7276
O.S. Maldonado et al. / Tetrahedron 67 (2011) 7268e7279
CHCl3); 1H NMR (300 MHz, CDCl3)
d
7.39 (s, 1H, Harom), 7.23 (s, 1H,
was deprotected by following the general procedure. The reaction
Harom), 5.28 (m, 2H, H-2, H-4), 5.13 (t,1H, J¼9.4 Hz, H-3), 5.03 (d,1H,
J¼7.4 Hz, H-1), 4.18 (m, 4H, H-6, H-60, OCH2R), 3.87 (dd, 1H, J¼7.8,
5.6 Hz, H-5), 2.05 (m, 12H, COOCH3), 1.69 (dd, 2H, J¼13.9, 6.7 Hz,
crude was purified by flash chromatography (hexane/ethyl acetate
from 2:1 to 1:2) affording compound 48 as an oil (44 mg, 65%); ½a D22
ꢄ
ꢀ12.5 (c 1 in CHCl3); 1H NMR (400 MHz, CDCl3)
d 7.45 (d, 1H,
OCH2CH2R), 1.32 (m, 16H, 8ꢁ CH2), 0.85 (t, 3H, J¼6.4 Hz, CH3). 13
C
J¼1.8 Hz, Harom), 7.16 (d, 1H, J¼1.8 Hz, Harom), 7.11, 5.77 (2br s, 2H,
OH), 5.41e5.31 (m, 3H, H-2, H-3, H-4), 5.10 (d, 1H, J¼7.12 Hz, H-1),
4.26 (t, 2H, J¼6.6 Hz, COOCH2), 4.20 (d,1H, J¼9.6 Hz, H-5), 3.78 (s, 3H,
COOCH3), 2.15, 2.08, 2.07 (3 s,12H, O]CCH3),1.78e1.71 (m, 2H, CH2),
1.46e1.25 (m, 10H, 5ꢁ CH2), 0.90 (t, 3H, J¼7.5 Hz, CH3). 13C NMR
NMR (75 MHz, CDCl3) d 170.9, 170.4, 170.2, 169.6 (C]O), 166.0 (C]
O), 144.8, 143.9139.1, 122.4 (Cqarom), 113.2 (CHarom), 111.0 (CHarom),
101.2 (C-1), 72.5 (C-3), 72.2 (C-5), 71.4 (C-2), 68.1 (C-4), 65.3
(OCH2R), 61.7 (C-6), 31.9 (CH2), 29.7 (CH2), 29.68 (CH2), 29.61 (CH2),
29.40 (CH2), 29.37 (CH2), 28.79 (CH2), 26.09 (CH2), 22.74 (CH2), 20.8,
20.7, 20.6 (COOCH3), 14.17 (CH3). HRMS (ESþ) calcd for
C33H48O14Na, 691.2942. Found; 691.2925.
(101 MHz, CDCl3)
d 170.0, 169.9, 169.5, 167.0, 165.9 (C]O), 145.1,
143.6, 139.6, 122.6 (Carom), 113.4, 112.2 (Carom), 101.6 (C-1), 72.4 (C-5),
71.2, 71.1, 68.9 (C-2, C-3, C-4), 65.2 (COOCH2R), 53.2 (OCH3), 31.8,
29.3, 29.2, 28.7, 26.0, 22.6 (CH2) 20.7, 20.6 20.5 (COOCH3), 14.1 (CH3).
HRMS (ESþ) calcd for C28H38NaO14 (MþNaþ) 621.2159. Found:
621.2140.
4.4.6. Hexadecyl 3-O-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranoside)-
4,5-dihydroxybenzoate 42. Compound 35 (222 mg, 0.30 mmol) was
deprotected by following the general procedure. The reaction crude
was purified by flash chromatography (hexane/ethyl acetate from 2:1
4.4.10. Hexadecyl
3-O-(methyl-2,3,4-tri-O-acetyl-b-D-glucopyr-
to 1:2) affording compound 42(169 mg, 80%); ½a D22
ꢄ
ꢀ2.0 (c 1 in CHCl3);
anosyluronate)-4,5-dihydroxybenzoate 49. Compound 46 (337 mg,
0.45 mmol) was deprotected by following the general procedure.
