1234
X. Cai et al. / Carbohydrate Research 345 (2010) 1230–1234
4.15 (dd, 1H, J2,3 2.3 Hz, J1,2 6.4 Hz, H-2), 3.95 (m, 1H, H-5), 3.79 (s,
3H, CH3O), 1.56, 1.42 (2s, 6H, C(CH3)2), 1.32, 1.23 (2d, 6H, J 6.5 Hz,
H-6, H-60). Anal. Calcd for C36H40O12: C, 65.05; H, 6.07. Found: C,
64.82; H, 6.31.
uene. The crude mixture thus obtained was purified by flash
chromatography using petroleum ether–EtOAc (3:1) to get a white
foam. Then the white foam was dissolved in satd NH3–MeOH
(40 mL). After 96 h at rt, the reaction mixture was concentrated,
and the residue was purified by chromatography on Sephadex
LH-20 (MeOH) to afford 1 (0.21 g, 75% over two steps) as a foamy
1.10. p-Methoxyphenyl 3-O-acetyl-2,4-di-O-benzoyl-6-deoxy-
-talopyranosyl-(1?2)-3,4-di-O-acetyl-6-deoxy- -talopyran-
osyl trichloroacetimidate (11)
a-
L
a
-L
solid. ½a 2D5
ꢃ
ꢁ70 (c 1.0, H2O). 1H NMR (300 MHz, D2O) d: 6.99–6.86
(2d, 4H, J 9.0 Hz, C6H4OCH3), 5.40, 5.13, 5.06, 5.02 (4s, 4H, 4 ꢂ H-
1), 4.11–3.87 (m, 13H), 3.71 (s, 3H, CH3O), 3.69–3.66 (m, 3H),
1.20, 1.18, 1.16, 1.13 (4d, 12H, J 6.5 Hz, 4 ꢂ C-CH3). 13C NMR
(300 MHz, D2O) d: 157.2, 152.1, 121.0(2), 117.3(2) (Ar-C), 105.9,
105.7, 101.2, 99.4 (4 ꢂ C-1), 57.9 (C6H4OCH3), 18.0(2), 17.9, 17.8
(4 ꢂ C-CH3). HRMS calcd for C31H48O18Na (M+Na)+: 731.2738,
found: 731.2716.
Deisopropylidenation of compound 10 (1.3 g, 2.0 mmol) was
carried out in 70% aq AcOH (30 mL) at 70 °C for 3 h, at the end of
which time TLC (petroleum ether–EtOAc; 2:1) indicated comple-
tion of the reaction. The mixture was concentrated under dimin-
ished pressure and then co-evaporated with toluene (2 ꢂ 20 mL)
to give the crude product. The crude product was then acetylated
with Ac2O (5 mL) in pyridine (20 mL) without purification to ob-
tain its acetylated derivative. The disaccharide trichloroacetimi-
date 11 was prepared by following the same procedure as
described above for the preparation of compound 8. After purifica-
tion by column chromatography on silica gel (petroleum ether–
EtOAc; 4:1), 11 (0.97 g, 66% over four steps) was obtained as a
Acknowledgments
This work was supported by the Innovation Experiment Pro-
gram for University Students of CAU (No. 0810010929), the Na-
tional Basic Research Program of China (2010CB126105), and
NSFC (No. 20902108) of China.
white foam. ½a 2D5
ꢃ
ꢁ43 (c 1.0, CHCl3). 1H NMR (300 MHz, CDCl3) d:
8.68 (s, 1H, CNHCCl3), 8.18–7.15 (m, 10H, Bz-H), 6.47 (d, 1H, J1,2
References
1.4 Hz, H-1), 5.62 (t, 1H, J2 ,3 , J3 ,4 3.8 Hz, H-30), 5.55 (m, 1H, H-
20), 5.37 (m, 1H, H-4), 5.32–5.30 (m, 2H, H-10, H-40), 5.30 (t, 1H,
J2,3, J3,4 3.6 Hz, H-3), 4.55 (m, 1H, H-5), 4.39 (m, 1H, H-50), 4.12
(m, 1H, H-2), 2.28, 2.10, 2.00 (3s, 9H, 3 ꢂ CH3CO), 1.34, 1.27 (2d,
0
0
0
0
1. Asikainen, S.; Lai, C. H.; Alaluusua, S.; Slots, J. Oral Microbiol. Immunol. 1991, 6,
115–118.
2. Slots, J.; Reynolds, H. S.; Genco, R. J. Infect. Immun. 1980, 29, 1013–1020.
3. Zambon, J. J. J. Clin. Periodontol. 1985, 12, 1–20.
4. Slots, J.; Bragd, L.; Wikstrom, M.; Dahlen, G. J. Clin. Periodontol. 1986, 13, 570–
577.
