862
O. M. Cociorva, T. L. Lowary / Carbohydrate Research 339 (2004) 853–865
3.23. Octyl 2,3-di-O-benzoyl-5-O-methyl-a-
furanosyl-(1 fi 5)-2,3-di-O-benzoyl-a-
oside (35)
D
-arabino-
D-arabinofuran-
66.64, 32.25, 29.97, 29.84, 29.70, 26.59, 23.07, 14.50;
ESIMS: m=z calcd for [C46H49N3O12]Naþ: 858.3208.
Found: 858.3279.
Disaccharide 35 was prepared from 2143 (43 mg,
0.09 mmol) and 25 (52 mg, 0.11 mmol) and powdered
ꢀ
molecular sieves (4 A, 100 mg) in dry CH2Cl2 (10 mL) as
3.25. Octyl 2,3-di-O-benzoyl-5-deoxy-5-fluoro-a-
nofuranosyl-(1 fi 3)-2,5-di-O-benzoyl-a-
oside (37)
D
-arabi-
D-arabinofuran-
described for the synthesis of 34 using N-iodosuccin-
imide (50 mg, 0.22 mmol) and silver triflate (10 mg,
0.04 mmol). Purification of the product by chromato-
graphy (4:1 hexanes–EtOAc) gave 35 (70 mg, 94%) as an
Disaccharide 37 was prepared from 2343 (50 mg,
0.10 mmol), and 24 (60 mg, 0.13 mmol) and powdered
ꢀ
molecular sieves (4 A, 150 mg) in dry CH2Cl2 (10 mL) as
oil: Rf 0.12 (4:1 hexanes–EtOAc); ½a +84.9ꢁ (c 0.7,
described for the synthesis of 34 using N-iodosuccin-
imide (29 mg, 0.13 mmol) and silver triflate (11 mg,
0.04 mmol). Purification of the product by chromato-
graphy (4:1 hexanes–EtOAc) to give 37 (75 mg, 92%) as
D
CHCl3); 1H NMR (500 MHz, CDCl3): dH, 8.00–7.96 (m,
4H), 7.94–7.93 (m, 2H), 7.88–7.86 (m, 2H), 7.53–7.48
(m, 2H), 7.44–7.41 (m, 1H), 7.39–7.35 (m, 5H), 7.33–
7.30 (m, 2H), 7.23–7.18 (m, 2H), 5.53 (d, 1H, J 4.8 Hz),
5.52 (d, 1H, J 1.2 Hz), 5.42 (d, 1H, J 1.2 Hz), 5.36 (s,
1H), 5.33 (d, 1H, J 4.6 Hz), 5.13 (s, 1H), 4.50–4.47 (m,
1H), 4.38–4.36 (m, 1H), 4.13 (dd, 1H, J 4.6, 11.2 Hz),
3.86 (dd, 1H, J 3.0, 11.2 Hz), 3.73 (dd, 1H, J 3.1,
10.6 Hz), 3.69–3.65 (m, 2H), 3.44–3.39 (m, 1H), 3.38 (s,
3H), 1.30–1.29 (m, 2H), 1.23–1.16 (m, 10H), 0.80–0.77
(m, 3H); 13C NMR (125 MHz, CDCl3): dC, 166.21,
166.08, 165.85, 165.58, 133.84, 133.80, 133.75, 133.62,
130.35, 130.24, 129.84, 129.77, 129.59, 129.89, 128.86,
128.82, 128.71, 106.45, 106.01, 82.73, 82.21, 81.97,
78.12, 77.81, 72.55, 67.85, 66.69, 59.89, 32.25, 29.98,
29.84, 29.70, 26.60, 23.07, 14.50; ESIMS: m=z calcd for
[C47H52O13]Naþ: 847.3300. Found: 847.3230.
an oil: Rf 0.43 (4:1 hexanes–EtOAc); ½a +121.6ꢁ (c 0.8,
D
CHCl3); 1H NMR (400 MHz, CDCl3): dH, 8.02–7.96 (m,
4H), 7.93–7.87 (m, 4H), 7.53–7.48 (m, 2H), 7.42–7.31
(m, 6H), 7.21–7.17 (m, 4H), 5.62 (s, 1H), 5.57 (s, 1H),
5.35 (d, 1H, J 4.2 Hz), 5.31 (s, 1H), 5.22 (s, 1H), 4.74–
4.66 (m, 1H), 4.62–4.54 (m, 2H), 4.48–4.43 (m, 1H),
4.36–4.26 (m, 3H), 3.71–3.65 (m, 1H), 3.48–3.41 (m,
1H), 1.56–1.51 (m, 2H), 1.30–1.17 (m, 10H), 0.81–0.77
(m, 3H); 13C NMR (100 MHz, CDCl3): dC, 166.40,
165.97, 165.75, 165.36, 133.78, 133.73, 133.63, 133.30,
130.19, 130.13, 130.05, 129.87, 129.50, 129.31, 128.74,
128.69, 128.51, 106.09, 105.55, 83.47 (d, J 19.0 Hz),
83.11, 82.11 (d, J 172.7 Hz), 81.44, 81.39, 77.48, 77.05
(d, J 6.4 Hz), 67.94, 32.04, 39.65, 29.52, 29.44, 26.25,
22.84, 14.29; ESIMS: m=z calcd for [C46H49FO12]Naþ:
835.3100. Found: 835.3092.
3.24. Octyl 5-azido-2,3-di-O-benzoyl-5-deoxy-a-
nofuranosyl-(1 fi 5)-2,3-di-O-benzoyl-a-
oside (36)
D
-arabi-
D-arabinofuran-
3.26. Octyl 2,3-di-O-benzoyl-5-O-methyl-a-
furanosyl-(1 fi 3)-2,5-di-O-benzoyl-a-
oside (38)
D
-arabino-
D-arabinofuran-
Disaccharide 36 was prepared from 2143 (100 mg,
0.21 mmol), and 26 (113 mg, 0.23 mmol) and powdered
Disaccharide 38 was prepared from 2343 (20 mg,
0.05 mmol), and 25 (55 mg, 0.11 mmol) and powdered
ꢀ
molecular sieves (4 A, 150 mg) in dry CH2Cl2 (10 mL) as
described for the synthesis of 34 using N-iodosuccin-
imide (50 mg, 0.22 mmol) and silver triflate (10 mg,
0.04 mmol). Purification of the product by chromato-
graphy (4:1 hexanes–EtOAc) gave 38 (40 mg, 97%) as an
ꢀ
molecular sieves (4 A, 100 mg) in dry CH2Cl2 (10 mL) as
described for the synthesis of 34 using N-iodosuccin-
imide (70 mg, 0.31 mmol) and silver triflate (10 mg,
0.04 mmol). Purification of the product by chromato-
graphy (6:1 hexanes–EtOAc) gave 36 (155 mg, 88%) as
an oil: Rf 0.62 (4:1 hexanes–EtOAc); ½a +103.7ꢁ (c 0.7,
D
CHCl3); 1H NMR (500 MHz, CDCl3): dH, 8.02–8.01 (m,
2H), 7.97–7.95 (m, 4H), 7.86–7.84 (m, 2H), 7.54–7.50
(m, 2H), 7.49–7.44 (m, 1H), 7.43–7.31 (m, 7H), 7.22–
7.18 (m, 2H), 5.57 (d, 1H, J 0.8 Hz), 5.52 (d, 1H, J
5.1 Hz), 5.43 (d, 1H, J 1.2 Hz), 5.38 (s, 1H), 5.28 (d, 1H,
J 4.5 Hz), 5.14 (s, 1H), 4.51–4.49 (m, 1H), 4.37–4.34 (m,
1H), 4.12 (dd, 1H, J 4.6, 11.2 Hz), 3.88 (dd, 1H, J 2.9,
11.2 Hz), 3.73 (dd, 1H, J 2.9, 13.2 Hz), 3.68–3.63 (m,
1H), 3.54 (dd, 1H, J 4.8, 13.2 Hz), 3.44–3.39 (m, 1H),
1.53–1.50 (m, 2H), 1.21–1.16 (m, 10H), 0.80–0.77 (m,
3H); 13C NMR (125 MHz, CDCl3): dC, 166.33, 166.11,
165.85, 165.59, 133.98, 133.88, 133.80, 133.76, 130.31,
130.23, 129.75, 129.57, 129.36, 128.96, 128.84, 128.75,
106.26, 105.98, 83.27, 82.22, 82.21, 81.94, 78.83, 67.86,
oil: Rf 0.31 (4:1 hexanes–EtOAc); ½a +78.9ꢁ (c 0.9,
D
CHCl3); 1H NMR (400 MHz, CDCl3): dH, 8.09–7.97 (m,
8H), 7.59–7.57 (m, 4H), 7.51–7.34 (m, 6H), 7.28–7.24
(m, 2H), 5.66 (s, 1H), 5.60 (d, 1H, J 1.3 Hz), 5.44 (dd,
1H, J 0.8, 4.5 Hz), 5.39 (d, 1H, J 0.8 Hz), 5.23 (s, 1H),
4.73 (dd, 1H, J 2.8, 12.1 Hz), 4.61–4.52 (m, 1H), 4.48 (s,
1H), 4.50–4.45 (m, 1H), 4.37–4.35 (m, 1H), 3.84–3.67
(m, 3H), 3.56–3.47 (m, 1H), 3.39 (s, 3H), 1.64–1.61 (m,
2H), 1.36–1.24 (m, 10H), 0.87–0.84 (m, 3H); 13C NMR
(100 MHz, CDCl3): dC, 166.61, 166.09, 165.91, 165.57,
134.06, 133.28, 133.77, 133.51, 133.41, 130.39, 130.31,
130.24, 130.18, 130.14, 130.11, 129.76, 129.75, 129.67,
128.99, 128.87, 128.81, 128.75, 128.67, 106.32, 105.72,