242
G. Adiwidjaja et al. / Carbohydrate Research 325 (2000) 237–244
tilled off under diminished pressure. The
residue was dissolved in EtOAc, the solids
were filtered off and the crude product ob-
tained after removal of the solvent was chro-
matographed twice (SiO2, 1:1 EtOAc–
petroleum ether, Rf 0.38) to yield 4 (1.32 g,
80%) as a crystalline solid, mp 152 °C. [h]D20
+206° (c 1.0, CHCl3). IR: w 3025, 2930, 2920,
1352, 1177, 1066, 917, 859, 526, 502. 1H NMR
(400 MHz, CDCl3): l 5.19 (dd, 1 H, H-2),
5.13 (d, 1 H, J1,2 2.9 Hz, H-1), 5.10 (dd, 1 H,
J3,4 6.2, J2,3 9.4 Hz, H-3), 4.65–4.61 (m, 2 H,
H-4, H-5), 3.55 (dd, 1 H J5,6%, 3.8 Hz, H-6%),
3.47 (s, 3 H, OCH3), 3.14 (s, 3 H, CH3SO2),
3.07 (s, 3 H, CH3SO2), 2.68 (d, 1 H, J6,6% 10.4
Hz, H-6). 13C NMR (100.6 MHz, CDCl3): l
98.20 (C-1), 75.20 (C-2), 73.31 (C-3), 72.84
(C-5), 56.32 (CH3O), 41.95 (C-4), 39.05
tion mixture was stirred at rt for 24 h under
monitoring with TLC (3:2 EtOAc–petroleum
ether, Rf 0.60). The precipitate was filtered off
and the filtrate washed with a satd NaHCO3
soln until it was neutral. After evaporation
under diminished pressure, the crude product
was chromatographed (370 g SiO2, 1:1
EtOAc–petroleum ether, Rf 0.45) to yield 7
(4.94 g, 83%) as a yellowish solid, mp 115 °C
(dec). [h]2D0 +77° (c 1.0, acetone). IR: w 3030,
3015, 3005, 2947, 1356, 1201, 1180, 1093,
1
1049, 987, 908, 849, 717, 523. H NMR (400
MHz, acetone-d6): l 4.87 (d, 1 H, H-1), 4.71
(dd, 1 H, H-3), 4.56 (dd, 1 H, J2,3 9.6, J1,2 3.7
Hz, H-2), 3.90 (dd, 1 H, J3,4 9.6 Hz, H-4), 3.78
(m, 1 H, H-6%), 3.69 (dd, 1 H, J6,6% 10.4 Hz,
H-6), 3.54 (ddd, 1 H, J5,6 5.4, J4,5 10.0, J5,6% 0.5
Hz, H-5), 3.33 (s, 3 H, CH3O), 3.07 (s, 3 H,
CH3SO2), 3.06 (s, 3 H, CH3SO2), 1.43 (d, 3 H,
J 0.5 Hz, CH3), 1.27 (d, 3 H, J 0.5 Hz, CH3).
13C NMR (100.6 MHz, acetone-d6): l 100.36
[(CH3)2C], 99.26 (C-1), 78.13 (C-3), 76.68 (C-
2), 72.28 (C-4), 63.9 (C-5), 62.15 (C-6), 55.44
(CH3O), 38.86 (CH3SO2), 37.95 (CH3SO2),
28.71 (CH3), 18.92 (CH3). FABMS: m/z (%)
391 (100) [MH+], 375 (18), 359 (7), 301 (38),
237 (27), 223 (14), 205 (42); FABHRMS
Calcd for C12H23O10S2: 391.0733. Found
391.0724.
(CH3SO2), 38.62 (CH3SO2), 28.10 (C-6). EIMS
+
(70 eV): m/z (%) 348 (9) [M ], 317 (20)
[M+−OCH3], 209 (11), 207 (9), 206 (8), 192
(11), 176 (7), 175 (14), 166 (20), 157 (6), 152
(20), 148 (7), 139 (7), 132 (7), 126 (7), 117 (9),
115 (7), 114 (14), 113 (22), 111 (15), 101 (7), 99
(8), 97 (38), 96 (7), 87 (27), 86 (9), 85 (100), 81
(21), 79 (52), 74 (10), 73 (87), 72 (12), 71 (16),
70 (11), 69 (12), 68 (9), 61 (15), 60 (8), 58 (7),
56 (7), 54 (7), 48 (8), 41 (41).
X-ray structural data. C9H16O8S3: crystal di-
mensions 0.55×0.32×0.30 mm, orthorhom-
bic, P212121, a=547.6(1) pm, b=1557.8(2)
pm, c=1722.4(2) pm, h=i=k=90°, V=
Methyl 2,3-di-O-mesyl-h- -glucopyranoside
D
(8).—Acetyl chloride (0.20 mL, 0.23 g, 2.90
mmol) was dissolved in MeOH (40 mL). After
30 min stirring, the methanolic HCl soln was
added to 7 (4.89 g, 12.52 mmol) and the
mixture was stirred for 2 h. Sodium carbonate
was added in two portions (2×0.18 g, 0.34
mmol) and, after 30 min, the MeOH was
removed. The residue was extracted with a
sufficient amount of CH2Cl2. Drying (MgSO4)
and evaporation under diminished pressure
yielded 8 (4.12 g, 94%) as a colorless solid, mp
150 °C (dec) (Ref. [8]: 150.6 °C, Ref. [10]:
150–151 °C). [h]2D0 +83° (c 1.1, MeOH) [Ref.
[9]: [h]2D5 +82.4° (c, 1.06, MeOH)] IR: w 3533
(OH), 3350, 3040, 2984, 2934, 2887, 2851,
1353, 1341, 1181, 1052, 1010, 971, 849, 771,
731, 660, 562, 501. 1H NMR (400 MHz, D2O):
l 5.06 (d, 1 H, J1,2 3.1 Hz, H-1), 4.78–4.74 (m,
2 H, H-2, H-3), 3.81 (dd, 1 H, H-6%), 3.71 (dd,
1 H, J4,5 1.5, J3,4 7.3 Hz, H-4), 3.70 (dd, 1 H,
J6,6% 12.2 Hz, H-6), 3.66 (dd, 1 H, J5,6 1.8, J5,6%
1.4693(4) nm3, Z=4, zcalcd =1.58 g cm−3
,
v=4.944 mm−1, r−2r scan, 2775 indepen-
dent reflections, 2331 significant reflections
[I\2|(I)], parameters 210, R factor 0.05419,
Rw factor 0.13804.
Methyl 4,6-O-isopropylidene-2,3-di-O-me-
syl-h-
D
-glucopyranoside (7).—Methyl 4,6-O-
isopropylidene-a-
D
-glucopyranoside (6) (3.58
g, 15.3 mmol) [8] was dissolved in CH2Cl2
(250 mL). Mesyl chloride (8.92 mL, 13.1 g,
114.5 mmol) was added at −20 °C. The reac-
4 The discrepancy between R and Rw is due to the program
used for refinement [16]: the weighted R index based on F2o is
(for compelling statistical reasons) much higher than the
conventional R index based on Fo with a threshold of Fo\
4|(Fo). For comparison with structures refined against F, the
latter is, therefore, printed as well. Despite the fact that Rw
and not R is the quantity minimized, R has the advantage
that it is relatively insensitive to the weighting scheme [16].