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A. Borbás et al. / Tetrahedron: Asymmetry 11 (2000) 549–566
5×OCH2Ph), 4.49 (2H, s, OCH2Ph), 4.35, 4.18 (2H, 2 d, OCH2Ph), 4.34 (1H, d, J1,2=8.0 Hz, H-1), 4.23
0
(1H, d, H0-1a), 4.22 (1H, d, J3 ,4 =9.5 Hz, H -3), 4.16 (1H, m, J5 ,6 =9.8 Hz, J6 ,7a =3.0 Hz, J6 ,7b =1.0
0
0
0
0
0
0
0
0
0
Hz, H0-6), 4.03 (2H, m, SO3CH2CH3), 3.99 (1H, t, J4 ,5 =9.2 Hz, H -4), 3.77 (1H, d, J4,3=3.2 Hz, J4,5
0
0
<0.5 Hz, H-4), 3.70 (1H, dd, J3,2=9.0 Hz, H-3), 3.68 (1H, t, H0-5), 3.65 (2H, d, J6,5=5.7 Hz, H-6a,b),
3.54 (1H, dd, H-2), 3.50 (1H, d, H0-1b), 3.39 (1H, t, H-5), 3.27 (1H, dd, J7a ,7b =11.5 Hz, H -7a), 3.21
(1H, dd, H0-7b), 1.03 (3H, t, J=7.0 Hz, SO3CH2CH3). 13C NMR (CDCl3, 125 MHz) δ (ppm): 102.25
(C-1), 99.59 (C0-2), 82.96 (C0-4), 79.81 (C0-3), 77.72 (C0-5), 77.72 (C-2), 75.33, 75.15, 74.93, 74.86
(4×OCH2Ph), 74.26 (C-3), 73.50, 72.98 (2×OCH2Ph), 72.91 (C-5), 72.43 (C0-6), 70.65 (OCH2Ph),
69.13 (C-6), 68.78 (C-4), 68.17 (SO3CH2CH3), 68.10 (C0-7), 53.15 (C0-1), 15.07 (SO3CH2CH3). Anal.
calcd for C64H70O14S: C 70.17, H 6.45, S 2.92. Found: C 70.34, H 6.47, S 3.01.
0
0
0
Compound 21 (18%): [α]D +30.55 (c 0.63, CHCl3), Rf 0.24 (hexane:ethyl acetate 7:3). 1H NMR (500
MHz, benzene-d6) δ (ppm): 5.16, 4.99; 5.05, 4.90; 4.89, 4.57; 4.73, 4.38; 4.71, 4.65 (10 d, each 1H,
5×OCH2Ph), 4.59 (1H, d, H0-3), 4.47 (1H, d, J1,2=7.4 Hz, H-1), 4.43 (1H, m, H0-6), 4.39, 4.26 (2H,
0
0
0
0
0
0
0
0
d, OCH2Ph), 4.29 (1H, d, J1a ,1b =14.8 Hz, H -1a), 4.26 (1H, t, J3 ,4 =J4 ,5 =9.5 Hz, H -4), 4.19, 4.14
(2H, d, OCH2Ph), 4.11 (2H, q, J=7.1 Hz, SO3CH2CH3), 3.81 (1H, m, H-2), 3.79 (2H, m, H-6a,b), 4.73,
4.38 (2H, d, OCH2Ph), 3.67 (1H, d, H0-1b), 3.66 (1H, d, J3,4=1 Hz, H-4), 3.66 (1H, dd, H0-7a), 3.60
0
0
0
0
0
0
0
(1H, dd, J3,2=9.9 Hz, H-3), 3.56 (1H, t, J5 ,6 =9.5 Hz, H -5), 3.49 (1H, dd, J7a ,7b =10.2 Hz, J6 ,7b =7.0
Hz, H0-7b), 3.44 (1H, m, H-5), 0.98 (3H, t, J=7.1 Hz, SO3CH2CH3). 13C NMR (125 MHz, benzene-
d6) δ (ppm): 103.20 (C-1), 99.67 (C0-2), 83.21 (C0-4), 81.15 (C0-3), 80.86 (C-2), 78.89 (C0-5), 75.80,
75.22, 75.22, 74.99 (4×OCH2Ph), 74.11 (C-5), 73.79 (C-3), 73.54 (OCH2Ph), 73.36 (C0-6), 72.94 (C-4),
72.94, 70.92 (2×OCH2Ph), 69.56 (C-6), 69.34 (C0-7), 67.83 (SO3CH2CH3), 52.52 (C0-1, JC1 ,H3 =4.5
Hz), 15.02 (SO3CH2CH3).