The reaction crude was purified by flash chromatography (hexane/
ethyl acetate from 2:1 to 1:1) affording compound 49 as an oil
1H NMR (300 MHz, CDCl3)
d 7.40 (s,1H, Harom), 7.26 (s,1H, Harom), 5.28
(m, 2H, H-2, H-4), 5.14 (t,1H, J¼9.4 Hz, H-3), 5.04 (d,1H, J¼7.5 Hz, H-1),
4.23 (m, 4H, H-6, H-60, OCH2R), 4.89 (m, 1H, H-5), 2.05 (m, 12H,
COOCH3), 1.70 (m, 2H, OCH2CH2R),1.33 (m, 26H,13ꢁ CH2), 0.85 (t, 3H,
a 22
(200 mg, 62%); ½ ꢄD ꢀ9.4 (c 1 in CHCl3); 1H NMR (300 MHz, CDCl3)
J¼6.5Hz, CH3).13CNMR(75MHz, CDCl3)
d
170.9,170.3,170.1,169.5(C]
d 7.19 (s, 1H, Harom), 7.05 (s, 1H, Harom), 6.92, 5.77 (2br s, OH),
O),166.0 (C]O),144.7,143.8,139.1,122.4 (Cqarom),113.2 (CHarom), 111.2
(CHarom), 101.2 (C-1), 72.4 (C-3), 72.1 (C-5), 71.4 (C-2), 68.0 (C-4), 65.2
(OCH2R), 61.6 (C-6), 31.9, 29.8, 29.7, 29.5, 29.4, 29.3, 29.2, 28.9, 26.0,
22.7 (CH2), 20.9, 20.7, 20.6, 20.5 (COOCH3), 14.1 (CH3). HRMS (ESþ):
mass calculated for C37H56O14Na 747.3568. Found; 747.3622.
5.18e5.04 (m, 3H, H-2, H-3, H-4), 4.89 (d, 1H, J¼7.5 Hz, H-1),
4.04e3.97 (m, 3H, H-5, OCH2), 3.52 (s, 3H, COOCH3), 1.90, 1.83, 1.82
(3 s, 12H, O]CCH3), 1.52e1.45 (m, 2H, CH2), 1.23e1.00 (m, 26H, 13ꢁ
CH2), 0.65 (t, 3H, J¼7.5 Hz, CH3). 13C NMR (75 MHz, CDCl3)
d 170.0,
169.9, 169.5, 167.0, 165.9 (C]O), 145.0, 143.7, 139.6, 122.5 (Carom),
113.4, 112.0 (Carom), 101.4 (C-1), 72.3 (C-5), 71.3, 71.1, 68.9 (C-2, C-3,
C-4), 65.2 (COOCH2R), 53.2 (OCH3), 31.9, 29.7, 29.6, 29.5, 29.45, 29.4,
29.3, 29.2 28.7, 26.0, 22.7(CH2), 20.6, 20.5 (COOCH3), 14.1 (CH3).
HRMS (ESþ) calcd for C36H54NaO14 (MþNaþ) 733.3411. Found:
773.3398.
4.4.7. Octadecyl 3-O-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranoside)-
4,5-dihydroxybenzoate 43. Compound 36 (200 mg, 0.25 mmol) was
deprotected by following the general procedure. The reaction crude
was purified by flash chromatography (hexane/ethyl acetate from
2:1 to 1:1) affording compound 43 (158 mg, 83%); ½a D22
ꢄ þ0.2 (c 1 in
CHCl3); 1H NMR (300 MHz, CDCl3)
d
7.39 (s, 1H, Harom), 7.24 (s, 1H,
4.5. General procedure for acetyl deprotection
Harom) 5.28 (m, 2H, H-2, H-4), 5.13 (t, 1H, J¼9.4 Hz, H-3), 5.03 (d, 1H,
J¼7.4 Hz, H-1), 4.21 (m, 4H, H-6, H-60, COOCH2R), 3.88 (m, 1H, H-5),
2.05 (m, 12H, COOCH3), 1.70 (m, 2H, COOCH2CH2R), 1.32 (m, 30H,
Compounds 37e43 and 47e49 were dissolved in methanol
(2 mL for each 100 mg) and Na2CO3 (0.3 equiv) was then added. The
reaction mixture was stirred for 1 h and when starting material had
disappeared, IR-120 was then added until pH¼7. The reaction
mixture was then filtered and solvents removed to afford com-
pounds 11e20 in high yields.
CH2), 0.85 (t, 3H, J¼6.6 Hz, CH3). 13C NMR (75 MHz, CDCl3)
d 170.9,
170.4, 170.2, 169.6 (C]O), 166.1 (C]O), 144.8, 143.9, 139.1, 122.4
(Cqarom), 113.2 (CHarom), 111.0 (CHarom), 101.19 (C-1), 72.5 (C-3), 72.3
(C-5), 71.4 (C-2), 68.1 (C-4), 65.3 (OCH2R), 61.7 (C-6), 32.0 (CH2),
29.76 (CH2), 29.73 (CH2), 29.69 (CH2), 29.64 (CH2), 29.42 (CH2),
29.39 (CH2), 28.80 (CH2), 26.10 (CH2), 22.75 (CH2), 20.64, 20.61,
20.60, 20.58 (COOCH3), 14.18 (CH3). HRMS (ESþ): mass calculated
for C39H60O14Na (MþNa); 775.3881. Found; 775.3942.
