2638
P. Pahari et al. / Tetrahedron Letters 48 (2007) 2635–2638
15. Mitchell, A. S.; Russell, R. A. Tetrahedron 1997, 53, 4387–
4410.
tors for the Hauser annulation. With the successes
described in entries 4, 6 and 7, we have established that
the annulation with sulfonylphthalides can be extended
to the synthesis of anthraquinone-steroid hybrids22
(i.e., 23), fused indoloquinones (i.e., 28) and fluoroana-
logs of angucyclines (i.e., 31).
16. Representative annulation procedure: To a stirred solution
of 1 (82 mg, 0.3 mmol) in THF (4 mL) at À60 ꢁC
(chloroform/liquid N2 bath) under an inert atmosphere
was added solid lithium tert-butoxide (72 mg, 0.9 mmol).
The resulting yellowish solution was stirred at À60 ꢁC for
15 min, after which a solution of 13 (50 mg, 0.3 mmol) in
THF (2 mL) was added. The cooling bath was removed
after about 30 min at À60 ꢁC and the reaction mixture was
brought to room temperature and further stirred for 2–3 h.
The reaction was then quenched with 10% aqueous NH4Cl
solution (5 mL) and the residue diluted with ether
(10 mL). The aqueous layer was extracted with ether
(2 · 10 mL) and the combined organic layers were washed
with H2O (2 · 10 mL), brine (5 mL), dried (Na2SO4) and
concentrated. The crude product was purified by column
chromatography on silica gel (10% ethyl acetate in
petroleum ether).
Acknowledgements
Financial support for this work was provided by
the CSIR, New Delhi and the DST, New Delhi. P.P.
gratefully acknowledges the receipt of his senior
research fellowship from the CSIR, New Delhi.
References and notes
17. Permutter, H. D.; Kristol, D. S.; Tomkins, R. P. T. J. Am.
Chem. Soc. 1984, 106, 341–343.
18. Mal, D.; Dey, S. Tetrahedron 2006, 62, 9589–9602.
19. Mal, D.; Senapati, B.; Pahari, P. Tetrahedron, in review.
20. Selected data: Compound 23 (red solid): mp 205–207 ꢁC;
mmax (KBr, cmÀ1): 1735, 1635, 1272, 769; 1H NMR
(CDCl3, 200 MHz): d 12.88 (s, 1H), 8.26–8.12 (m, 2H),
7.80–7.73 (m, 2H), 7.02 (s, 1H), 3.49–3.41 (m, 1H), 3.10–
2.75 (m, 1H), 2.60–2.45 (m, 1H), 2.25–1.10 (m, 12H), 0.92
(s, 3H); 13C NMR (CDCl3, 50 MHz): d 220.2, 188.7, 186.6,
160.4, 149.8, 137.9, 135.2, 134.6, 133.8, 133.5, 132.2, 127.2,
126.2, 123.3, 116.3, 50.4, 48.6, 46.3, 40.3, 36.0, 35.8, 32.4,
30.6, 23.9, 21.5, 14.5; HRMS ESI: for C26H25O4 [M+H]+
calcd. 401.1753, found 401.1720. Compound 25 (light
yellow liquid): mmax (KBr, cmÀ1): 2954, 1735, 1677, 1436,
1. (a) Thomson, R. H. Naturally Occurring Quinones III.
Recent Advances; Chapman & Hall: UK, 1987; (b)
Thomson, R. H. Naturally Occurring Quinones IV. Recent
Advances; Chapman & Hall: UK, 1997.
2. Dhananjeyan, M. R.; Milev, Y. P.; Kron, M. A.; Nair, M.
G. J. Med. Chem. 2005, 48, 2822–2830.
3. Szechner, B.; Achmatowicz, O.; Maurin, J. K. Tetrahedron
2005, 61, 1981–1985.
4. Malerich, J. P.; Maimone, T. J.; Elliot, G. I.; Trauner, D.
J. Am. Chem. Soc. 2005, 127, 6276–6283.
5. (a) Pirrung, M. C.; Liu, Y.; Deng, L.; Halstead, D. K.; Li,
Z.; May, J. F.; Wedel, M.; Austin, D. A.; Webster, N. J.
G. J. Am. Chem. Soc. 2005, 127, 4609–4624; (b) Jung, Y.
S.; Joe, B. Y.; Cho, S. J.; Konishi, Y. Bioorg. Med. Chem.
Lett 2005, 15, 1125–1129.
1
1068, 883; H NMR (CDCl3, 200 MHz): d 6.80 (dd, 1H,
J = 10.1, 6.2 Hz), 6.24 (dt, 1H, J = 10.1, 1.5 Hz), 6.08 (s,
1H), 3.70 (s, 3H), 3.10–2.85 (m, 2H), 2.80–2.45 (m, 3H),
2.40–2.35 (m, 2H); 13C NMR (CDCl3, 50 MHz): d 185.2
(d, J = 4.9 Hz), 174.0, 156.4 (d, J = 18.7 Hz), 144.7 (d,
J = 21.0 Hz), 129.8 (d, J = 7.6 Hz), 124.6 (d, J = 4.6 Hz),
86.6 (d, J = 164.4 Hz), 52.1, 39.7 (d, J = 24.6 Hz), 37.9,
30.7, 29.6; HRMS ESI: for C12H14FO3 [M+H]+ calcd.
