942
M. Kojima et al. / Tetrahedron Letters 50 (2009) 939–942
14. Usually MeOH is used to elute fluorous compounds from
a
FluoroFlashÒ
by FSPE. The fluorous Car group was selectively removed without
damaging the benzoyl and benzylidene groups under common
reaction conditions for a non-fluorous Car group. In order to dem-
onstrate the versatility of FCar groups, studies examining its appli-
cation to fluorous syntheses of other bioactive oligosaccharides are
currently underway.
column. When the fluorous compounds were sparingly soluble in MeOH, EtOAc
was used to quickly elute the fluorous compounds from the column.
15.
L-Ribose is commercially available from Tokyo Chemical Industry Co., Ltd.
ˇ
16. (a) Koóš, M.; Micová, J.; Steiner, B.; Alföldi, J. Tetrahedron Lett. 2002, 43, 5405;
(b) Koóš, M.; Mosher, H. S. Carbohydr. Res. 1986, 146, 335; (c) Nachman, R. J.;
Hönel, M.; Williams, T. M.; Halaska, R. C.; Mosher, H. S. J. Org. Chem. 1986, 51,
4802; (d) Ho, P.-T. Can. J. Chem. 1979, 57, 381.
17. (a) Kim, Y.-J.; Wang, P.; Navarro-Villalobos, M.; Rohde, B. D.; Derryberry, J.; Gin,
D. Y. J. Am. Chem. Soc. 2006, 128, 11906; (b) Zhu, X.; Yu, B.; Hui, Y.; Schmidt, R.
R. Eur. J. Org. Chem. 2004, 5, 965.
References and notes
18. Chan, L.; Just, G. Tetrahedron 1990, 46, 151.
1. Zhang, W. In The Handbook of Fluorous Chemistry; Gladysz, J. A., Curran, D. P.,
Horváth, I. T., Eds.; Wiley-VCH: Weinheim , 2004; pp 222–235.
2. For reviews on FSPE, see: (a) Zhang, W.; Curran, D. P. Tetrahedron 2006, 62,
11837; (b) Curran, D. P. In The Handbook of Fluorous Chemistry; Gladysz, J. A.,
Curran, D. P., Horváth, I. T., Eds.; Wiley-VCH: Weinheim, 2004; pp 101–127; (c)
Curran, D. P. Synlett 2001, 1488.
3. (a) Kojima, M.; Nakamura, Y.; Takeuchi, S. Tetrahedron Lett. 2007, 48, 4431; (b)
Kojima, M.; Nakamura, Y.; Ishikawa, T.; Takeuchi, S. Tetrahedron Lett. 2006, 47,
6309.
4. (a) Nakamura, Y.; Takeuchi, S. QSAR Comb. Sci. 2006, 25, 703; (b) Nakamura, Y.;
Okumura, K.; Kojima, M.; Takeuchi, S. Tetrahedron Lett. 2006, 47, 239.
5. Koike, K.; Li, W.; Liu, L.; Hata, E.; Nikaido, T. Chem. Pharm. Bull. 2005, 53,
225.
6. (a) Hase, K.; Kadota, S.; Basnet, P.; Namba, T.; Takahashi, T. Phytother. Res. 1996,
10, 387; (b) Xia, H. C.; Li, F.; Zhang, Z. C. Cell Res. 2003, 13, 369.
7. Beck, E. In Plant Carbohydrates; Loewus, F. A., Tanner, W., Eds.; Springer: New
York, 1982.
8. (a) Zhong, X.-N.; Otsuka, H.; Ide, T.; Hirata, E.; Takushi, S.; Takeda, Y.
Phytochemistry 1998, 49, 2149–2153; (b) Zhong, X.-N.; Otsuka, H.; Ide, T.;
Hirata, E.; Takeda, Y. Phytochemistry 1999, 52, 923–927; (c) Duynstee, H. I.;
de Koning, M. C.; van der Marel, G. A.; van Boom, J. H. Tetrahedron 1999,
55, 9881; (d) Hettinger, P.; Schildknecht, H. Liebigs Ann. Chem. 1984, 6,
1230.
9. Sato, K.; Sakai, K.; Tsushima, K.; Akai, S. Tetrahedron Lett. 2007, 48, 3745.
10. Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 3rd ed.; John
Wiley and Sons: New York, 1999.
19. Physical data of disaccharide 17: ½a D23
ꢂ
ꢁ27.6 (c 0.51, CHCl3); 1H NMR (250 MHz,
CDCl3) d 7.99–6.89 (23H, m, aromatic protons), 6.73 (1H, br s, –NH), 5.91 (1H, s,
PhCH–), 5.56 (1H, s, PhCH–), 5.51 (1H, s, H-10(Api)), 5.39 (1H, t, J3,4 = 9.3 Hz, H-
3(Glc)), 5.06 (1H, d, J1,2 = 7.3 Hz, H-1(Glc)), 4.65 (1H, s, H-20(Api)), 4.59, 4.48
(2H, each d, J5,5 = 11.9 Hz, J5 ,5 = 11.9 Hz, H-5, 50(Api)), 4.37 (1H, dd,
J6eq,5 = 4.7 Hz, J6eq,6ax = 10.3 Hz, H-6eq(Glc)), 4.25 (2H, s, H-40(Api)), 4.11 (1H,
dd, J2,1 = 7.4 Hz, J2,3 = 8.6 Hz, H-2(Glc)), 3.79 (1H, t, J6ax,5 = 10.2 Hz,
J6ax,6eq = 10.2 Hz, H-6ax(Glc)), 3.77 (1H, t, J4,3 = 9.4 Hz, J4,5 = 9.4 Hz, H-4(Glc)),
3.68 (3H, s, –COOCH3), 3.66–3.57 (1H, m, H-5(Glc)), 3.52 (2H, s, –CH2COOCH3),
2.63 (2H, t, J = 7.4 Hz, CH2CH2CH2C8F17), 2.16–1.82 (4H, m, CH2CH2CH2C8F17);
13C NMR (63 MHz, CDCl3) d 172.0, 165.8, 155.6, 152.3, 136.7, 136.1, 135.7,
135.6, 133.3, 130.6, 129.9, 129.7, 129.4, 129.1, 128.8, 128.7, 128.6, 128.5, 128.4,
128.2, 127.0, 126.2, 126.1, 119.4, 116.5, 107.0, 106.3, 101.4, 89.9, 87.0, 78.4,
77.2, 75.7, 75.0, 73.6, 68.6, 66.2, 64.5, 52.0, 40.3, 34.3, 30.2 (t), 21.4. MS (ESI-
pos.) calcd for C59H49F17O14Na (M+Na)+ 1342.2857, found: 1342.2901.
