T. Fukuda et al. / Tetrahedron 64 (2008) 328e338
337
was purified by column chromatography over Silica Gel 60N
134.07, 156.70, 157.13, 157.61, 162.15. HREIMS m/z calcd
þ
(
low powder (12.9 mg, 52%). Mp 145e210 C (dec) (sealed
hexaneeethyl acetate¼1:1wethyl acetate) to give 26 as yel-
for C H NO (M ): 401.1263. Found: 401.1254.
5
2
4
19
ꢀ
capillary); IR (KBr): 3310, 1687, 1509, 1486, 1441, 1370,
1
Acknowledgements
ꢁ
1 1
251, 1177, 1085, 835 cm ; H NMR (400 MHz, acetone-
d ): d 3.64 (s, 3H), 6.67 (d, J¼8.8 Hz, 2H), 6.76 (d,
6
We thank the Ministry of Education, Culture, Sports, Sci-
ence and Technology of Japan for financial support; Grant-
in-Aid for Scientific Research (C) (No. 18510188).
J¼8.8 Hz, 2H), 6.96 (d, J¼8.8 Hz, 2H), 7.06 (d, J¼8.8 Hz,
2
1
1
1
H), 7.14 (d, J¼3.2 Hz, 1H), 8.23 (br s, 2H), 10.90 (br s,
1
3
H);
15.77, 120.02, 121.37, 126.90, 126.97, 127.45, 129.73,
C NMR (100 MHz, acetone-d ): 50.99, 115.18,
6
References and notes
30.22, 132.80, 156.50, 157.01, 161.89. HREIMS m/z calcd
þ
ꢀ
1. For reviews, see: (a) Cironi, P.; Albericio, F.; Alvarez, M. Prog. Hetero-
for C H NO (M ): 309.1001. Found: 309.0983.
4
1
8
15
cycl. Chem. 2004, 16, 1e26; (b) Bailly, C. Curr. Med. Chem.: Anti-Cancer
Agents 2004, 4, 363e378; (c) Bellina, F.; Rossi, R. Tetrahedron 2006, 62,
4
.7.8. Methyl 1,3,4-tris(4-isopropoxyphenyl)pyrrole-2-
7
213e7256.
carboxylate (34)
Underanargonatmosphere, a suspensionof4-isopropoxyphe-
nylboronic acid (137 mg, 0.762 mmol) and powdered molecular
2
. Loya, S.; Rudi, A.; Kashman, Y.; Hizi, A. Biochem. J. 1999, 344, 85e92.
. Kashman, Y.; Koren-Goldshlager, G.; Gravalos, M. D. G.; Schleyer, M.
Tetrahedron Lett. 1999, 40, 997e1000.
3
˚
4. Quesada, A. R.; Gravalos, M. D. G.; Puentes, J. L. F. Br. J. Cancer 1996,
4, 677e682.
sieves 4 A (350 mg) in dichloromethane (5.0 mL) was stirred for
h. After successive addition of 28 (100 mg, 0.254 mmol),
pyridine (82.2 mL, 1.02 mmol), and Cu(OAc)2 (92.3 mg,
7
3
5
. (a) Facompr e´ , M.; Tardy, C.; Bal-Mahieu, C.; Colson, P.; Perez, C.;
Manzanares, I.; Cuevas, C.; Bailly, C. Cancer Res. 2003, 63, 7392e
0
8
.508 mmol) to the suspension, the mixture was stirred for
7 h. The mixture was passed through a pad of Celite and the fil-
7
399; (b) Marco, E.; Laine, W.; Tardy, C.; Lansiaux, A.; Iwao, M.;
Ishibashi, F.; Bailly, C.; Gago, F. J. Med. Chem. 2005, 48, 3796e3807;
c) Kluza, J.; Gallego, M.-A.; Loyens, A.; Beauvillain, J.-C.; Sousa-
Faro, J.-M. F.; Cuevas, C.; Marchetti, P.; Bailly, C. Cancer Res. 2006,
6, 3177e3187.
(
trate was evaporated under reduced pressure. The residuewas pu-
rified by column chromatography over Silica Gel 60N
6
(
dichloromethane) to give 34 as pale yellow semisolid (127 mg,
6
. Reddy, M. V. R.; Rao, M. R.; Rhodes, D.; Hansen, M. S. T.; Rubins, K.;
Bushman, F. D.; Venkateswarlu, Y.; Faulkner, D. J. J. Med. Chem. 1999,
42, 1901e1907.
ꢁ1
9
5%). IR (KBr): 1708, 1509, 1373, 1243, 1120, 951, 835 cm ;
1
H NMR (400 MHz, CDCl ): d 1.30 (d, J¼6.0 Hz, 6H), 1.35
3
7
8
9
. Warabi, K.; Matsunaga, S.; van Soest, R. W. M.; Fusetani, N. J. Org.
(
d, J¼6.0 Hz, 6H), 1.37 (d, J¼6.0 Hz, 6H), 3.46 (s, 3H), 4.42e
Chem. 2003, 68, 2765e2770.
. Banwell, M. G.; Goodwin, T. E.; Ng, S.; Smith, J. A.; Wong, D. J. Eur. J.
Org. Chem. 2006, 3043e3060.
4
6
7
.63 (m, 3H), 6.71 (d, J¼8.8 Hz, 2H), 6.83 (d, J¼8.8 Hz, 2H),
.92 (d, J¼8.8 Hz, 2H), 6.99 (s, 1H), 7.01 (d, J¼8.8 Hz, 2H),
13
.18 (d, J¼8.8 Hz, 2H), 7.27 (d, J¼8.8 Hz, 2H); C NMR
. Banwell, M. G.; Flynn, B. L.; Hamel, E.; Hockless, D. C. R. Chem.