225.0927, found 225.0907; for C10H10FO [MÀCOOMe]+
calcd. 165.0716, found 165.0672. Compound 29 (yellow
solid): mp 173–175 ꢁC; mmax (KBr, cmÀ1): 1650, 1584,
1240, 973, 752; 1H NMR (CDCl3, 200 MHz): d 8.41 (d,
1H, J = 7.3 Hz), 7.50–7.26 (m, 3H), 6.97 (s, 1H), 4.20 (s,
3H), 3.99 (s, 3H), 3.50–3.30 (m, 2H), 3.00–2.75 (m, 2H),
1.90–1.65 (m, 4H); 13C NMR (CDCl3, 50 MHz): d 184.4,
179.7, 174.7, 158.3, 147.4, 139.3, 135.4, 134.0, 133.7, 126.5,
123.8, 123.6, 120.9, 118.5, 118.1, 110.5, 56.3, 31.9, 29.7,
28.9, 23.5, 21.9; HRMS ESI: for C22H20NO3 [M+H]+
calcd. 346.1443, found 346.1405. Compound 31 (red
solid): mp 205–207 ꢁC; mmax (KBr, cmÀ1): 1648, 1570,
6. (a) Snieckus, V. Chem. Rev. 1990, 90, 879–933; (b)
Mitchell, A. S.; Russell, R. A. Tetrahedron 1995, 51,
5207–5236; (c) Brimble, M. A.; Nairn, M. R.; Prabaharan,
H. Tetrahedron 2000, 56, 1937–1992.
7. (a) Snider, B. B.; Gao, X. J. Org. Chem. 2005, 70, 6863–
6869; (b) Nicolaou, K. C.; Lim, Y. H.; Papageorgiou, C.
D.; Piper, J. L. Angew. Chem., Int. Ed. 2005, 44, 7917–
7921; (c) Mal, D.; Patra, A.; Roy, H. Tetrahedron Lett.
2004, 45, 7895–7898.
8. (a) Ghorai, S. K.; Roy, H. N.; Bandopadhyay, M.; Mal,
D. J. Chem. Res. (S) 1999, 30–31; (b) Hauser, F. M.;
Dorsch, W. A.; Mal, D. Org. Lett. 2002, 4, 2237–2240.
9. Russell, R. A.; Pilley, B. A.; Irvine, R. W.; Warrener, R.
N. Aust. J. Chem. 1987, 40, 311–323.
10. (a) Bordwell, F. G.; Brannen, W. T. J. Am. Chem. Soc.
1964, 86, 4645–4650; (b) Mal, D.; Roy, H. N.; Hazra, N.
K.; Adhikari, S. Tetrahedron 1997, 53, 2177–2184; (c) Mal,
D.; Roy, H. N. J. Chem. Soc., Perkin Trans. 1 1999, 3167–
3171.
1
1340, 952, 759; H NMR (CDCl3, 200 MHz): d 12.52 (s,
1H), 9.60 (d, 1H, J = 8.2 Hz), 8.30–8.22 (m, 2H), 8.10–
11. (a) Sasaki, T.; Gomi, D.; Sezaki, M.; Takeuchi, Y.;
Kodama, Y.; Kawamura, K. J. Antibiot. 1988, 41, 843–
848; (b) Imamura, N.; Kakinuma, K.; Ikekawa, N.;
Tanaka, H.; Omura, S. J. Antibiot. 1982, 35, 602–606;
(c) Tsuchida, T.; Sawa, R.; Takahasi, Y.; Linuma, H.;
Sawa, T.; Naganawa, H.; Takeuchi, T. J. Antibiot. 1995,
48, 1148–1152.
8.05 (m, 1H), 7.85–7.75 (m, 2H), 7.65–7.59 (m, 2H); 13C
NMR (CDCl3, 50 MHz):
d 190.1, 184.1, 149.7 (d,
J = 258.9 Hz), 143.6 (d, J = 12.7 Hz), 135.3, 134.8,
133.5, 131.7, 129.6 (d, J = 3.1 Hz), 128.7, 128.4 (d,
J = 2.2 Hz), 128.1, 127.9 (d, J = 22.2 Hz), 127.4, 126.4,
125.2, 120.6 (d, J = 4.3 Hz), 119.4 (d, J = 6.6 Hz); HRMS
ESI: for C18H10FO3 [M+H]+ calcd. 293.0614, found
293.0583.
12. Pravst, I.; Iskra, M. P.; Jereb, M.; Zupan, M.; Stavber, S.
Tetrahedron 2006, 62, 4474–4481.
21. Carreno, M. C.; Lopez, M. G.; Urbano, A. Angew. Chem.,
Int. Ed. 2006, 45, 2737–2741.
22. De Riccardis, F.; Izzo, I.; Di Filippo, M.; Sodano, G.;
Acquisto, F. D.; Carnuccio, R. Tetrahedron 1997, 53,
10871–10882.
13. Karam, O.; Martin-Mingot, A.; Jouannetaud, M.-P.;
Jacquesy, J.-C.; Cousson, A. Tetrahedron 2004, 60,
6629–6638.
14. Stavber, G.; Zupan, M.; Jereb, M.; Stavber, S. Org. Lett.
2004, 6, 4973–4976.