b) Kang, S.-K.; Yamagushi, Y.;
Kim, T.-H.; Ho, P.-S. J. Org. Chem. 1996, 61, 9082.
(c) Bumagin, N. A.; Luzikova, E. V.; Sukhomlinova, L. I.;
Tolstaya, T. P.; Beletskaya, I. P. Russ. Chem. Bull. 1995, 44,
385. (d) Kang, S.-K.; Jung, K.-Y.; Park, C.-H.; Jang, S.-B.
Tetrahedron Lett. 1995, 36, 8047. (e) Moriarty, R. M.; Epa,
W. R.; Awashti, A. K. J. Am. Chem. Soc. 1991, 113, 6315.
(f) Moriarty, R. M.; Epa, W. R. Tetrahedron Lett. 1992, 33,
4095. (g) Hinkle, R. J.; Poulter, G. T.; Stang, P. J. J. Am.
Chem. Soc. 1993, 115, 11626.
p-Bromobiphenyl (3c)
Mp 83–85 °C (Lit.11 85–87 °C).
IR (KBr): 3064, 3031, 1477, 1393, 1080, 830, 767, 691 cm–1.
1H NMR (CDCl3): d = 7.33–7.37 (m, 1 H), 7.42–7.46 (m, 4 H),
7.52–7.57 (m, 4 H).
MS (75 eV, EI): m/z (%) = 234 (M + 1), 233 (M+, 13.3), 232 (100).
(5) (a) Chen, Z.-C.; Jin, Y.-Y.; Stang, P. J. J. Org. Chem. 1987,
52, 4115. (b) Chen, K.; Koser, G. F. J. Org. Chem. 1991, 56,
5764. (c) Stang, P. J.; Blume, T.; Zhdankin, V. V. Synthesis
1993, 35. (d) Kurihara, Y.; Sodeoka, M.; Shibasaki, M.
Chem. Pharm. Bull. 1994, 42, 2357. (e) Ochiai, M.;
Takaoka, Y.; Nagao, Y. J. Am. Chem. Soc. 1988, 110, 6565.
(f) Ochiai, M.; Sueda, T.; Uemura, K.; Masaki, Y. J. Org.
Chem. 1995, 60, 2624. (g) Ochiai, M.; Ito, T.; Takaoka, Y.;
Masaki, Y.; Kunishima, M.; Tani, S.; Nagao, Y. Chem.
Commun. 1990, 118. (h) Bachi, M. D.; Bar-Ner, N.; Stang,
P. J.; Williamson, B. L. J. Org. Chem. 1993, 58, 7923.
(i) Ochiai, M.; Kunishima, M.; Nagao, Y.; Fuji, Y.; Shiro,
M.; Fujita, E. J. Am. Chem. Soc. 1986, 108, 8281.
(6) Beringer, F. M.; Drexler, M.; Gindler, E. M.; Lumpkin, C. C.
J. Am. Chem. Soc. 1953, 2705.
p-Methoxybiphenyl (3d)
Mp 86–87 °C (Lit.12 88 °C).
IR (KBr): 3068, 3033, 1262, 1035, 835, 761 cm–1.
1H NMR (CDCl3): d = 3.83 (s, 3 H), 6.96–6.98 (m, 2 H), 7.27–7.31
(m, 1 H), 7.38–7.42 (m, 2 H), 7.51–7.55 (m, 4 H).
MS (70 eV, EI): m/z (%) = 184 (M+, 100).
m-Nitrobiphenyl (3e)
Mp 56–58 °C (Lit.13 58–60 °C).
IR (KBr): 3064, 3036, 1536, 1362, 877, 772, 733 cm–1.
1H NMR (CDCl3): d = 7.40–7.67 (m, 6 H), 7.83–7.95 (m, 1 H),
8.11–8.23 (m, 1 H), 8.40–8.45 (m, 1 H).
MS (75 eV, EI): m/z (%) = 199 (M+, 100).
(7) Beringer, F. M.; Drexler, M.; Gindler, E. M.; Lumpkin, C. C.
J. Am. Chem. Soc. 1959, 4321.
(8) Margida, A. J.; Koser, G. F. J. Org. Chem. 1984, 49, 3643.
(9) Budavari, S.; O’Nell, M. J.; Smith, A.; Hevkelman, P. E. In
The Merck Index, 11th ed.; Merck and Co. Inc.: Rahway NJ,
1989, 3314.
2-Phenylthiophene (3f)
Oil.4a
IR (KBr): 3103, 3062, 3036, 1496, 1451, 747 cm–1.
1H NMR (CDCl3): d = 7.10–7.13 (m, 1 H), 7.30–7.34 (m, 2 H),
7.37–7.40 (m, 1 H), 7.46–7.49 (m, 2 H), 7.62–7.66 (m, 2 H).
(10) Beilstein Handbuch der Organischen Chemie, 4th ed., EIII,
Vol. 5; Springer: Berlin, 1964, 1802.
MS (70 eV, EI): m/z (%) = 160 (M+, 100).
(11) Beilstein Handbuch der Organischen Chemie, 4th ed., EIII,
Vol. 5; Springer: Berlin, 1964, 1742.
(12) Beilstein Handbuch der Organischen Chemie, 4th ed., EIII,
Vol. 6; Springer: Berlin, 1967, 3321.
(13) Beilstein Handbuch der Organischen Chemie, 4th ed., EIII,
Vol. 5; Springer: Berlin, 1964, 1750.
Acknowledgment
Financial support from the Zhejiang Province Natural Science
Foundation of China (Project Y404016) and Zhejiang Province
Education Foundation of China (Project 20040569) is greatly ap-
preciated.
Synthesis 2006, No. 6, 943–945 © Thieme Stuttgart · New York