Helvetica Chimica Acta – Vol. 92 (2009)
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DMF (30 ml) NaN3 (700 mg, 10.77 mmol) was added. The mixture was stirred for 17 h at 808. Then, the
solvent was eliminated, and the residue was purified by CC (SiO2; CHCl3) to give 11 (441 mg, 0.39 mmol,
21% yield from 9) and 12 (210 mg, 0.19 mmol, 10%).
Data of 11: M.p. 104.5 – 106.58. [a]2D2 ¼ þ33.1 (c ¼ 1, CHCl3). IR (neat): 2104, 1722, 1259, 1089, 1066,
1025. 1H-NMR (CDCl3,): 7.99 – 7.93 (m, 10 arom. H); 7.84 (d, J ¼ 8.8, HꢀC(3’’), HꢀC(5’’)); 7.73 (d, J ¼
7.5, 2 arom. H); 7.67 – 7.60 (m, 2 arom. H); 7.54 – 7.47 (m, 5 arom. H); 7.42 – 7.29 (m, 7 arom. H); 7.25 – 7.17
(m, 4 arom. H); 6.95 (d, J ¼ 8.8, HꢀC(2’’), HꢀC(6’’)); 5.86 (t, J ¼ 9.4, HꢀC(3)); 5.76 – 5.71 (m, HꢀC(2),
HꢀC(2’)); 5.61 (d, J ¼ 2.9, HꢀC(4’)); 5.38 – 5.34 (m, HꢀC(1), HꢀC(3’)); 4.89 (d, J ¼ 7.8, HꢀC(1’)); 4.66
(d, J ¼ 11.9, HꢀC(6a)); 4.48 (dd, J ¼ 4.8, 11.9, HꢀC(6b)); 4.34 (t, J ¼ 9.4, HꢀC(4)); 4.07 (dd, J ¼ 4.8, 9.4,
HꢀC(5)); 3.85 (s, MeO); 3.69 (t, HꢀC(5’)); 2.73 (dd, J ¼ 5.3, 12.9, HꢀC(6a’)); 2.64 (dd, J ¼ 7.2, 12.9,
HꢀC(6b’)). 13C-NMR (CDCl3): 166.2 – 164.6 (6 C¼O); 159.9 (C(1’’)); 133.5 – 116.1 (arom. C); 100.6
(C(1’)); 98.2 (C(1)); 75.5 (C(4’)); 73.1 (C(5)); 72.8 (C(5’)); 72.5 (C(3)); 71.5 (C(3’)); 71.2, 69.6 (C(2),
C(2’)); 67.9 (C(4)); 62.2 (C(6)); 51.7 (MeO); 49.2 (C(6’)). HR-ESI-MS: 1125.3054 (C62H51N3Oþ18 ; calc.
1125.3168).
Data of 12: M.p. 191 – 1928. [a]2D2 ¼ þ33.9 (c ¼ 1, CHCl3). IR (neat): 1718, 1267, 703. 1H-NMR
(CDCl3): 7.99 – 7.92 (m, 8 arom. H); 7.83 (d, J ¼ 7.9, 5 arom. H); 7.62 – 7.56 (m, 2 arom. H); 7.52 – 7.25 (m,
15 arom. H); 7.11 (t, J ¼ 7.7, 2 arom. H); 6.95 (d, J ¼ 8.6, HꢀC(2’’), HꢀC(6’’)); 5.90 – 5.85 (m, HꢀC(3),
HꢀC(2’), HꢀC(4’)); 5.72 (t, J ¼ 7.9, HꢀC(2)); 5.43 (dd, J ¼ 3.2, 9.7, HꢀC(3’)); 5.38 (d, J ¼ 7.9, HꢀC(1));
5.01 (d, J ¼ 6.7, HꢀC(1’)); 4.65 (d, J ¼ 12.0, HꢀC(6a)); 4.63 (s, HꢀC(6a’)); 4.58 (s, HꢀC(6b’)); 4.49 (dd,
J ¼ 5.2, 12.0, HꢀC(6b)); 4.35 (t, J ¼ 9.2, HꢀC(4)); 4.08 (dd, J ¼ 5.2, 9.2, HꢀC(5)); 3.85 (s, MeO).
13C-NMR (CDCl3): 165.6 – 164.9 (6 C¼O); 160.0 (C(1’’)); 149.2 – 124.9 (arom. C); 116.3 (C(2’’), C(6’’));
102.9 (C(6’)); 101.7 (C(1’)); 98.4 (C(1)); 76.8 (C(4)); 73.3 (C(5)); 73.0 (C(3), C(2’) or C(4’)); 71.5 (C(2));
70.2 (C(3’)); 69.9, 68.8 (C(3), C(2’) or C(4’)); 62.5 (C(6)); 51.9 (MeO). HR-ESI-MS: 1082.2991
(C62H50Oþ18 ; 1082.2997).
