7632 J . Org. Chem., Vol. 63, No. 22, 1998
Dai and Martin
1
etate 3:2); yield: 96%. [R]20 +71.5 (c 1.9, CHCl3); H NMR
containing 2-iodo-3,4,5-trimethoxybenzoic acid (0.69 g, 2.05
mmol), DCC (0.452 g, 2.2 mmol), and DMAP (0.037 g) was
stirred at room temperature for 24 h. The solids were then
removed by filtration, and the solvent was evaporated. Ether
(10 mL) was added, the insoluble fraction was removed by
filtration, and the filtrate was concentrated. The residue was
submitted twice to flash chromatography (hexane-ethyl ac-
D
(CDCl3) δ 3.50 (s, 3H), 3.75 (s, 3H), 3.81-3.89 (several s, 27H),
3.93 (s, 3H), 3.96 (s, 3H) (13 OCH3), 4.41 (ddd, 1H, J 4,5 ) 9.9,
J 5,6A ) 4.5, J 5,6B ) 1.9 Hz, H-5), 4.53 (dd, 1H, J 6A,6B ) 12.3 Hz,
H-6A), 4.75 (dd, 1H, H-6B), 5.18 (dd, 1H, J 1,2 ) 3.5, J 2,3 ) 9.9
Hz, H-2), 5.30 (d, 1H, H-1), 5.78 (t, 1H, J 3,4 ) J 4,5 ) 9.9 Hz,
H-4), 6.10 (t, 1H, H-3), 6.92 (s, 1H) and 7.44 (s, 1H) (2 ArH),
7.19 (s, 2H) and 7.27 (s, 2H) (2 ArH2); 13C NMR (CDCl3) δ 56.0,
56.2, 56.5, 60.4, 60.9, 61.0, 61.1, 63.6, 67.3, 69.4, 71.0, 72.5,
83.5, 84.1, 97.2, 107.2, 107.4, 110.2, 111.1, 123.9, 124.0, 130.4,
130.5, 142.8, 142.9, 145.1, 145.2, 153.0, 153.5, 153.9, 154.0,
165.5, 165.6, 166.0; HR-FABMS calcd for C47H52I2O22 m/z
1222.1039, found 1222.1063.
etate 2:1) which afforded pure 15 (0.62 g, 97% based on the
1
benzoic acid): [R]20 -19.3 (c 1.5, CHCl3); H NMR (CDCl3) δ
D
3.71, 3.72, 3.86, 3.86, 3.87, 3.90, 3.91, 3.92, 3.93 (9s, 9 × 3H,
9 OCH3), ∼3.9 (occluded m, 1H, H-6A), 4.34 (d, 1H, J 6A,6B
)
7.9 Hz, H-6B), 4.89 (br d, 1H, J 5,6A ) 5.5 Hz, H-5), 5.10 (d,
1H), 5.17 (d, 1H) (H-2,4), 5.70 (t, 1H, J 2,3 = J 3,4 ) 3.6 Hz, H-3),
5.72 (s, 1H, H-1), 7.23, 7.24, 7.30 (3s, 3H, 3 ArH); 13C NMR
(CDCl3) δ 56.3, 56.4, 60.8, 60.9, 61.0, 61.1, 66.5, 70.7, 72.1,
72.9, 74.8, 84.1, 84.3, 84.7, 100.0, 111.0, 111.2, 111.5, 129.1,
129.7, 129.8, 145.5, 145.6, 153.4, 153.6, 154.0, 165.0, 165.3,
165.4. HR-FABMS calcd for C36H37I3O17 m/z 1121.9164, found
1121.9114.
