Y. Ikeda et al. / Tetrahedron Letters 45 (2004) 487–489
489
methylated natural product,14;15 and this revealed the
(R)-configuration of the biaryl moiety in the synthetic
compound. Cleavage of the methyl ethers of 2 under
several reaction conditions was pointless because the
cleavage of the anomeric ester competed against the
demethylations.16
7. (a) Liu, K. C.; Lin, M.; Lee, S.; Chiou, J.; Ren, S.; Lien, E.
J. Planta Med. 1999, 65, 43–46; (b) Lim, Y. A.; Mei, M.
C.; Kusumoto, I. T.; Miyashiro, H.; Hattori, M.; Gupta,
M. P.; Correa, M. Phytother. Res. 1997, 11, 22–27.
8. (a) Cheng, J.; Lin, T.; Hsu, F. Can. J. Physiol. Pharmacol.
1995, 73, 1425–1429; (b) Lin, T. C.; Hsu, F. L.; Cheng,
J. T. J. Nat. Prod. 1993, 56, 629–632.
9. Okabe, S.; Suganuma, M.; Imayoshi, Y.; Taniguchi, S.;
Yoshida, T.; Fujiki, H. Biol. Pharm. Bull. 2001, 24, 1145–
1148.
In conclusion, nonamethylcorilagin was synthesized,
which contains a 3,6-bridged HHDP group with a 1C4/B
glucose core, one of the common structures in the
ellagitannin family. The construction of the 3,6-bridged
biaryl moiety required pre-opening of the pyranose ring.
The Ullmann coupling took place in a highly stereo-
selective manner to give the (R)-HHDP moiety.
10. (a) Feldman, K. S.; Ensel, S. M.; Minard, R. D. J. Am.
Chem. Soc. 1994, 116, 1742–1745; (b) Quideau, S.;
Feldman, K. S. Chem. Rev. 1996, 96, 475–503; (c)
Khanbabaee, K.; van Ree, T. Synthesis 2001, 1585–1610.
11. Formations of 2,4-HHDP bridge have been reported
starting from substrates whose ring conformation are pre-
fixed with the 1,6- or 3,6-ethereal bridge structures. (a)
Dai, D.; Martin, O. R. J. Org. Chem. 1998, 63, 7628–7633;
(b) Feldman, K. S.; Iyer, M. R.; Liu, Y. J. Org. Chem.
2003, 68, 7433–7438.
Acknowledgements
Financial supports by the Naito Foundation (Japan),
the Sunbor Grant (Suntory Institute for Bioorganic
Research, Japan), the Cosmetology Research Founda-
tion (Japan) are gratefully acknowledged. Thanks are
also due to Professor Takashi Yoshida (Okayama Uni-
versity, Japan) for providing the natural corilagin and
his helpful discussions, and to Dr. Hiroshi Imagawa
(Tokushima Bunri University, Japan) for assistance with
the structure determination of 15.
12. Motawia, M. S.; Olsen, C. E.; Enevoldsen, K.; Marcussen,
J.; Møller, B. L. Carbohydr. Res. 1995, 277, 109–123.
13. Although we reported the similar 3,6-selective protection
of 8 with bulky silyl protecting groups, the following
benzylation of the 2,4-hydroxyl groups was difficult due to
the bulkiness of the protections. Ikeda, Y.; Furukawa, K.;
Yamada, H. Carbohydr. Res. 2002, 337, 1499–1501.
14. (a) Yoshida, T.; Okuda, T. Heterocycles 1980, 14, 1743–
1749; (b) Tanaka, T.; Nonaka, G.; Nishioka, I. Phyto-
chemistry 1985, 24, 2075–2078; (c) Saijo, R.; Nonaka, G.;
Nishioka, I. Chem. Pharm. Bull. 1989, 37, 2624–2630.
15. As a supplement for the partial lack of detailed spectral
data in the literature, the following data should be listed.
References and Notes
22
22
½aꢀ )154.7ꢁ (c 0.10, CHCl3), lit.14c ½aꢀ )166.9ꢁ (c 0.8,
D
D
CHCl3); IR (ZnSe) 3441, 2944, 2847, 1744, 1709, 1591,
1. Hexahydroxydiphenoyl group is a trivial name of 6,60-
dicarbonyl-2,20,3,30,4,40-hexahydroxydiphenoyl group.