0
0
20. Rocaboy, C.; Rutherford, D.; Bennett, B. L.; Gladysz, J. A. J. Phys. Org. Chem. 2003,
13, 596. The 1H and 13C NMR data of 21 were identical with those reported. 1
H
NMR (250 MHz, CDCl3) d 7.34–7.17 (5H, m, aromatic protons), 2.71 (2H, t,
J = 7.2 Hz, Ar-CH2), 2.19–1.88 (4H, m, CH2CH2C8F17), [lit. 1H NMR (400 MHz,
CDCl3) d 7.37–7.20 (5H, m, aromatic protons), 2.73 (2H, t, J = 7.0 Hz, Ar-CH2),
2.21–1.93 (4H, m, CH2CH2C8F17)], 13C NMR (63 MHz, CDCl3) d 140.6 (s), 128.6
(s), 128.3 (s), 126.3 (s), 35.0 (s), 30.3 (t), 21.8 (br s), [lit. 13C NMR (100 MHz,
CDCl3) d 140.9 (s), 128.8 (s), 128.6 (s), 126.6 (s), 35.3 (s), 30.6 (t), 22.1 (br s)].
21. Physical data of synthetic cucurbitoside A: ½a D17
ꢂ
ꢁ75.5 (c 1.1, MeOH) [lit. ½a D24
ꢂ
ꢁ76.1 (c 1.1, MeOH)5]; 1H NMR (250 MHz, CD3OD) d 7.92 (2H, dd, J = 8.5,
1.4 Hz, benzoyl), 7.58 (1H, tt, J = 8.1, 1.3 Hz, benzoyl), 7.41 (2H, t, J = 7.8 Hz,
benzoyl), 6.93 (2H, d, J = 9.2 Hz, aromatic protons), 6.88 (2H, d, J = 9.1 Hz,
aromatic protons), 5.51 (1H, d, J1,2 = 1.0 Hz, H-10(Api)), 4.91 (1H, d, J1,2 = 7.4 Hz,
11. Shioiri, T.; Ninomiya, K.; Yamada, S. J. Am. Chem. Soc. 1972, 94, 6203.
12. FluoroFlashÒ Silica Gel 40
lm is available from Fluka.
13. Typical procedure of FSPE. Washing: A new FluoroFlashÒ silica gel (5 g) column
was washed with acetone (10 ml). Preconditioning: The column was washed
with 80% aq MeOH (15 ml). Sample loading: The residue, including compound
4, (610 mg) was dissolved in 2 ml of CH2Cl2. To the solution was added
FluoroFlashÒ silica gel (1 g), and the solvent was then evaporated. The powder
was loaded onto the column. Fluorophobic elution: The column was eluted with
80% aq MeOH (30 ml) to give a fraction containing the organic compound 3.
Fluorophilic elution: The column was eluted with MeOH (30–50 ml) to give a
fraction containing the fluorous compound 4 (516 mg, y. 75%). Final washing:
To regenerate the FluoroFlashÒ silica gel for reuse, the column was washed
with acetone (10 ml).
H-1(Glc)), 4.35, 4.27 (2H, each d, J5,5 = 11.5 Hz, J5 ,5 = 11.4 Hz, H-50(Api)), 4.34,
0
0
3.92 (2H, each d, J4,4 = 9.7 Hz, J4 ,4 = 9.5 Hz, H-40(Api)), 3.98 (1H, d, J2,1 = 1.1 Hz,
0
0
H-20(Api)), 3.86 (1H, br d, J6,6 = 12.7 Hz, H-6(Glc)), 3.70–3.55 (2H, m, H-3,
0
60(Glc)), 3.63 (1H, dd, J2,3 = 9.4 Hz, J2,1 = 7.5 Hz, H-2(Glc)), 3.60 (2H, t, J = 7.3 Hz,
Ph-CH2CH2OH), 3.43–3.34 (2H, m, H-4, 5(Glc)), 2.63 (t, J = 7.3 Hz, Ph-
CH2CH2OH); 13C NMR (63 MHz, CD3OD) d 167.6, 157.3, 134.3, 133.9, 131.1,
130.9, 130.7, 129.5, 117.2, 110.3 (C-10 (Api)), 100.7 (C-1(Glc)), 79.2 (C-30 (Api)),
78.8 (C-3(Glc)), 78.6 (C-20(Api)), 78.1 (C-2(Glc)), 78.0 (C-5(Glc)), 75.4 (C-
40(Api)), 71.5 (C-4(Glc)), 68.5 (C-50(Api)), 62.5 (C-6(Glc)), 64.3 (PhCH2CH2OH),
39.4 (PhCH2CH2OH). MS (ESI-pos.) calcd for C26H32O12Na (M+Na)+ 559.1791,
found: 559.1798.