G. Agnihotri, A. K. Misra / Tetrahedron Letters 47 (2006) 8493–8497
8497
53.0, 25.6 (CCH3), 21.2, 21.0; ESI-MS: m/z 385.2 [M+Na];
Anal. Calcd for C15H22O10 (362): C, 49.72; H, 6.12.
Found: C, 49.48; H, 6.30.
aq Na2S2O3, satd NaHCO3, water, dried (Na2SO4) and
concentrated to a syrupy product. Column chromatogra-
phy of the crude product over SiO2 using hexane–EtOAc
25
Allyl 3-O-acetyl-2-deoxy-4,6-O-[(S)-(1-methoxycarbonyl)-
ethylidene]-2-phthalimido-b-D-glucopyranoside 6: yellow
(2:1) afforded pure 15 (1.25 g, 73%) as glassy solid; ½aꢁD
+105.4 (c 1.0, CHCl3); IR (KBr): 2961, 2363, 1753, 1597,
25
oil; ½aꢁD +17.7 (c 1.0, CHCl3); IR (neat): 3452, 2918,
1353, 1223, 1098, 766, 709 cmꢀ1 1H NMR (300 MHz,
;
2364, 1748, 1448, 1116, 1057, 748 cmꢀ1
;
1H NMR
CDCl3): d 7.95–7.92 (m, 3H, aromatic protons), 7.49–7.26
(m, 12H, aromatic protons), 5.77 (t, J = 9.6 Hz each, 1H),
5.54 (s, 1H, CHC6H5), 5.46–5.37 (m, 3H), 5.05–4.97 (m,
3H), 4.93 (d, J = 3.6 Hz, 1H), 4.89–4.80 (m, 2H), 4.78 (t,
J = 7.8 Hz, 1H), 4.43 (dd, J = 10.2, 4.8 Hz, 1H), 4.18 (t,
J = 6.0 Hz, 1H), 4.14–4.04 (m, 2H), 3.98–3.81 (m, 4H),
3.68 (t, J = 4.8 Hz, 1H), 3.55–3.49 (m, 1H), 2.07, 2.03,
2.00, 1.97 (4s, 21H, 7COCH3); 13C NMR (75 MHz,
CDCl3): d 170.4, 170.2, 170.0, 169.9, 169.8, 169.6 (2C),
166.2, 166.1, 133.3–126.5 (aromatic carbons), 102.3
(PhCH), 101.8, 92.3, 91.9, 79.0, 72.3, 72.1, 70.7 (2C),
70.3 (3C), 69.5 (2C), 68.9, 68.7, 68.4, 67.1, 62.2, 20.9 (2C),
20.8 (3C), 20.7 (2C); ESI-MS: m/z 1072 [M+Na]; Anal.
Calcd for C53H58O25 (1095): C, 58.13; H, 5.34. Found: C,
58.10; H, 5.49.
(300 MHz, CDCl3):
d 7.87–7.74 (m, 4H, aromatic
protons), 5.73–5.62 (m, 2H), 5.41 (d, J = 8.4 Hz, 1H),
5.10–5.04 (m, 1H), 4.27–4.21 (m, 2H), 4.14 (dd, J = 10.8,
3.9 Hz, 1H), 4.02 (dd, J = 12.9, 6.3 Hz, 1H), 3.86 (s, 3H,
COOCH3), 3.80–3.74 (m, 1H), 3.72–3.68 (m, 1H), 3.66–
3.61 (m, 2H), 1.96 (s, 3H, COCH3), 1.54 (s, 3H, CCH3);
13C NMR (75 MHz, CDCl3): d 170.4, 170.1, 134.4, 133.6,
131.9, 123.9, 118.1, 99.6, 97.9, 75.6, 70.5, 70.4, 70.2, 66.1,
65.4, 55.6, 52.9, 25.6 (CCH3), 20.9; ESI-MS: m/z 498
[M+Na]; Anal. Calcd for C23H25NO10 (475): C, 58.10; H,
5.30. Found: C, 57.82; H, 5.58.
1,2-O-Isopropylidene-5,6-O-(1-methoxycarbonyl)ethylidene]-
25
3-O-octyl-a-D-glucofuranose 10: yellow oil; ½aꢁD ꢀ18.2 (c
1.0, CHCl3); IR (neat): 2933, 2363, 1595, 1351, 1084,
670 cmꢀ1
;
1H NMR (300 MHz, CDCl3): d 5.86 (dd,
36. Agnihotri, G.; Misra, A. K. Tetrahedron Lett. 2006, 47,
3653–3658.