2. Okuda, T.; Yoshida, T.; Hatano, T. Hydrolyzable Tannins
and Related Polyphenols. In Progress in the Chemistry of
Organic Natural Products, Herz, W., Kirby, G. W.,
Moore, R. E., Steglich, W., Tamm, Ch. Eds.; Springer:
Wein, 1995; Vol. 66; pp 1–117.
1462, 1338, 1209, 1167, 1121, 1101 cmꢁ1
;
1H NMR
(400 MHz in acetone-d6) d 7.23 (2H, s), 6.92 (1H, s), 6.88
(1H, s), 6.46 (1H, dd, J ¼ 1:0, 1.0 Hz, H-1), 5.24 (1H, d,
J ¼ 6:9 Hz, 4-OH), 5.23 (1H, d, J ¼ 8:6 Hz, 2-OH), 5.08
(1H, dd, J ¼ 11:6, 10.4 Hz, H-6), 4.87 (1H, dddd, J ¼ 3:4,
2.5, 1.0, 1.0, H-3), 4.62 (1H, dddd, J ¼ 11:6, 7.8, 1.1,
1.0 Hz, H-5), 4.54 (1H, dddd, J ¼ 6:9, 3.4, 1.4, 1.1 Hz, H-
4), 4.33 (1H, dd, J ¼ 10:4, 7.8 Hz, H-6), 4.18 (1H, dddd,
J ¼ 8:6, 2.5, 1.4, 1.0 Hz, H-2), 3.91 (3H, s, OCH3), 3.90
(3H, s, OCH3), 3.90 (3H, s, OCH3), 3.83 (3H, s, OCH3),
3.70 (3H, s, OCH3), 3.67 (2 · 3H, s, OCH3), 3.66 (3H, s,
OCH3), 3.20 (3H, s, OCH3); 13C NMR (100 MHz in
acetone-d6) d 168.4 (C), 166.7 (C), 165.1 (C), 154.4 (2 · C),
154.3 (C), 153.6 (C), 153.4 (C), 153.3 (C), 145.8 (C), 144.9
(C), 144.0 (C), 129.9 (C), 128.1 (C), 125.0 (C), 124.6 (C),
123.0 (C), 108.8 (CH), 107.8 (2 · CH), 106.0 (CH), 96.7
(CH), 75.1 (CH), 69.5 (CH), 67.6 (CH), 64.7 (CH2), 61.7
(CH), 61.0 (CH3), 60.9 (CH3), 60.7 (CH3), 60.6 (CH3),
56.9 (2 · CH3), 56.5 (CH3), 55.6 (2 · CH3); HRMS (ESI)
m=z calcd for C36H40O18 (Mþ+Na) 783.2112, found
783.2124.
3. (a) Jochims, J. C.; Taigel, G.; Schmidt, O. T. Justus
ꢀ
Liebigs Ann. Chem. 1968, 717, 169–185; (b) Latte, K. P.;
Kolodziej, H. Phytochemistry 2000, 54, 701–708; (c)
Gaudreaut, R.; Van, D. V.; Theo, G. M.; Whitehead,
M. A. J. Mol. Model. 2002, 8, 73–80.
4. (a) Schmidt, O. T.; Lademann, R. Justus Liebigs Ann.
Chem. 1951, 571, 232–237; (b) Schmidt, O. T.; Schmidt, D.
M.; Herok, J. Justus Liebigs Ann. Chem. 1954, 587, 67–74;
(c) Okuda, T.; Yoshida, T.; Hatano, T. Tetrahedron Lett.
1980, 21, 2561–2564.
5. Shimizu, M.; Shiota, S.; Mizushima, T.; Ito, H.; Hatano,
T.; Yoshida, T.; Tsuchiya, T. Antimicrob. Agents Chemo-
ther. 2001, 3198–3201.
6. (a) Burapadaja, S.; Bunchoo, A. Planta Med. 1995, 61,
365–366; (b) Adesina, S. K.; Idowu, O.; Ogundaini, A. O.;
Oladimeji, H.; Olugbade, T. A.; Onawunmi, G. O.; Pais,
M. Phytother. Res. 2000, 14, 371–374.
€
16. Khanbabaee, K.; Lotzerich, K. Tetrahedron 1997, 53,
10725–10732.