5. Perry, M. B.; MacLean, L. M.; Brisson, J. R.; Wilson, M. E. Eur. J. Biochem. 1996,
242, 682–688.
6. Gmur, R.; McNabb, H.; van Steenbergen, T. J.; Baehni, P.; Mombelli, A.; van
Winkelhoff, A. J.; Guggenheim, B. Oral Microbiol. Immunol. 1993, 8, 116–120.
7. Kaplan, J. B.; Perry, M. B.; MacLean, L. L.; Furgang, D.; Wilson, M. E.; Fine, D. H.
Infect. Immun. 2001, 69, 5375–5384.
8. Saarela, M.; Asikainen, S.; Alaluusua, S.; Pyhuala, L.; Lai, C. H.; Jousimies-Somer,
H. Oral Microbiol. Immunol. 1992, 7, 277–279.
6H, J 6.2 Hz, J 6.5 Hz, 2 ꢂ C-CH3). Anal. Calcd for C34H36Cl3NO14
:
C, 51.76; H, 4.60; N, 1.78. Found: C, 51.53; H, 4.78; N, 1.92.
1.11. p-Methoxyphenyl 3-O-acetyl-2,4-di-O-benzoyl-6-deoxy-
talopyranosyl-(1?2)-3,4-di-O-acetyl-6-deoxy- -talopyran-
osyl-(1?3)-2,4-di-O-benzoyl-6-deoxy- -talopyranosyl-(1?2)-
3,4-O-isopropylidene-6-deoxy- -talopyranoside (12)
a-L-
a-L
a-L
a-L
9. Zambon, J. J.; Slots, J.; Genco, R. J. Infect. Immun. 1983, 41, 19–27.
10. Roberts, I. S. Annu. Rev. Microbiol. 1996, 50, 285–315.
11. Shibuya, N.; Amano, K.; Azuma, J.; Nishihara, T.; Noguchi, T.; Koga, T. J. Biol.
Chem. 1991, 266, 16318–16323.
12. Chatterjee, D.; Bozic, C.; Aspinall, G. O.; Brennan, P. J. J. Biol. Chem. 1988, 263,
4092–4097.
13. Aspinall, G. O.; Crane, A. M.; Gammon, D. W.; Ibrahim, I. H.; Khare, N. K.;
Chatterjee, D.; Rivoire, B.; Brennan, P. J. Carbohydr. Res. 1991, 216, 337–355.
14. Aspinall, G. O.; Khare, N. K.; Sood, R. K.; Chatterjee, D.; Rivoire, B.; Brennan, P. J.
Carbohydr. Res. 1991, 216, 357–373.
15. Daubenspeck, J. M.; Zeng, H.; Chen, P.; Dong, S.; Steichen, C. T.; Krishna, N. R.;
Pritchard, D. G.; Turnbough, C. L. J. Biol. Chem. 2004, 279, 30945–30953.
16. Zahringer, U.; Rettenmaier, H.; Moll, H.; Senchenkova, S. N.; Knirel, Y. A.
Carbohydr. Res. 1997, 300, 143–151.
17. Forsberg, L. S.; Bhat, U. R.; Carlson, R. W. J. Biol. Chem. 2000, 275, 18851–18863.
18. Zatonsky, G. V.; Kocharova, N. A.; Veremeychenko, S. P.; Zdorovenko, E. L.;
Shashkov, A. S.; Zdorovenko, G. M.; Knirel, Y. A. Carbohydr. Res. 2002, 337,
2365–2370.
19. Castro, C. D.; Gargiulo, V.; Lanzetta, R.; Parrilli, M. Biomacromolecules 2007, 8,
1047–1051.
20. Turska-Szewczuk, A.; Palusinska-Szysz, M.; Russa, R. Carbohydr. Res. 2008, 343,
477–482.
21. Liptak, A.; Kerekgyarto, J.; Popsavin, V.; Kajtar-Peredy, M.; Radies, L. J.
Carbohydr. Chem. 1988, 7, 337–357.