J = 9.9, 3.3 Hz, 1H), 4.54–4.52 (m, 1H), 4.44–429 (m,
1H), 4.28–4.22 (m, 2H), 4.14 (t, J = 5.4 Hz, 1H), 3.88 (dd,
J = 12.0, 3.3 Hz, 1H), 3.79 (s, 3H, OCH3), 3.63–3.58 (m,
1H), 3.58–3.54 (m, 1H), 1.59, 1.56 (2s, 6H, C(CH3)2), 1.50
(s, 3H, CCH3), 1.31–128 (m, 12H), 0.90 (t, J = 6.0 Hz,
3H); 13C NMR (75 MHz, CDCl3): d 170.1, 111.8, 105.3,
100.1, 82.5, 82.1, 80.6, 73.6, 70.7, 69.1, 31.8, 29.7, 29.2,
26.8, 26.3, 26.0, 22.6 (CCH3), 14.0; ESI-MS: m/z 439
[M+Na]; Anal. Calcd for C21H36O8 (416): C, 60.56; H,
8.71. Found: C, 60.31; H, 8.83.
37. (2,3-Di-O-benzoyl-4,6-O-[(S)-(1-methoxycarbonyl)ethyl-
idene]-b-D-glucopyranosyl)-(1!6)-(2,3,4,6-tetra-O-acet-
yl-a-D-glucopyranosyl)-(1!1)-2,3,4-tri-O-acetyl-a-D-gluco-
pyranose 17: Prepared following the NIS-TfOH promoted
25
general reaction protocol. Yield 55%; yellow oil; ½aꢁD
+98.9 (c 1.0, CHCl3); IR (neat): 1749, 1225, 1038,
713 cmꢀ1; H NMR (200 MHz, CDCl3): d 7.96–7.34 (m,
1
10H, aromatic protons), 5.58 (t, J = 9.6 Hz each, 1H),
5.40–5.25 (m, 3H), 4.99–4.89 (m, 3H), 4.83–4.75 (m, 2H),
4.70 (d, J = 4.8 Hz, 1H), 4.17–4.11 (m, 2H), 4.02–3.96 (m,
2H), 3.92–3.87 (m, 2H), 3.83 (s, 3H, COOCH3), 3.76–3.68
(m, 3H), 3.58–3.44 (m, 2H), 2.08, 2.06, 2.02, 2.00, 1.98,
1.96 (6s, 21H, 7COCH3), 1.49 (s, 3H, CCH3); 13C NMR
(50 MHz, CDCl3): d 170.4 (2C), 170.0, 169.8 (2C), 169.6
(2C), 165.7, 165.1, 133.7–128.7 (aromatic carbons), 102.1,
99.6 (CCH3), 92.3, 91.8, 75.0, 72.2 (2C), 70.8, 70.3 (2C),
69.5 (2C), 68.8 (2C), 66.8, 66.7, 66.6, 65.2, 62.2, 52.9
(COOCH3), 25.5 (CCH3), 20.9 (3C), 20.8 (4C); ESI-MS:
m/z 1113.3 [M+Na]; Anal. Calcd for C50H58O27 (1090): C,
55.05; H, 5.36. Found: C, 54.87; H, 5.50.
Methyl (3-O-acetyl-2-deoxy-4,6-O-[(S)-(1-methoxycarbon-
yl)ethylidene]-2-phthalimido-b-D-glucopyranosyl)-(1!6)-
25
2,3,4-tri-O-acetyl-a-D-glucopyranoside 12: yellow oil; ½aꢁD
+45.2 (c 1.0, CHCl3); IR (neat): 3406, 2363, 1746, 1228,
1038, 770 cmꢀ1; 1H NMR (300 MHz, CDCl3): d 8.28–8.12
(m, 4H, aromatic protons), 6.04 (t, J = 9.0 Hz each, 1H),
5.78 (d, J = 8.4 Hz, 1H), 5.64 (t, J = 9.9 Hz each, 1H),
5.12 (t, J = 9.6 Hz each, 1H), 5.02 (dd, J = 10.2, 3.6 Hz,
1H), 4.88 (d, J = 3.3 Hz, 1H), 4.58–4.50 (m, 2H), 4.18 (s,
3H), 4.17–4.08 (m, 3H), 4.05–4.00 (m 2H), 3.87–3.75 (m,
1H), 3.45 (s, 3H), 2.39, 2.32, 2.29, 2.22 (4s, 12H, 4
COCH3), 1.90 (s, 3H, CCH3); 13C NMR (50 MHz,
CDCl3): d 170.2, 169.6 (2C), 169.3, 167.9 (2C), 134.3–
123.7 (aromatic carbons), 99.5 (CCH3), 99.3, 96.6, 79.4,
75.4, 74.2, 73.3, 70.6, 70.1, 69.2, 68.0, 55.7, 55.4, 55.1, 52.9,
55.3, 54.9, 25.5 (CCH3), 20.9 (2C), 20.7 (2C); ESI-MS: m/z
760 [M+Na]; Anal. Calcd for C33H39NO18 (737): C, 53.73;
H, 5.33. Found: C, 53.60; H, 5.58.