Methyl 4-{[2,3,6-Tri-O-benzoyl-4-O-(2,3-di-O-benzoyl-b-d-galactopyranosyl)-b-d-glucopyranosyl]-
oxy}benzoate (13). To a soln. of 9 (8 g, 7.37 mmol) in CH2Cl2 (50 ml) were added CF3CO2H (8 ml,
108.05 mmol) and H2O (0.4 ml). The mixture was stirred vigorously for 10 h at r.t. Then, it was diluted
with CH2Cl2 (60 ml) and washed with H2O (2 ꢁ 40 ml), sat. aq. NaHCO3 soln. (2 ꢁ 40 ml), and again with
H2O (3 ꢁ 30 ml). The org. phase was dried (Na2SO4) and concentrated under reduced pressure. The
residue was purified by CC (SiO2; CH2Cl2/MeOH 95 :5) to afford 13 (4.7 g, 4.71 mmol, 64%). White
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solid. M. p. 237 – 2388. [a]2D3 ¼ þ34.9 (c ¼ 1, DMSO). IR (neat): 1717, 1265, 704. H-NMR ((CD3)2SO):
7.96 – 7.90 (m, 4 arom. H); 7.86 – 7.81 (m, 6 arom. H); 7.71 – 7.36 (m, 15 arom. H); 7.30 (t, J ¼ 7.5, 2 arom.
H); 7.01 (d, J ¼ 8.8, HꢀC(2’’), HꢀC(6’’)); 5.91 (d, J ¼ 7.9, HꢀC(1)); 5.84 – 5.79 (m, HꢀC(3)); 5.51 – 5.45
(m, HꢀC(2), HꢀC(2’)); 5.22 (d, J ¼ 5.4, HOꢀC(4’)); 5.18 (dd, J ¼ 3.0, 10.4, HꢀC(3’)); 5.02 (d, J ¼ 8.0,
HꢀC(1’)); 4.57 – 4.47 (m, HꢀC(6a), HꢀC(6b)); 4.48 (t, J ¼ 5.0, HOꢀC(6’)); 4.38 – 4.34 (m, HꢀC(4),
HꢀC(5)); 4.06 (br. t, HꢀC(4’)); 3.78 (s, MeO); 3.55 (br. t, HꢀC(5’)); 3.09 – 3.06 (m, HꢀC(6a’)); 2.95 (td,
J ¼ 5.0, 10.0, HꢀC(6b’)). 13C-NMR ((CD3)2SO): 165.6 – 165.6 (6 C¼O); 159.6 (C(1’’)); 133.8 – 133.3
(arom. C); 130.9 (C(3’’), C(5’’)); 129.4 – 123.7 (arom. C); 115.9 (C(2’’), C(6’’)); 100.5 (C(1’)); 96.0 (C(1));
76.0 (C(4)); 74.8 (C(3’)); 74.6 (C(5’)); 72.9 (C(3)); 72.6 (C(5)); 71.7, 70.2 (C(2), C(2’)); 64.6 (C(4’)); 62.9
(C(6)); 58.2 (C(6’)); 51.9 (MeO). HR-ESI-MS: 996.2760 (C55H48Oþ18 ; calc. 996.2840).
Methyl 4-{[2,3,6-Tri-O-benzoyl-4-O-(2,3-di-O-benzoyl-6-deoxy-6-iodo-b-d-galactopyranosyl)-b-d-
glucopyranosyl]oxy}benzoate (14). To a stirred soln. of Ph3P (3.2 g, 12.2 mmol) and 1H-imidazole
(1.66 g, 24.44 mmol) in PhMe/MeCN 2 :1 (380 ml), I2 (2.5 g, 12.21 mmol) was added. After 10 min, 13
(4.8 g, 4.81 mmol) was added dropwise, and the resulting mixture was stirred at 608 for 9 h. Then, the
mixture was concentrated under reduced pressure. The residue was partitioned between CH2Cl2 and
H2O, and the aq. layer was extracted with CH2Cl2 (2 ꢁ 150 ml). The combined org. layers were dried
(Na2SO4) and concentrated under reduced pressure. The crude residue was washed with Et2O to afford
14 (4.03 g, 3.71 mmol, 77% crude yield) that was used in subsequent reactions without further
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purification. H-NMR (CDCl3): 8.08 (d, J ¼ 7.0, 2 arom. H); 7.95 – 7.87 (m, arom. H); 7.81 (d, J ¼ 8.8,
HꢀC(3’’), HꢀC(5’’)); 7.64 – 7.20 (m, arom. H); 6.93 (d, J ¼ 8.8, HꢀC(2’’), HꢀC(6’’)); 5.89 (t, J ¼ 8.8,
HꢀC(3)); 5.76 – 5.66 (m, HꢀC(2), HꢀC(2’)); 5.41 (d, J ¼ 7.4, HꢀC(1)); 5.15 (dd, J ¼ 3.1, 10.3,
HꢀC(3’)); 4.82 (d, J ¼ 7.8, HꢀC(1’)); 4.68 (br. d, J ¼ 11.0, HꢀC(6a)); 4.47 – 4.26 (m, HꢀC(4), HꢀC(4’),
HꢀC(6b)); 4.15 (m, HꢀC(5)); 3.84 (s, MeO); 3.56 (t, J ¼ 6.8, HꢀC(5’)); 2.88 (dd, J ¼ 6.8, 10.1,