4.5.1. Butyl 3-O-(b-D-glucopyranosyl)-4,5-dihydroxybenzoate
11. Compound 37 (289 mg, 0.52 mmol) was deprotected by fol-
lowing the general procedure affording compound 11 (200 mg,
quantitative); ½a D22
ꢀ53.0 (c 1 in MeOH); dH (300 MHz, MeOD) 7.19
ꢄ
4.4.8. Butyl
3-O-(methyl-2,3,4-tri-O-acetyl-b-D-glucopyranosyluro-
(d, 1H, J¼1.9 Hz, Harom), 7.02 (d, 1H, J¼1.9 Hz, Harom), 4.61 (d, 1H,
J¼6.6 Hz, H-1), 4.08 (t, 2H, J¼6.6 Hz, OCH2), 3.70 (m, 1H, H-6), 3.57
(dd, 1H, J¼4 and 12.3 Hz, H-60), 3.32e3.25 (m, 3H, H-2, H-3, H-4),
3.09e3.08 (m, 1H, H-5), 1.52e1.43 (m, 2H, CH2), 1.27e1.19 (m, 2H,
nate)-4,5-dihydroxybenzoate 47. Compound 44 (242 mg, 0.41 mmol)
was deprotected by following the general procedure. The reaction
crude was purified by flash chromatography (hexane/ethyl acetate
from 2:1 to 1:2) affording compound 47 (180 mg, 81%); ½a D22
ꢄ
ꢀ17.0 (c
CH2), 0.75 (t, 3H, J¼7.35 Hz, CH3);
d
13C (62.5 MHz, MeOD) 166.8
1 in CHCl3); 1H NMR (300 MHz, CDCl3)
d
7.36 (s, 1H, Harom), 7.20 (s,
(O]Cbenzoate), 145.4, 145.3, 140.2, 120.6, 111.8, 110.3 (Carom), 102.6
(C-1), 76.8 (C-3), 76.1 (C-5), 73.4 (C-2), 69.6 (C-4), 64.4 (CH2O), 60.7
(C-6), 30.5, 18.9 (CH2), 12.8 (CH3). HRMS (ESþ) calcd for
C17H24NaO10 (MþNaþ) 411.1267. Found: 411.1263.
1H, Harom), 7.06, 5.87 (2br s, 2H, OH), 5.31e5.19 (m, 3H, H-2, H-3, H-
4), 5.03 (d,1H, J¼7.47 Hz, H-1), 4.19 (t, 2H, J¼6.5 Hz, COOCH2), 4.13 (d,
1H, J¼9.0 Hz, H-5), 3.68 (s, 3H, COOCH3), 2.05,1.99 (s s, 9H, O]CCH3),
1.67e1.60 (m, 2H, CH2), 1.41e1.30 (m, 2H, CH2), 0.89 (t, 3H, J¼7.5 Hz,
CH3). 13C NMR (101 MHz, CDCl3)
d
170.1, 170.0,169.6, 167.1, 166.0 (C]
4.5.2. Hexyl 3-O-(b-D-glucopyranosyl)-4,5-dihydroxybenzoate
O), 145.1, 143.7, 139.7, 122.3 (Carom), 113.4, 111.8 (Carom), 101.2 (C-1),
72.3 (C-5), 71.3, 71.1, 68.9 (C-2, C-3, C-4), 64.9 (COOCH2R), 53.2
(OCH3), 30.7 (CH2), 20.6, 20.5 20.4 (COOCH3), 19.2 (CH2), 13.7 (CH3).
HRMS (ESþ) calcd for C24H30NaO14 (MþNaþ) 565.1533. Found:
565.1539.
12. Compound 38 (293 mg, 0.52 mmol) was deprotected by fol-
lowing the general procedure affording compound 12 (200 mg,
96%); ½a 2D2
ꢀ53.6 (c 1 in MeOH); dH (400 MHz, MeOD) 7.44 (d, 1H,
ꢄ
J¼2.0 Hz, Harom), 7.25 (d, 1H, J¼2.0 Hz, Harom), 4.84 (d, 1H, J¼6.6 Hz,
H-1), 4.24 (t, 2H, J¼6.6 Hz, OCH2), 3.91 (dd,1H, J¼2.2 ans 12.2 Hz, H-
6), 3.79 (dd, 1H, J¼4.48 and 12.2 Hz, H-60), 3.55e3.45 (m, 3H, H-2,
H-3, H-4), 3.34e3.32 (m, 1H, H-5), 1.77e1.70 (m, 2H, CH2),
4.4.9. Octyl
3-O-(methyl-2,3,4-tri-O-acetyl-b-D-glucopyranosyluro-
nate)-4,5-dihydroxybenzoate 48. Compound 45 (72 mg, 0.11 mmol)
1.48e1.33 (m, 6H, 3ꢁ CH2), 0.92 (t, 3H, J¼6.88 Hz, CH3);
d
13C