Commun. 1997, 207e208.
(
100 MHz, CDCl ): 22.08, 22.10, 22.15, 50.83, 69.74, 69.83,
3
1
0. Liu, J.-H.; Yang, Q.-C.; Mak, T. C. W.; Wong, H. N. C. J. Org. Chem.
000, 65, 3587e3595.
7
1
1
0.22, 115.06, 115.52, 115.57, 121.25, 124.96, 126.49, 126.65,
26.98, 127.16, 129.33, 131.03, 131.83, 133.78, 156.31,
56.75, 157.29, 161.73. HREIMS m/z calcd for C H NO
2
1
1. F u¨ rstner, A.; Krause, H.; Thiel, O. R. Tetrahedron 2002, 58, 6373e6380.
2. (a) Banwell, M. G.; Bray, A. M.; Edwards, A. J.; Wong, D. J. J. Chem.
Soc., Perkin Trans. 1 2002, 1340e1343; (b) Heinrich, M. R.; Steglich,
W.; Banwell, M. G.; Kashman, Y. Tetrahedron 2003, 59, 9239e9247.
3. Iwao, M.; Takeuchi, T.; Fujikawa, N.; Fukuda, T.; Ishibashi, F. Tetra-
hedron Lett. 2003, 44, 4443e4446.
3
3
37
5
1
þ
M ): 527.2672. Found: 527.2678.
(
1
1
4
.7.9. Lamellarin R (27)
Under an argon atmosphere, a heptane solution of BCl3
1.0 M, 358 mL, 0.358 mmol) was added dropwise to a solution
4. (a) Fujikawa, N.; Ohta, T.; Yamaguchi, T.; Fukuda, T.; Ishibashi, F.; Iwao,
M. Tetrahedron 2006, 62, 594e604; (b) Yamaguchi, T.; Fukuda, T.;
Ishibashi, F.; Iwao, M. Tetrahedron Lett. 2006, 47, 3755e3757.
(
of 34 (21.0 mg, 0.0398 mmol) in dichloromethane (5.0 mL) at
ꢀ
ꢁ
78 C. After being stirred for 30 min at this temperature, the
15. Handy, S. T.; Zhang, Y.; Bregman, H. J. Org. Chem. 2004, 69, 2362e
366.
ꢀ
2
reaction mixture was allowed to warm to 0 C and stirred for
an additional 2 h. The mixture was quenched with water and
extracted with ethyl acetate. The extract was washed with brine,
1
1
1
6. Smith, J. A.; Ng, S.; White, J. Org. Biomol. Chem. 2006, 4, 2477e2482.
7. Zonta, C.; Fabris, F.; De Lucchi, O. Org. Lett. 2005, 7, 1003e1006.
8. (a) Muchowski, J. M.; Naef, R. Helv. Chim. Acta. 1984, 67, 1168e1172;
(b) Alvarez, A.; Guzm a´ n, A.; Ruiz, A.; Velarde, E.; Muchowski, J. M.
J. Org. Chem. 1992, 57, 1653e1656; (c) Shum, P. W.; Kozikowski,
A. P. Tetrahedron Lett. 1990, 31, 6785e6788; (d) Sugiura, K.; Ushiroda,
K.; Johnson, M. T.; Miller, J. S.; Sakata, Y. J. Mater. Chem. 2000, 10,
dried over Na SO , and evaporated under reduced pressure. The
2
residue was purified by column chromatography over Silica Gel
6
brown powder (9.2 mg, 58%). Mp 140e240 C (dec) (sealed
capillary); IR (KBr): 3347, 1670, 1611, 1519, 1441, 1373,
4
0N (hexaneeethyl acetate¼1:1wethyl acetate) to give 27 as
ꢀ
2
507e2514; (e) Synder, L. B.; Meng, Z.; Mate, R.; D’Andrea, S. V.;
Marinier, A.; Quesnelle, C. A.; Gill, P.; DenBleyker, K. L.; Fung-Tomc,
J. C.; Frosco, M.; Martel, A.; Barrett, J. F.; Bronson, J. J. Bioorg. Med.
Chem. Lett. 2004, 14, 4735e4739.
ꢁ
1
1
1
238, 1130, 834 cm
d 3.40 (s, 3H), 6.68 (d, J¼8.7 Hz, 2H), 6.78 (d, J¼8.7 Hz,
H), 6.92 (d, J¼8.7 Hz, 2H), 7.00 (d, J¼8.7 Hz, 2H), 7.08 (d,
J¼8.7 Hz, 2H), 7.12 (s, 1H), 7.24 (d, J¼8.7 Hz, 2H), 8.20 (br
;
H NMR (400 MHz, acetone-d6):
1
9. (a) Urban, S.; Butler, M. S.; Capon, R. J. Aust. J. Chem. 1994, 47, 1919e
2
1
924; (b) Urban, S.; Hobbs, L.; Hooper, J. N. A.; Capon, R. J. Aust. J.
Chem. 1995, 48, 1491e1494.
1
3
s, 1H), 8.28 (br s, 1H), 8.61 (br s, 1H); C NMR (100 MHz, ac-
etone-d ): 50.90, 115.28, 115.83, 116.09, 122.42, 125.82,
2
0. Boger, D. L.; Boyce, C. W.; Labroli, M. A.; Sehon, C. A.; Jin, Q. J. Am.
6
Chem. Soc. 1999, 121, 54e62.
ꢀ
1
26.64, 126.85, 127.17, 127.55, 130.24, 131.24, 132.71,
21. Marfil, M.; Albericio, F.; Alvarez, M. Tetrahedron 2004, 60, 8659e8668.