0
0
4.17. Methyl 3-O-(1-deoxy-1-tetrabutylammoniumsulfonato-α-D-gluco-hept-2-ulopyranosyl)-β-D-
galactopyranoside 22
Compound 17 (120 mg, 0.1 mM) was treated with Bu4NBr (40 mg, 1.2 equiv.) in acetonitrile (3 mL)
at reflux temperature for 1 h, when TLC showed the disappearance of 17. The mixture was evaporated,
the residue was dissolved in ethanol (3 ml), and 10% Pd–C (10 mg) was added. The mixture was stirred
for 2 days under H2, when TLC (acetone:water 9:1, Rf 0.3) indicated a complete conversion, then it was
filtered and concentrated. Column chromatography (acetone:water 9:1) of the residue gave 22 (83%),
1
0
0
having [α]D +44.3 (c 1.10, H2O). H NMR (500 MHz,0D2O) δ (ppm): 4.84 (1H, dd, J7a ,7b =12.5 Hz,
H-7a0), 4.38 (1H, 0m, J6 ,7a =2.6 Hz, J6 ,7b =5.2 Hz, H-6 ), 4.36 (1H, d, J1,2=7.9 Hz, H-1), 4.12 (1H, d,
0
0
0
0
0
0
0
0
0
J3 ,4 =9.8 Hz, H-3 ), 4.00 (1H, H-3), 4.00 (1H, H-4), 3.85 (1H, t, J4 ,5 =9.8 Hz, H-4 ), 3.78 (1H, H-6a),
3.74 (1H, dd, H-7b0), 3.73 (1H, H-6b) 3.72 (1H, H-5), 3.59 (1H, H-2), 3.53 (1H, d, J1a ,1b =14.0 Hz,
0
0
H-1a0), 3.47 (1H, d, H-1b0), 3.46 (1H, t, J5 ,6 =9.7 Hz, H-5 ), 3.18, 1.64, 1.35, 0.93 (nBu). 13C NMR
0
0
0
(125 MHz, D2O) δ (ppm): 106.52 (C1), 102.78 (C02), 77.28 (C5), 75.82 (C06), 75.62 (C3), 75.32 (C04),
74.80 (C03), 72.37 (C2), 71.95 (C05), 71.60 (C4), 63.75 (C6), 63.46 (C07), 56.96 (C01, JC1 ,H3 =2.0 Hz),
60.82, 25.82, 21.84, 15.50 (nBu). Anal. calcd for C30H61O14SN: C 52.08, H 8.89, S 4.63, N 2.02. Found:
C 52.06, H 8.90, S 4.61, N 2.00.
0
0
4.18. Hydroxyethyl 2,3,4-tri-O-benzyl-α-L-fucopyranoside 24
To a solution of ethyl 2,3,4-O-tri-O-benzyl-1-thio-α-L-fucopyranoside23 (500 mg, 1.0 mM) and
ethylene glycol (0.58 mL, 10.4 mM, 10 equiv.), in dichloromethane:DMF 3:1, 4 Å molecular sieves
were added, and the mixture was stirred overnight under Ar. Then Bu4N−Br+ (330 mg, 1.0 mM, 1 ekv.)