Meth yl 2,3-Di-O-ben zyl-4,6-bis-O-(2-iod o-3,4,5-tr im eth -
oxyben zoyl)-r-D-glu cop yr a n osid e (6b ). Prepared from
methyl 2,3-di-O-benzyl-R-D-glucopyranoside24 and purified by
FCC (hexane-ethyl acetate 1:1); yield: 86.7%. [R]20 +3.6 (c
D
2.8, CHCl3); 1H NMR (CDCl3) δ 3.43, 3.65, 3.845, 3.855, 3.89,
3.90, 3.92 (7s, 7 × 3H, 7 OCH3), 3.66 (occluded dd, 1H, H-2),
4.10 (t, 1H, J 2,3 = J 3,4 ) 9.8 Hz, H-3), 4.18 (ddd, 1H, J 4,5
10.2, J 5,6A ) 4.8, J 5,6B ) 2.3 Hz, H-5), 4.39 (dd, 1H, J 6A,6B
)
)
Meth yl 3,6-An h yd r o-2,4-bis-O-(2-iod o-3,4,5-tr im eth oxy-
ben zoyl)-r-D-glu cop yr a n osid e (16). Prepared from methyl
3,6-anhydro-R-D-glucopyranoside27 and purified by FCC (hex-
ane-ethyl acetate 1:1); yield: 26%. [R]20D +34.2 (c 1.6, CHCl3);
1H NMR (CDCl3) δ 3.48, 3.51, 3.56, 3.80, 3.82, 3.83, 3.84 (7s,
7 × 3H, 7 OCH3), 4.11 (dd, 1H, J 5,6A ) 3.2, J 6A,6B ) 10.8 Hz,
H-6A), 4.31 (d, 1H, J 5,6B ) 0, H-6B), 4.69 (t, 1H, J 4,5 ) 2.9 Hz,
H-5), 4.89 (t, 1H, J 2,3 ) 4.0, J 3,4 ) 5.3 Hz, H-3), 5.02 (dd, 1H,
H-4), 5.19 (d, 1H, J 1,2 ) 3.8 Hz, H-1), 5.42 (t, 1H, H-2), 6.72 (s,
1H), 7.21 (s, 1H) (2 ArH); 13C NMR (CDCl3) δ 56.0, 56.1, 57.6,
60.7, 60.9, 68.7, 68.9, 70.5, 71.8, 73.3, 83.2, 84.1, 96.3, 110.3,
112.4, 128.9, 130.7, 144.6, 145.3, 152.8, 152.9, 153.7, 165.8,
166.1. HR-FABMS calcd for C27H30I2O13 m/z 815.9775, found
815.9772.
12.3 Hz, H-6A), 4.62 (dd, 1H, H-6B), ∼4.64 (d, 1H, J ) 12.1
Hz) and 4.79 (d, 1H) (OCHAHBPh), 4.65 (d, 1H, J 1,2 ) 3.7 Hz,
H-1), 4.71 (d, 1H, J ) 11.6 Hz) and 4.95 (d, 1H) (OCHAHBPh),
5.41 (t, 1H, H-4), 6.99 (s, 1H) and 7.38 (s, 1H) (2 ArH), 7.15-
7.35 (m, 10H, 2 Ph); 13C NMR (CDCl3) δ 55.8, 56.2, 56.6, 60.8,
61.0, 63.9, 67.3, 71.2, 73.5, 75.3, 79.1, 79.8, 83.9, 84.0, 98.3,
110.5, 111.2, 127.3, 127.4, 128.0, 128.1, 128.2, 128.5, 130.5,
130.5, 137.9, 138.3, 145.0, 145.1, 153.4, 153.5, 153.8, 153.9,
165.2, 166.1. Anal. Calcd for C41H44I2O14: C, 48.54; H, 4.37;
I, 25.02. Found: C, 48.65; H, 4.43; I, 25.12.
