4644
C. Yang et al. / Tetrahedron Letters 44 (2003) 4641–4644
Breslow, R.; Dong, S. D. Chem. Rev. 1998, 98, 1997–
2011.
was stirred at 60°C for 5 h, benzenesulfonyl chloride (767
mg, 4.35 mmol) was added and the reaction mixture was
stirred for an additional 30 min. Propanol (5 mL) was
then added carefully and ice-water (200 mL) was added
to precipitate the cyclodextrin species. The precipitates
were filtered off and dissolved in 100 mL benzene,
washed successively with dilute hydrochloric acid,
aqueous NaHCO3 solution and water, and dried over
Na2SO4. The solvent was evaporated off and the residue
was purified by column chromatography on silica gel
with an eluent of benzene–ethyl acetate (4:1) to afford 4
(665 mg, 71%). 1H NMR (300 MHz, CDCl3, TMS): l
5.15 (1H, s), 4.04 (1H, d, J=9.0), 3.85 (1H, dd, J=3.4,
J=9.3), 3.66 (1H, d, J=11.4), 3.50 (1H, m), 3.30 (1H, d,
J=3.4), 3.08 (1H, d, J=3.5), 0.84 (9H, s), 0.00 (6H, s).
13C NMR (75 MHz, CDCl3, TMS): l 96.2, 69.5, 68.0,
62.2, 53.8, 49.4, 25.9, 18.3, −4.9, −5.1.
3. (a) Yang, J.; Gabriele, B.; Belvedere, S.; Huang, Y.;
Breslow, R. J. Org. Chem. 2002, 67, 5057–5067; (b)
Cardin, D. J. Adv. Mater. 2002, 14, 553–563; (c) Baugh,
S. D. P.; Yang, Z.; Leung, D. K.; Wilson, D. M.;
Breslow, R. J. Am. Chem. Soc. 2001, 123, 12488–12494;
(d) Harada, A. Acc. Chem. Res. 2001, 34, 456–464; (e)
Hedges, A. R. Chem. Rev. 1998, 98, 2035–2044; (f)
Uekama, K.; Hirayama, F.; Irie, T. Chem. Rev. 1998, 98,
2045–2076.
4. Lichtenthaler, F. W.; Immel, S. J. Inclsion Phenom. Mol.
Recognit. Chem. 1996, 25, 2–16.
5. (a) Kawamura, M.; Uchiyama, T.; Kuramoto, T.;
Tamura, Y.; Mizutani, K. Carbohydr. Res. 1989, 192,
83–90; (b) Oguma, T.; Horiuchi, T.; Kobayashi, M.
Biosci. Biotechnol. Biochem. 1993, 57, 1225–1227; (c)
Breedveld, M. W.; Miller, K. Microbiol. Rev. 1994, 58,
145–161.
9. Preparation of 2: LiAlH4 (60 mg, 1.58 mmol) was added
to a solution of 4 (100 mg, 0.048 mmol) in THF (25 ml)
cooled at 0°C and the resultant solution was stirred at rt
for 2 h and then at 65°C for 7 days until no further
changes can be detected on TLC. After cooled down to
room temperature, the reaction mixture was treated by
the addition of ethyl acetate (1 ml) to decompose the
excess LiAlH4. After evaporation of the solvent, the
residue was taken in distilled water (50 ml), adjusted to
neutral pH with 1 M HCl, filtered and applied to
reversed-phase chromatography on a Merck pre-packed
Lobar column (LiChrom Rp-18, size B). A gradient
elution of the column from 5% to 30% aqueous EtOH
afforded the title product 2 in good yield (31 mg, 55%).
Anal. calcd for C48H80O32: C, 49.31; H, 6.90. Found: C,
6. Gattuso, G.; Nepogodiev, S. A.; Stoddart, J. F. Chem.
Rev. 1998, 98, 1919–1958.
