I. Robina et al. / Tetrahedron 58 (2002) 521±530
527
0
0
H-6b), 3.73 (m, 1H, H-5), 3.71 (dd, 1H, J2 ,3 8.9 Hz,
(71 mg, 2.36 mmol) was added. The mixture was stirred at
rt for 15 min, cooled to 08C and then BnBr (280 mL,
2.36 mmol) was added. The reaction mixture was stirred
for 24 h at rt, diluted with dichloromethane and ®ltered
through celite. The ®ltrate was washed successively with,
saturated aq NaHCO3 and water, dried (Na2SO4) and evapo-
rated to drynesss. Column chromatography of the residue
(toluene±acetone, 40:1) gave 17 (48 mg, 80%) as a white
solid that crystallised from acetone had mp 66±688C;
[a]D-48 (c 0.9, dichloromethane).
0
0
0
J3 ,4 9.5 Hz, H-3 ), 3.71 (s, 3H, C6H4OCH3), 3.56 (t, 1H,
J5 ,6 b10.3 Hz, H-60b), 3.48 (t, 1H, J4 ,5 8.9 Hz, H-4 ),
3.48 (dd, 1H, H-20), 3.24 (td, 1H, H-50). 13C NMR
(75.4 MHz, CDCl3) d 167.7, 167.7 (2CO, Phth), 155.3
(C-4, C6H4OCH3), 150.6 (C-1, C6H4OCH3), 138.1±114.2
(28C aromatic), 103.4 (C-10), 101.7 (CHPh), 97.7 (C-1),
78.7 (C-4), 78.1 (C-3), 74.6 (C-5), 65.5 (C-50), 74.7, 73.2
(2C, CH2Ph), 73.5 (C-30), 68.7 (C-40), 67.9(C-6), 68.5
(C-60), 75.4 (C-20), 55.6 (C-2), 55.5 (C6H4OCH3).
FABMS: m/z 868 [100%, (M1Na)1]. Anal. Calcd for
C48H47NO13: C, 68.15; H, 5.60; N, 1.66. Found C, 68.21;
H, 5.98; N, 1.67.
0
0
0
0
0
1H NMR (300 MHz, CDCl3, 318 K) d 7.99±6.79 (m, 39H,
Phth, Ph, C6H4OCH3), 6.25 (m, 1H, H-1), 5.42 (s, 1H,
CHPh), 5.33±5.06 (m, 4H, 2CH2Ph), 4.91, 4.77 (d, 1H
2
3.1.8. p-Methoxyphenyl 2,3-di-O-benzyl-4,6-O-benzyl-
idene-b-d-glucopyranosyl-(1!4)-3,6-di-O-benzyl-2-deoxy-
2-phthalimido-b-d-glucopyranoside (16). To a solution of
each, JH,H11.4 Hz, CH2Ph), 4.86, 4.81 (d, 1H each,
2JH,H11.1 Hz, CH2Ph), 4.59 (m, 2H, H-10, H-2), 4.56,
2
4.38 (d, 1H each, JH,H12.0 Hz, CH2Ph), 4.55 (s, 2H,
0
0
0
0
0
p-methoxyphenyl
(4,6-O-benzylidene-b-d-glucopyrano-
CH2Ph), 4.15 (dd, 1H, J5 ,6 a4.5 Hz, J6 a ,6 b10.0 Hz, H-
60a), 4.07 (t, 1H, J3,4J4,59.2 Hz, H-4), 3.85 (dd, 1H,
J5,6a4.5 Hz, J6a,6b10.0 Hz, H-6a), 3.75 (s, 3H,
syl)-(1!4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-b-d-
glucopyranoside (14) (412 mg, 0.488 mmol) in dry DMF
(2 mL), NaH (80%) (89 mg, 2.93 mmol) was added. The
mixture was stirred at rt for 15 min, cooled to 08C and
then BnBr (521 mL, 4.39 mmol) was added. The reaction
mixture was stirred for 24 h at rt, diluted with dichloro-
methane and ®ltered through celite. The ®ltrate was washed
successively with, saturated aq NaHCO3 and water; dried
(Na2SO4) and evaporated to dryness. Column chroma-
tography of the residue (toluene±acetone, 15:1) gave 16
(370 mg, 74%) as a white solid that crystallised from
acetone had mp 68±708C; [a]D1148 (c0.9, dichloro-
methane).