Meth yl 4,6-Di-O-ben zyl-2,3-bis-O-(2-iod o-3,4,5-tr im eth -
oxyben zoyl)-r-D-m a n n op yr a n osid e (9). Prepared from
methyl 4,6-di-O-benzyl-R-D-mannopyranoside25 and purified by
3-O-Ben zyl-5,6-bis-O-(2-iod o-3,4,5-tr im eth oxyben zoyl)-
1,2-O-isop r op ylid en e-r-D-glu cofu r a n ose (17). Prepared
from 3-O-benzyl-1,2-O-isopropylidene-R-D-glucofuranose and
FCC (hexane-ethyl acetate 2:1); yield: 93%. [R]20 -16.2 (c
D
1.7, CHCl3); 1H NMR (CDCl3) δ 3.45, 3.49, 3.67, 3.82, 3.84,
3.85, 3.91 (7s, 7 × 3H, 7 OCH3), 3.76-3.92 (m, 2H, H-6A, 6B),
3.99 (br d, 1H, J 4,5 ) 9.9 Hz, H-5), 4.37 (t, 1H, J 3,4 ) 9.8 Hz,
H-4), 4.52 and 4.67 (2d, AB, 2H, J ) 12.0 Hz, OCHAHBPh),
4.56 and 4.71 (2d, AB, 2H, J ) 11.3 Hz, OCHAHBPh), 4.95 (s,
1H, H-1), 5.67 (narrow m, 1H, H-2), 5.81 (dd, 1H, J 2,3 ) 3.2
Hz, H-3), 6.92 (s, 1H, 1 ArH), 7.16-7.19 (m, 5H, 4 PhH, 1 ArH),
7.26-7.33 (m, 6H, 6 PhH); 13C NMR (CDCl3) δ 54.9, 55.7, 60.5,
60.6, 60.7, 68.5, 71.1, 71.3, 72.8, 72.9, 73.4, 74.2, 83.3, 84.2,
98.1, 110.1, 111.3, 127.2, 127.3, 127.4, 127.6, 128.0, 128.1,
129.5, 130.9, 137.6, 137.7, 144.5, 145.2, 152.9, 153.0, 153.5,
153.7, 164.9, 165.2. Anal. Calcd for C41H44I2O14: C, 48.54;
H, 4.37; I, 25.02. Found: C, 48.80; H, 4.53; I, 25.23.
purified by FCC (hexane-ethyl acetate 3:1); yield: 93%. [R]20
D
1
-51.3 (c 1.4, CHCl3); H NMR (CDCl3) δ 1.32, 1.48 (2s, 2 ×
3H, CMe2), 3.74 (s, 3H), 3.81 (s, 3H), 3.84 (s, 3H), 3.85 (s, 3H),
3.89 (s, 6H) (6 OCH3), 4.14 (d, 1H, J 3,4 ) 3.2 Hz, H-3), 4.58-
4.66 (m, 4H, H-2,4, OCH2Ph), 4.68 (dd, 1H, J 5,6A ) 6.4, J 6A,6B
) 12.4 Hz, H-6A), 4.95 (dd, 1H, J 5,6B ) 2.1 Hz, H-6B), 5.86 (m,
1H, H-5), 5.96 (d, 1H, J 1,2 ) 3.6 Hz, H-1), 7.1 (s, 1H, ArH),
7.21-7.36 (m, 6H, Ph, ArH); 13C NMR (CDCl3) δ 26.3, 27.0,
56.4, 60.8, 61.0, 64.7, 70.1, 72.4, 78.6, 81.6, 81.9, 84.0, 84.1,
105.4, 111.2, 111.3, 112.1, 127.9, 128.0, 128.5, 130.5, 130.6,
137.1, 145.1, 145.2, 153.4, 153.4, 153.9, 153.9, 165.1, 165.9.
HR-FABMS calcd for C36H40I2O14 m/z950.0507,found: 950.0470.