7. (a) Fujita, K.; Shimada, H.; Ohta, K.; Nogami, Y.; Nasu,
K.; Koga, T. Angew. Chem., Int. Ed. Engl. 1995, 34,
1621–1622; (b) Nogami, Y.; Nasu, K.; Koga, T.; Ohta,
K.; Fujita, K.; Immel, S.; Lindner, H. J.; Schmitt, G. E.;
Lichtenthaler, F. W. Angew. Chem., Int. Ed. Engl. 1997,
36, 1899–1902.
8. (a) Coleman, A. W.; Zhang, P.; Ling, C.-C.; Mahuteau,
J.; Parrot-Lopez, H.; Miocque, M. Supramol. Chem.
1992, 1, 11–14; (b) Kahn, A. R.; Barton, L.; D’Souza, V.
T. J. Chem. Soc., Chem. Commun. 1992, 1112–1114.
Preparation of 3: Dried g-CD (4 g, 3.08 mmol) was
dissolved in dry pyridine (30 mL). To this solution was
added dropwise pyridine solution (20 mL) containing
tert-butyldimethylsilyl chloride (4.5 g, 30 mmol). The
reaction mixture was stirred at rt for 24 h, and then
poured into 400 mL ice-water. The resultant precipitates
were dissolved in ethyl acetate (150 mL), washed with 5%
HCl solution, saturated NaHCO3 solution and distilled
water. After dried over anhydrous Na2SO4 the solvent
was removed to afford (6.26 g, 92%) of crude product.
Column chromatography of the crude product on silica
gel with ethyl acetate–ethanol–water (18:4:1) as eluent
gave the pure 3 (5.69 g, 83%). 1H NMR (300 MHz,
CDCl3, TMS): l 4.83 (1H, d, J=2.7), 3.94ꢀ3.85 (2H,
m), 3.65 (1H, d, J=10.5), 3.56ꢀ3.53 (2H, m), 3.44 (1H,
d, J=9.0), 0.83 (9H, s), 0.00 (6H, s). 13C NMR (75 MHz,
CDCl3, TMS): l 102.0, 81.7, 73.6, 73.4, 72.5, 61.6, 25.9,
18.3, −5.1, −5.2.
49.46; H, 7.10. FAB-MS: m/z 1169 [M+H+] and 1191
1
[M+Na+]. H NMR (500 MHz, D2O, CH3OH int.: lCH
=
3.30): l 1.95 (ddd, 1H, Ha-3), 2.01 (ddd, 1H, Hb-3), 3.77
(dd, 1H, Ha-6), 3.79 (dd, 1H, Hb-6), 3.84 (ddd, 1H, H-2),
3.89 (ddd, 1H, H-5), 3.93 (td, 1H, H-4), 4.72 (d, 1H,
H-1). J1,2=3.33, J2,3a:3.6, J2,3b:5.9, J3a,3b=13.6, J3a,4
=
8.1, J3b,4=5.4, J4,5=8.1, J5,6a:5.3, J5,6b:3.3, J6a,6b
:
12.4. 13C NMR (125 MHz, D2O, CH3OH int.: lC=49.0):
l 31.9 (C-3), 61.0 (C-6), 67.4 (C-2), 70.7 (C-4), 73.6 (C-5),
99.4 (C-1).
10. Kelly, D. R.; Mish’al, A. K. Tetrahedron: Asymmetry
1999, 10, 3627–3648.
11. Schneider, H.-J.; Hacket, F.; Rudiger, V.; Ikeda, H.
Chem. Rev. 1998, 98, 1755–1785.
12. Takaguchi, Y.; Tajima, T.; Ohta, K.; Motoyoshiya, J.;
Aoyama, H.; Wakahara, T.; Akasaka, T.; Fujitsuka, M.;
Ito, O. Angew. Chem., Int. Ed. 2002, 41, 817–819.
13. Andersson, T.; Nilsson, K.; Sundahl, M.; Westman, G.;
Wennerstrom, O. J. Chem. Soc., Chem. Commun. 1992,
604.
Preparation of 4: Sodium hydride (65% in mineral oil,
540 mg, 14.6 mmol) was washed with hexane, dried under
vacuum and added to a dry DMF (25 mL) solution
containing 3 (1 g, 0.45 mmol). After the resultant mixture