C6H4OCH3), 3.69 (m, 3H, H-3, H-5, H-6b), 3.62 (t, 1H,
0
0
0
0
0
0
0
J2 ,3 J3 ,4 8.9 Hz, H-3 ), 3.52 (t, 1H, J4 ,5 8.9 Hz,
H-40), 3.39 (t, 1H, H-20), 3.28 (t, 1H, J5 ,6 b4.5 Hz,
H-60b), 3.18 (td, 1H, H-50). 13C NMR (75.4 MHz, CDCl3)
y d 172.8, 164.8 (2CO, Phth), 154.8 (C-4, C6H4OCH3),
151.4 (C-1, C6H4OCH3), 138.9±114.2 (46C aromatic),
102.7 (C-1) 100.9 (CHPh), 97.8 (C-10), 82.6 (C-20), 81.5
(C-40), 80.8 (C-30), 78.6 (C-4), 78.0, 75.5, 74.8, 73.8, 73.1
(5C, CH2Ph), 74.6 (C-50),75.2 (C-5), 68.5 (C-60), 67.7
(C-6), 66.7 (C-3), 64.4 (NCH2Ph), 56.4 (C-2), 55.5
(C6H4OCH3). FABMS: m/z 1246 [100%, (M1Na)1].
Anal. Calcd for C76H73NO14: C, 74.55; H, 5.90; N, 1.14.
Found: C, 74.05; H, 5.95; N, 1.22.
0
0
1H NMR (500 MHz, CDCl3) d 7.69 (m, 4H, Phth), 7.51±
6.91 (m, 25H, 5Ph), 6.84±6.68 (m, 4H, C6H4OCH3), 5.61 (d,
1H, J1,28.5 Hz, H-1), 5.49 (s, 1H, CHPh), 4.93, 4.79 (d, 1H
3.1.10. p-Methoxyphenyl 2,3-di-O-benzyl-b-d-gluco-
pyranosyl-(1!4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-
b-d-glucopyranoside (17). To a solution of p-methoxy-
2
each, JH,H11.3 Hz, CH2Ph), 4.87, 4.83 (d, 1H each,
2JH,H11.1 Hz, CH2Ph), 4.81, 4.47 (d, 1H each, JH,H
2
0
0
0
12.3 Hz, CH2Ph), 4.59 (d, 1H, J1 ,2 7.8 Hz, H-1 ), 4.58,
phenyl
(2,3-di-O-benzyl-4,6-O-benzylidene-b-d-gluco-
2
4.40 (d, 1H each, JH,H12.0 Hz, CH2Ph), 4.43 (dd, 1H,
pyranosyl)-(1!4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-
b-d-glucopyranoside (16) (350 mg, 0.34 mmol) in MeOH±
dioxane (1:1, 10 mL), TsOH´H2O (7 mg, 0.03 mmol) was
added. The reaction mixture was left to stand at 658C for
15 min and at 858C for 3 h, then made neutral with Et3N and
evaporated to dryness. Column chromatography of the resi-
due on silica gel (ether±petroleum ether, 5:1) gave 17
(263 mg, 82%) as a white solid that crystallised from
ether had mp 64±668C; [a]D1168 (c 1, dichloromethane).
