ORDER
REPRINTS
p-Tolyl Diazido-2-S-(p-tolyl)-disaccharide
45
then filtered and concentrated. Column chromatography with 3 : 1 toluene–EtOAc gave 4
1
(2.3 g, 71.8%); [a]2D5 þ22.5 (c 0.8, CHCl3). H NMR (CDCl3) d 7.49–6.86 (13 H,
aromatic protons), 4.77, 4.67 (2 d, 4H, J ¼ 9.96 Hz, CH2C6H5, CH2C6H4OCH3), 4.51
(d, 1H, J1,2 ¼ 9.5 Hz, H-1), 3.81 (s, 3H, CH2C6H4OCH3), 3.64 (t, 1H, J ¼ 9.36 Hz, H-2),
3.55 (m, 2H, H-3, H-5), 2.32 (s, 3H, CH3C6H4S), 1.35 (d, 3H, J ¼ 6.39 Hz, H-6). 13C
NMR d 159.35–113.8 (aromatic carbons), 87.86 (H-1), 82.96, 76.57, 75.35, 74.16, 72.16,
69.46 (ring carbons), 55.31 (OCH3) 21.13 (SC6H4CH3), 16.75 (C-6). Anal. Calcd for
C28H32O5S: C, 69.97; H, 6.67. Found: C, 69.55; H, 6.78.
p-Tolyl 4-Azido-3-O-benzyl-4,6-dideoxy-2-O-(4-Methoxybenzyl)-1-Thio-
b-D-glucopyranoside (6)
To a solution of 4 (3 g, 6.2 mmol) in dry dichloromethane (50 mL) containing pyridine
(1.6 mL) at 2258C was added Tf2O (1.99 mL, 11.8 mmol) under nitrogen. The mixture was
then allowed to reach room temperature. After 1 hr, TLC (9 : 1 toluene–EtOAc) indicated a
single faster moving spot. The reaction mixture was then diluted with dichloromethane
(50 mL) and washed successively with cold water (2 ꢀ 75 mL), cold saturated NaHCO3
solution (2 ꢀ 75 mL), and cold water (2 ꢀ 75 mL); dried (Na2SO4) and filtered. The
solution was concentrated to give compound 5 (3.84 g). A solution of 5 (3.84 g, 5.75 mmol)
in DMF (62 mL) containing sodium azide (1.04 g, 16.0 mmol) and 18-crown-6 (54 mg,
0.20 mmol) was stirred for 2 hr at room temperature. The mixture was then extracted with
ethyl ether (2 ꢀ 75 mL), and the extract was washed with saturated NaHCO3 (2 ꢀ 100 mL)
and water (2 ꢀ 100 mL), dried (Na2SO4) and concentrated. Column chromatography with
15 : 1 toluene–EtOAc gave pure 6 (2.85 g, 90%); [a]2D5 þ34.4 (c 0.7, CHCl3). 1H NMR d
7.45–6.86 (13 H, aromatic protons), 4.89, 4.82 (2 d, 2H, J ¼ 10.8 Hz, CH2C6H4OCH3),
4.82, 4.65 (2 d, 2H, J ¼ 9.9 Hz, CH2C6H5), 4.53 (d, 1H, J ¼ 9.34 Hz, H-1), 3.79 (s, 3H,
OCH3) 3.47 (m, 2H, H-2, H-3), 3.19 (m, 2H, H-4, H-5), 2.34 (s, 3H, CH3C6H4S), 1.36
(d, 3H, J ¼ 5.7 Hz, H-6). 13C NMR d 159.87–114.32 (aromatic carbons) 88.36 (C-1),
85.37, 81.09, 76.48, 75.51, 75.19, 68.18 (ring carbons), 55.85 (OCH3), 21.58 (SC6H4CH3);
19.19 (C-6). I.R. (thin film) 1346 cm21 (weak), 2113 cm21 (strong) [N3]. Anal. Calcd for
C28H31O4SN3: C, 66.51; H, 6.18; N, 8.31. Found: C, 66.48; H, 6.50; N, 8.69.
p-Tolyl 4-Acetamido-3-O-benzyl-4,6-dideoxy-2-O-(4-Methoxybenzyl)-
1-Thio-b-D-glucopyranoside (7)
A solution of 6 (100 mg, 0.2 mmol) in methanol (4 mL) containing Ac2O (0.2 mL) was
stirred under H2 in the presence of 10% Pd–C for 4 days. The mixture was filtered and the
filtrate was concentrated to a syrup. Column chromatography then gave pure 7 (62 mg,
1
60%); [a]2D5 218.4 (c 0.7, MeOH). H NMR d 7.47–6.86 (m, 13H, aromatic protons),
4.93 (d, 1H, J ¼ 8.4 Hz, NH), 4.85, 4.64 (2 d, 2H, J ¼ 10.9 Hz, CH2C6H5), 4.85, 4.61
(2 d, 2H, J ¼ 12.1 Hz, 4.56 (d, 1H, J1,2 ¼ 9.2 Hz, H-1), 3.80 (s, 3H, C6H4OCH3), 3.61
(t, 1H, J ¼ 9.3 Hz, H-2), 3.52 (m, 2H, H-3, H-4), 3.42 (m, 1H, H-5), 2.34 (s, 3H,
C6H4OCH3), 1.78 (s, 3H, NHCOCH3), 1.24 (d, 3H, J5,6 6.15 Hz, H-6). 13C NMR d 169.05
(COCH3), 158.39–112.84 (aromatic carbons), 86.65 (C-1), 81.32, 80.06, 74.31, 73.90,