LETTER
Synthesis of Functionalized Biaryls
965
References and Notes
O
O
1. Br2, CH2Cl2
1 h, 0 °C
(1) (a) Kawahara, N.; Masuda, K.; Sekita, S.; Satake, M. Chem.
Pharm. Bull. 2001, 49, 771. (b) Inouye, H.; Nakamura, Y.
Tetrahedron 1971, 27, 1951. (c) Kanamori, H.; Sakamoto,
I.; Mizuta, M.; Tanaka, O. Chem. Pharm. Bull. 1986, 34,
1663. (d) Lacaille-Dubois, M.-A.; Galle, K.; Wagner, H.
Planta Med. 1996, 62, 365. (e) Kawahara, N.; Masuda, K.;
Sekita, S.; Satake, M. Chem. Pharm. Bull. 2001, 49, 771.
(f) Li, J.-C.; Feng, L.; Sun, B.-H.; Ikeda, T.; Nohara, T. Biol.
Pharm. Bull. 2005, 28, 534.
EtO
EtO
2. Et3N, 15 min
Br
7a,b
R1
R1
3a,e
TMSO
R3
OTMS
R2
OH
O
R3
R2
4a,h
(2) (a) Shamma, M.; Tomlinson, H. H. J. Org. Chem. 1978, 43,
2852. (b) Ishii, H.; Ishikawa, T.; Ishikawa, Y.-i.; Sakamoto,
M.; Ishikawa, M.; Takahashi, T. Chem. Pharm. Bull. 1984,
32, 2984. (c) Matsuhashi, R.; Satou, T.; Koike, K.;
Yokosuka, A.; Mimaki, Y.; Sashida, Y.; Nikaido, T. Planta
Med. 2002, 68, 169.
(3) (a) Holker, J. S. E.; O’Brien, E.; Simpson, T. J. J. Chem.
Soc., Perkin Trans. 1 1983, 1365. (b) Stinson, E. E.;
Moreau, R. A. Phytochemistry 1986, 25, 2721. (c) Abe, H.;
Nishioka, K.; Takeda, S.; Arai, M.; Takeuchi, Y.; Harayama,
T. Tetrahedron Lett. 2005, 46, 3197. (d) Zhang, H.-W.;
Huang, W.-Y.; Song, Y.-C.; Chen, J.-R.; Tan, R.-X. Helv.
Chim. Acta 2005, 88, 2861. (e) Tanahashi, T.; Kuroishi, M.;
Kuwahara, A.; Nagakura, N.; Hamada, N. Chem. Pharm.
Bull. 1997, 45, 1183.
TiCl4, CH2Cl2
–78 to 20 °C, 12 h
Br
R1
8a–c
Scheme 4 Synthesis of 5-bromo-6-arylsalicylates 8a–c
Table 2 Synthesis of 5-Bromo-6-arylsalicylates 8a–c
3
7
4
8
R1
R2
R3
Yield of 7 Yield of 8
(%)a
(%)a
3a 7a
3a 7a
4a
4h
4h
8a
8b
8c
H
H
OMe
H
61
50
OMe Me
52
(4) (a) Kamisuki, S.; Takahashi, S.; Mizushina, Y.; Hanashima,
S.; Kuramochi, K.; Kobayashi, S.; Sakaguchi, K.; Nakata,
T.; Sugawara, F. Tetrahedron 2004, 60, 5695. (b) Uchida,
R.; Tomoda, H.; Dong, Y.; Omura, S. J. Antibiot. 1999, 52,
572. (c) Khan, K. A.; Shoeb, A. Phytochemistry 1984, 23,
765.
3e
7b
OMe OMe Me
36
48
a Yields of isolated products.
(5) (a) Takechi, M.; Tanaka, Y.; Takehara, M.; Nonaka, G.-I.;
Nishioka, I. Phytochemistry 1985, 24, 2245. (b) Tanaka, T.;
Tachibana, H.; Nonaka, G.-i.; Nishioka, I.; Hsu, F.-L. Chem.
Pharm. Bull. 1993, 41, 1214. (c) Yokozawa, T.; Chen, C. P.;
Tanaka, T.; Kitani, K. Biochem. Pharmacol. 2002, 63, 853.
(6) Gould, S. J.; Melville, C. R.; Chen, J. Tetrahedron 1997, 53,
4561.
(7) Miles, D. H.; Randle, S.; Shakir, R.; Atwood, J. L. J. Org.
Chem. 1981, 46, 2813.
(8) Lin, Y.-L.; Wu, Y.-M.; Kuo, Y.-H. Phytochemistry 1997, 45,
1057.
(9) Metal-Catalyzed Cross-Coupling Reactions; de Meijere, A.;
Diederich, F., Eds.; Wiley-VCH: Weinheim, 2004.
(10) (a) Chan, T.-H.; Brownbridge, P. J. Am. Chem. Soc. 1980,
102, 3534. (b) Brownbridge, P.; Chan, T.-H.; Brook, M. A.;
Kang, G. J. Can. J. Chem. 1983, 61, 688.
(11) Review of 1,3-bis(trimethylsilyloxy)-1,3-dienes in general:
Figure 2 Molecular structure of 8a (only one of the two symmetry-
independent molecules is shown)
Langer, P. Synthesis 2002, 441.
(12) Review: Feist, H.; Langer, P. Synthesis 2007, 327.
(13) Andersson, C.-M.; Hallberg, A. J. Org. Chem. 1988, 53,
4257.
(14) Typical Procedure for the Heck Reaction of Ethylvinyl
Ether with Acid Chlorides
context, the first [3+3] cyclizations of brominated sub-
strates are reported.
To a mixture of ethylvinyl ether (2.90 g, 40.0 mmol) and of
Et3N (1.20 g, 12.0 mmol) in a pressure tube was added
Pd(OAc)2 (20 mg, 0.1 mmol) under Ar atmosphere. The
mixture was stirred until a clear yellow solution was formed.
To the mixture were added benzoylchloride (1.20 g, 10.0
mmol), and the mixture was stirred at 80 °C for 24 h. The
mixture was poured into Et2O (50 mL) and the solid
(triethylammonium hydochloride) was filtered off. The
filtrate was concentrated under reduced pressure and the
residue was purified by chromatography (SiO2, heptanes–
EtOAc = 10:1 → 5:1) to give 3a as a slightly yellow oil (3.80
g, 55%).
Acknowledgment
Financial support by the State of Mecklenburg-Vorpommern is gra-
tefully acknowledged.
Synlett 2008, No. 7, 963–966 © Thieme Stuttgart · New York