Glycosylation between disaccharide acceptor 10 (0.40 g,
0.60 mmol) and donor 11 (0.77 g, 0.96 mmol) was accomplished
by following the same procedure as described above for the prep-
aration of disaccharide 9. After purification, tetrasaccharide 12
(0.94 g, 74%) was afforded as a white foamy solid. ½a D25
ꢁ10 (c
ꢃ
1.0, CHCl3). 1H NMR (300 MHz, CDCl3) d: 8.17–7.16 (m, 20H, Bz-
H), 7.02–6.98 (m, 2H, Ar-H), 6.88–6.85 (m, 2H, Ar-H), 5.61 (t, 1H,
J
, J
3.7 Hz, H-3000), 5.54–5.45 (m, 3H, H-40, H-4000, H-2000),
2000,3000
3000,4000
5.44 (d, 1H, J1,2 6.4 Hz, H-1), 5.35 (d, 1H, J 1 ,2 1.1 Hz, H-100), d
00 00
5.34 (d, 1H, J1 ,2 0.8 Hz, H-10), 5.31 (m, 1H, H-20), 5.32 (d, 1H, J
0
0
1000,2000
1.0 Hz, H-1000), 5.19 (m, 1H, H-400), 4.95 (m, 1H, J 2 ,3 , J 3 ,4 , 3.6 Hz,
00 00
00 00
H-300), 4.73 (dd, 1H, J2,3 2.4 Hz, J3,4 7.5 Hz, H-3), 4.56–4.51 (m, 2H,
0
0
0
0
0
2 ꢂ H-5), 4.45 (t, 1H, J2 ,3 , J3 ,4 , 3.9 Hz, H-3 ), 4.28 (m, 1H, H-5),
4.18 (dd, 1H, J3,4 7.5 Hz, J4,5 1.7 Hz, H-4), 4.15 (dd, 1H, J1,2 6.4 Hz,
J2,3 2.4 Hz, H-2), 3.98 (m, 1H, H-5), 3.79 (s, 3H, CH3O), 3.66 (m,
1H, H-200), 2.23, 1.97, 1.92 (3s, 9H, 3 ꢂ CH3CO), 1.58, 1.42 (2s, 6H,
C(CH3)2), 1.38, 1.34, 1.24, 1.20 (4d, 12H, J 6.5 Hz, 4 ꢂ C-CH3). 13C
NMR (300 MHz, CDCl3) d: 171.2, 169.8, 169.2 (3 ꢂ CH3CO), 166.5,
166.4, 166.2, 165.9 (4 ꢂ COPh), 110.6 (C(CH3)2), 98.8, 98.7, 96.9,
96.2 (4 ꢂ C-1), 55.6 (C6H4OCH3), 26.2, 25.5 (C(CH3)2), 20.7 (2),
20.6 (3 ꢂ CH3CO), 16.4, 16.3, 16.1, 15.3 (4 ꢂ C-CH3). Anal. Calcd
for C68H74O25: C, 63.25; H, 5.78. Found: C, 63.02; H, 5.71.
22. Zuurmond, H. M.; Veeneman, G. H.; Mare, G. A.; Boom, J. H. Carbohydr. Res.
1993, 241, 153–164.
23. Heidelberg, T.; Martin, O. R. J. Org. Chem. 2004, 69, 2290–2301.
24. Fekete, A.; Gyergyoi, K.; Kover, K. E.; Bajza, I.; Liptak, A. Carbohydr. Res. 2006,
341, 1312–1321.
25. Sarkar, K.; Mukherjee, I.; Roy, N. J. Carbohydr. Chem. 2003, 22, 95–107.
26. Liu, H. J.; Nyangulu, J. M. Tetrahedron Lett. 1988, 29, 3167–3170.
27. Yan, S.; Liang, X.; Diao, P.; Yang, Y.; Zhang, J.; Wang, D.; Kong, F. Carbohydr. Res.
2008, 343, 3107–3111.
28. Janos, K.; Zoltan, S.; Andras, L. Carbohydr. Res. 1993, 245, 65–80.
29. Yan, S. Q.; Wu, X. M.; Liang, X. M.; Zhang, J. J.; Wang, D. Q. Chin. Chem. Lett.
2009, 20, 582–585.
30. Schmidt, R. R. Angew. Chem., Int. Ed. Engl. 1986, 25, 212–235.
31. Zong, G. H.; Yan, S. Q.; Liang, X. M.; Zhang, J. J.; Wang, D. Q.; Kong, F. Z. Chin.
Chem. Lett. 2009, 20, 127–130.
1.12. p-Methoxyphenyl 6-deoxy-
deoxy- -talopyranosyl-(1?3)-6-deoxy-
(1?2)-6-deoxy- -talopyranoside (1)
a
-
L
-talopyranosyl-(1?2)-6-
a-L
a-L-talopyranosyl-
a-L
Compound 12 (0.51 g, 0.39 mmol) was dissolved in 70% aq
AcOH (25 mL) and the solution was stirred at 70 °C for 3 h. The sol-
vents were evaporated in vacuo and then co-evaporated with tol-