J2,310.7 Hz, H-2), 4.34 (dd, 1H, J3,48.5 Hz, H-3), 4.28
(dd, 1H, J5 ,6 a4.9 Hz, J6 a,6 b10.5 Hz, H-60a), 4.16 (dd,
0
0
0
0
1H, J4,59.9 Hz, H-4), 3.89 (dd, 1H, J5,6a4.2 Hz, J6a,6b
11.1 Hz, H-6a), 3.75 (dd, 1H, J5,6b1.6 Hz, H-6b), 3.71 (s,
0
0
0
0
3H, C6H4OCH3), 3.67 (dd, 1H, J2 ,3 8.7 Hz, J3 ,4 9.3 Hz,
H-30), 3.62 (ddd, 1H, H-5), 3.59 (t, 1H, J4 ,5 9.3 Hz, H-4 ),
0
0
0
3.48 (t, 1H, J5 ,6 b10.5 Hz, H-60b), 3.42 (dd, 1H, H-20),
3.23 (ddd, 1H, H-50). 13C NMR (125.7 MHz, CDCl3) d
155.3 (C-4, C6H4OCH3), 150.9 (C-1, C6H4OCH3), 138.5±
114.3 (40C aromatic), 103.0 (C-10), 101.1 (CHPh), 97.7
(C-1), 82.6 (C-20), 81.1 (C-30), 81.1 (C-40), 78.1 (C-4),
77.2 (C-3), 75.3 (C-5), 75.6, 74.9, 74.4, 73.2 (4C, CH2Ph),
68.7 (C-60), 67.7 (C-6), 65.7 (C-50), 55.5 (C-2), 55.5
(C6H4OCH3). FABMS: m/z 1048 [70%, (M1Na)1]. Anal.
Calcd for C62H59NO13: C, 72.57; H, 5.79; N, 1.36. Found: C,
72.28; H, 5.98; N, 1.44.
0
0
1H NMR (500 MHz, CDCl3) d 7.68 (m, 4H, Phth), 7.38±
6.92 (m, 20H, 4CH2Ph), 6.85±6.68 (m, 4H, C6H4OCH3),
5.63 (d, 1H, J1,28.4 Hz, H-1), 4.96, 4.72 (d, 1H each,
2
2JH,H11.5 Hz, CH2Ph), 4.91, 4.79 (d, 1H each, JH,H
2
11.2 Hz, CH2Ph), 4.84, 4.49 (d, 1H each, JH,H12.2 Hz,
2
CH2Ph), 4.61, 4.45 (d, 1H each, JH,H12.0 Hz, CH2Ph),
0
0
0
4.55 (d, 1H, J1 ,2 7.5 Hz, H-1 ), 4.45 (dd, J2,310.7 Hz,
H-2), 4.37 (dd, J3,48.5 Hz, H-3), 4.13 (dd, 1H, J4,5
9.9 Hz, H-4), 3.87 (dd, 1H, J5,6a4.3 Hz, J6a,6b11.0 Hz,
H-6a), 3.79 (dd, 1H, J5,6b1.5 Hz, H-6b), 3.76 (m, 1H,
3.1.9. p-Methoxyphenyl (2,3-di-O-benzyl-4,6-O-benzyl-
idene-b-d-glucopyranosyl)-(1!4)-3,6-di-O-benzyl-2-(N-
benzyl-N-benzyloxycarbonylbenzoyl)amino-2-deoxy-b-
d-glucopyranoside (15). To a solution of p-methoxyphenyl
(4,6-O-benzylidene-b-d-glucopyranosyl)-(1!4)-3,6-di-O-
benzyl-2-deoxy-2-phthalimido-b-d-glucopyranoside (14)
(50 mg, 0.059 mmol) in dry DMF (1 mL), NaH (80%)
J5 ,6 a3.3 Hz, J6 a,6 b12.2 Hz, H-60a), 3.71 (s, 3H,
0
0
0
0
0
0
C6H4OCH3), 3.67 (m, 1H, H-5), 3.48 (t, 1H, J4 ,5 9.3 Hz,
H-40), 3.46 (t, 1H, J5 ,6 b5.6 Hz, H-60b), 3.37 (m, 2H, H-20,
H-30), 3.20 (ddd, 1H, H-50). 13C NMR (125.7 MHz, CDCl3)
d 167.8, 167.8 (2CO, Phth), 155.4 (C-4, C6H4OCH3), 150.9
0
0