E. Duval, G. D. Cuny / Tetrahedron Letters 45 (2004) 5411–5413
5413
3. Kato, S.; Hawai, H.; Kawasaki, T.; Toda, Y.; Urata, T.;
Hatakawa, Y. J. Antibiot. 1989, 42, 1879.
4. Kotoda, N.; Shin-ya, K.; Furibata, K.; Hayakawa, Y.;
Seto, H. J. Antibiot. 1997, 50, 770.
€
5. For a review on carbazoles, see: Knolker, H.-J.; Reddy,
K. R. Chem. Rev. 2002, 102, 4303.
6. Cox, E. D.; Cook, J. M. Chem. Rev. 1995, 95, 1797.
7. Huang, Q.; Larock, R. C. J. Org. Chem. 2003, 68, 7342.
8. Witulski, B.; Alayrac, C. Angew. Chem., Int. Ed. 2002, 41,
3281.
R1
OH
Me
R1
OMe
Me
(a)
N
H
N
H
10a : R1 = H
10g : R1 = Cl
2 : R1 = H
3 : R1 = Cl
(b)
R
9. Abbiati, G.; Beccalli, E. M.; Marchesini, A.; Rossi, E.
Synthesis 2001, 16, 2477.
10. Dulenko, V. I.; Tolunov, S. V.; Alekseev, N. N. Chem.
Heterocycl. Comp. 1981, 1010.
11. Dulenko, V. I.; Luk’yanenko, V. I.; Kibal’nyi, A. V.;
Malienko, A. A.; Nikolyukin, Y. A. Chem. Heterocycl.
Comp. 1985, 302.
Me
13: R=OTf
N
H
(c)
(d)
14: R=H
15: R=CCSiMe3
Scheme 4. Further transformations of 3-hydroxycarbazoles. Reagents
and conditions: (a) MeI, K2CO3, acetone, reflux; (b) Tf2O, 2,6-lutidine,
CH2Cl2, 90%. (c) Pd(OAc)2, PPh3, Et3N, HCO2H, DMF, 86%; (d)
Pd(PPh3)2Cl2, CuI, Et3N, HCCTMS, DMF, 87%.
12. Wei, W.-G.; Yao, Z.-J. Tetrahedron 2003, 59, 6621.
€
€
13. Knolker, H.-J.; Knoll, J. Chem. Commun. 2003, 1170.
14. Mahboobi, S.; Eibler, E.; Koller, M.; Sumar, K. C. S.;
Popp, A. J. Org. Chem. 1999, 64, 4697.
15. Dillard, R. D.; Bach, N. J.; Draheim, S. E.; Berry, D. R.;
Carlson, D. G.; Chirgadze, N. Y.; Clawson, D. K.;
Hartley, L. W.; Johnson, L. M.; Jones, N. D.; McKinney,
E. R.; Mihelich, E. D.; Olkowski, J. L.; Schevitz, R. W.;
Smith, A. C.; Snyder, D. W.; Sommers, C. D.; Wery, J.-P.
J. Med. Chem. 1996, 39, 5119.
thuscompleted in five tsepsfrom readily available
indole-3-acetic acids.18 Carbazole 10a hasalos been
converted into derivatives 14 and 15 utilizing palladium-
catalyzed reactions.
16. (a) Moody, C. J.; Shah, P.; Knowles, P. J. Chem. Soc.,
Perkin Trans. 1 1988, 3249; (b) Kazembe, T. C.-G.;
Taylor, D. A. Tetrahedron 1980, 36, 2125; (c) Ihara, M.;
Taniguchi, N.; Noguchi, K.; Fukumoto, K.; Kametani, T.
J. Chem. Soc., Perkin Trans. 1 1988, 1277.
17. Moody, C. J. Syntlett 1994, 681.
18. For other syntheses of hyellazoles, see: (a) Witulski, B.;
Alayrac, C. Angew. Chem., Int. Ed. 2002, 41, 3281; (b)
In conclusion, a convergent route to highly substituted
carbazolesand b-carbolinesvia diketoindoles 9 was
devised. In addition, the application of this methodol-
ogy to the synthesis of the natural products hyellazole
and 6-chlorohyellazole was also presented. Further
applications of this methodology for the synthesis of
other highly substituted carbazole and b-carboline nat-
ural and non-natural compoundsare underway.
€
Knolker, H.-J.; Baum, E.; Hopfmann, T. Tetrahedron
1999, 55, 10391; (c) Choshi, T.; Sada, T.; Fujimoto, H.;
Nagayama, C.; Sugino, E.; Hibino, S. J. Org. Chem. 1997,
62, 2535; (d) Choshi, T.; Sada, T.; Fujimoto, H.; Naga-
yama, C.; Sugino, E.; Hibino, S. Tetrahedron Lett. 1996,
Supplementary data
€
37, 2593; (e) Knolker, H.-J.; Baum, E.; Hopfmann, T.
Detailed experimental proceduresand compound char-
acterizationsprovided.
Tetrahedron Lett. 1995, 36, 5339; (f) Beccalli, E. M.;
Marchesini, A.; Pilati, T. J. Chem. Soc., Perkin Trans. 1
1994, 579; (g) Kawasaki, T.; Nonaka, Y.; Akahane, M.;
Maeda, N.; Sakamoto, M. J. Chem. Soc., Perkin Trans. 1
1993, 1777; (h) Moody, C. J.; Shah, P. J. Chem. Soc.,
Perkin Trans. 1 1989, 376, p 2463; (i) Danheiser, R. L.;
Brisbois, R. G.; Kowalczyk, J. J.; Miller, R. F. J. Am.
Chem. Soc. 1990, 112, 3093; (j) Kawasaki, T.; Nonaka, Y.;
Sakamoto, M. Chem. Commun. 1989, 43; (k) Takano, S.;
Suzuki, Y.; Ogasawara, K. Heterocycles 1981, 16, 1479; (l)
Kano, S.; Sugino, E.; Hibino, S. Chem. Commun. 1980,
1241.
Acknowledgements
Financial support was provided by the Harvard Center
for Neurodegeneration and Repair (HCNR).
References and notes
19. (a) The following compounds have been described else-
where: (a) 10a Ghoshi, T.; Sada, T.; Fujimoto, H.;
Nagayama, C.; Sugino, E.; Hibino, S. J. Org. Chem.
1997, 62, 2535; (b) 10d Knoelker, H.-J.; Bauermeister, M.;
Pannek, J.-B.; Blaeser, D.; Boese, R. Tetrahedron 1993, 49,
841; (c) 11b Lin, G.; Zhang, A. Tetrahedron 2000, 56,
7163.
1. Doyle, T. W.; Balitz, R. E.; Nettletone, D. E.; Gould, S. J.;
Tann, C. H.; Moews, A. E. Tetrahedron Lett. 1981, 22,
4595.
2. Cardellina, J. H.; Kirkup, M. P.; Moore, R. E.; Mynderse,
J. S.; Self, K.; Simmons, C. J. Tetrahedron Lett. 1979, 20,
4915.