Meth yl 2,6-Di-O-ben zyl-3,4-bis-O-(2-iod o-3,4,5-tr im eth -
oxyben zoyl)-r-D-ga la ctop yr a n osid e (12). Prepared from
methyl 2,6-di-O-benzyl-R-D-galactopyranoside26 and purified
3-O-(2-Iod o-3,4,5-t r im et h oxyben zoyl)-1,2:5,6-d i-O-iso-
p r op ylid en e-r-D-glu cofu r a n ose (18). Prepared from 1,2:
5,6-di-O-isopropylidene-R-D-glucofuranose (0.39 g, 1.5 mmol),
2-iodo-3,4,5-trimethoxybenzoic acid (0.53 g, 1.58 mmol), DCC
(0.37 g, 1.8 mmol), and DMAP (0.056 g) according to the
general procedure; crude 18 was purified twice by flash
by FCC (hexane-ethyl acetate 3:1); yield 70%. [R]20 +34.9
D
1
(c 1.6, CHCl3); H NMR (CDCl3) δ 3.47, 3.59, 3.65, 3.84, 3.85,
3.87, 3.91 (7s, 7 × 3H, 7 OCH3), ∼3.62 (m, 2H, H-6A, 6B), 4.18
(dd, 1H, J 1,2 ) 3.5, J 2,3 ) 10.5 Hz, H-2), 4.33 (t, 1H, J 4,5 = 0,
J 5,6A = J 5,6B = 6.1 Hz, H-5), 4.51 (AB, 2H, J ) 11.9
Hz, OCHAHBPh), 4.65 (d, 1H, J ) 12.5 Hz) and 4.75 (d, 1H)
(AB, OCHAHBPh), 4.84 (narrow d, 1H, H-1), 5.76 (dd, 1H, J 3,4
) 3.3 Hz, H-3), 5.94 (narrow m, 1H, H-4), 7.04 (s, 1H) and
7.08 (s, 1H) (2 ArH), 7.23-7.31 (m, 10H, 2 Ph); 13C NMR
(CDCl3) δ 55.6, 56.1, 56.2, 60.8, 61.0, 61.1, 67.8, 68.7, 71.0,
71.2, 73.0, 73.6, 74.1, 83.6, 83.9, 98.6, 110.8, 111.2, 127.6, 127.7,
127.8, 127.9, 128.4, 128.5, 130.6, 131.3, 137.8, 138.0, 144.8,
145.2, 153.3, 153.8, 154.0, 165.5, 165.6. Anal. Calcd for
chromatography (hexane-ethyl acetate 5:1). Yield: 0.848 g
1
(97%). [R]20 -36.5 (c 3.0, CHCl3); H NMR (CDCl3) δ 1.30,
D
1.35, 1.43, 1.56 (4s, 4 × 3H, 2 CMe2), 3.88 (s, 6H), 3.92 (s, 3H)
(3 OCH3), 4.05-4.15 and 4.30-4.37 (2m, 4H, H-4,5,6A,6B),
4.75 (d, 1H, J 1,2 ) 3.7 Hz, J 2,3 ) 0, H-2), 5.46 (d, 1H, J 3,4 ) 2.3
Hz, H-3), 5.97 (d, 1H, H-1), 7.17 (s, 1H, ArH); 13C NMR (CDCl3)
δ 25.4, 26.3, 26.8, 26.9, 56.3, 60.9, 61.1, 67.5, 72.8, 77.7, 80.0,
83.3, 83.8, 105.3, 109.4, 110.8, 112.5, 130.7, 145.3, 153.5, 154.0,
165.4. HR-FABMS calcd for C22H29IO10 m/z 580.0805, found
580.0780.
C
41H44I2O14: C, 48.54; H, 4.37; I, 25.02. Found: C, 48.63; H,
6-O-(2-Iod o-3,4,5-t r im et h oxyben zoyl)-1,2:3,4-d i-O-iso-
p r op ylid en e-r-D-ga la ctop yr a n ose (19). Prepared from 1,2:
3,4-di-O-isopropylidene-R-D-galactopyranose as described for
4.41; I, 25.51.
1,6-An h yd r o-2,3,4-tr is-O-(2-iod o-3,4,5-tr im eth oxyben -
zoyl)-r-D-glu cop yr a n ose (15). A suspension of 1,6-anhydro-
â-D-glucopyranose (0.162 g, 1.0 mmol) in CH2Cl2 (12 mL)
the preparation of 18 and purified by FCC (hexane-ethyl
1
acetate 5:1); yield: 97%. [R]20 -32 (c 1.7, CHCl3); H NMR
D
(CDCl3) δ 1.32, 1.35, 1.48, 1.51 (4s, 4 × 3H, 2CMe2), 3.87, 3.88,
(24) Giuliano, R. M.; Buzby, J . H. J . Carbohydr. Chem. 1987, 6, 541-
3.91 (3s, 3 × 3H, 3 OCH3), 4.20 (ddd, 1H, J 4,5 ) 1.8, J 5,6A
)
552.
(25) Kong, F.; Schuerch, C. Carbohydr. Res. 1983, 112, 141-147.
(26) Schneider, J .; Lee, Y. C.; Flowers, H. M. Carbohydr. Res. 1974,
36, 159-166.
(27) Haworth, W. N., Owen, L. N.; Smith, F. J . Chem. Soc. 1941,
88-102.