38. 4,6-O-[(S)-(1-Sodium carboxylate)ethylidene]-b-D-gluco-
pyranosyl-(1!6)-a-D-glucopyranosyl-(1!1)-D-a-Glcp 18:
A solution of compound 17 (400 mg, 0.36 mmol) in
0.05 M sodium methoxide in methanol (5.0 mL) was
stirred at room temperature for 5 h. Then five drops of
distilled water were added to the reaction mixture which
was allowed to stir at room temperature for 12 h. The
reaction mixture was neutralized with Dowex 50W-X8
(H+), filtered and the filtrate was evaporated to dryness to
give a glassy solid, which was again dissolved in distilled
water and treated with Dowex 50W-X8 (Na+) and
concentrated. The crude product was purified through
Sephadex LH-20 using 80% aqueous EtOH as eluant to
give pure trisaccharide 18 as its sodium salt (185 mg, 86%);
32. Ohta, M.; Pan, Y. T.; Laine, R. A.; Elbein, A. D. Eur. J.
Biochem. 2002, 269, 3142–3149.
33. Saadat, S.; Ballou, C. E. J. Biol. Chem. 1983, 258, 1813–
1818.
´
´
´
´
34. Szurmai, Z.; Kerekgyarto, J.; Harangi, J.; Liptak, A.
Carbohydr. Res. 1987, 164, 313–325.
35. 2,3-Di-O-benzoyl-4,6-O-benzylidene-b-D-glucopyranosyl)-
(1!6)-(2,3,4,6-tetra-O-acetyl-a-D-glucopyranosyl)-(1!1)-
2,3,4-tri-O-acetyl-a-D-glucopyranose 15: To a solution of
compound 13 (1.28 g, 2.46 mmol) and compound 14
(1.0 g, 1.57 mmol) in anhydrous CH2Cl2: toluene (1:1;
25
glassy solid; ½aꢁD +14 (c 1.0, H2O); IR (KBr): 3760, 2375,
1595, 1352 cmꢀ1 1H NMR (300 MHz, D2O): d 5.12 (d,
;
J = 3.3 Hz, 1H, H-1), 5.10 (d, J = 3.3 Hz, 1H, H-10), 4.51
(d, J = 8.1 Hz, 1H, H-100), 4.04–4.02 (m, 1H), 3.97 (d,
J = 4.8 Hz, 1H), 3.84–3.77 (m, 5H), 3.72–3.71 (m, 2H),
3.68 (d, J = 4.5 Hz, 1H), 3.61–3.56 (m, 4H), 3.47 (t,
J = 9.6 Hz, 1H), 3.42–3.36 (m, 3H), 1.41 (s, 3H); 13C
NMR (75 MHz, D2O): d 170.0, 102.1 (C-100), 100.2 (ketal-
C), 92.0 (2C), 74.6, 72.7, 71.5, 71.2 (2C), 70.9, 69.7 (2C),
68.4, 68.1, 67.4, 64.6, 62.9, 59.3 (2C), 23.4; ESI-MS: m/z
619.1 [M+Na]; Anal. Calcd for C21H33NaO18 (596): C,
42.29; H, 5.58. Found: C, 42.05; H, 5.80.
˚
20 mL) was added powdered 4 A MS (3.0 g) and the
mixture was stirred under argon for 1 h. N-Iodosuccini-
mide (580 mg, 2.58 mmol) was added to the reaction
mixture at room temperature which was then cooled to
ꢀ40 °C. Trifluoromethanesulfonic acid (22 lL, 0.25 mmol)
was added to the reaction mixture and it was allowed to
stir for 30 min at ꢀ40 °C. The reaction mixture was
filtered through Celite and the filtrate was washed with 5%