A. Kornienko et al./Carbohydrate Research 310 (1998) 141±144
143
toluene. TLC and preparative TLC were per-
formed using Baker glass-backed silica gel plates
(0.25 mm thickness) with 254-nm ¯uorescent indi-
cator. The chromatograms were visualized by (a)
ultraviolet illumination and (b) dipping in the
Hanes±Isherwood solution (1 g of (NH4)6Mo7
suciently pure diacetate 5 was obtained; 1H NMR
(CDCl3, inositol numbering is the same as in 5): ꢃ
7.42±7.28 (m, 20 H, aromatic), 5.41 ( t, 1 H, J5,6,
J6,1 3.6 Hz, H-6), 5.34 (dd, 1 H, J4,5, 9.5 Hz, J5,6
3.6 Hz, H-5), 4.93, 4.82 (2d, 2 H, Jgem 10.4 Hz,
CH2Ph), 4.86, 4.70 (2d, 2 H, Jgem 11.6 Hz, CH2Ph),
4.73 (s, 2 H, CH2Ph), 4.69, 4.57 (2d, 2 H, Jgem
11.7 Hz, CH2Ph), 4.04 ( t, 1 H, J2,3, J3,4 9.5 Hz, H-
3), 3.79 ( t, 1 H, J3,4, J4,5 9.5 Hz, H-4), 3.72 (dd, 1
H, J1,2 3.6, J2,3 9.5 Hz, H-2), 3.70 ( t, 1 H, J6,1, J1,2
3.6 Hz, H-1), 2.00 (s, 3 H, OAc), 1.97 (s, 3 H, OAc).
1,2,3,4-Tetra-O-benzyl-5-O-p-methoxybenzyl-d-
chiro-inositol (6).ÐA suspension of 5 (20 mg,
37 ꢂmol) and dibutyltin oxide (10 mg, 41 ꢂmol) in
20 mL of benzene was ®tted with aꢀdistillation head
and placed in an oil bath at 110 C until most of
the benzene had distilled. An additional portion of
benzene (10 mL) was added to the residue and the
mixture was heated until again most of the benzene
had distilled. The reaction mixture was cooled and
treated with p-methoxybenzyl chloride (7.5 ꢂL,
55 ꢂmol) and tetrabutylammonium bromide
(13 mg, 41 ꢂmol). The mixture was then heated at
re¯ux for 45 min more, then NaHCO3 (2 mL of
1 M solution) was added and the mixture was
extracted with CH2Cl2 (3Â5 mL). The combined
organic extracts were dried (MgSO4) and evapo-
rated to dryness. Preparative TLC (1:1 hexanes±
.
24 4H2O, 10 mL of 1N HCl, 3 mL of HClO4 in
O
90 mL of H2O) followed by heating. Flash chro-
matography was performed on Baker silica gel (40
mesh). Ozone was generated using an ozonator
purchased from Ozone Pure Water, Inc. (model
2HD). NMR spectra were recorded on a Bruker
AM300 spectrometer using Me4Si as an internal
standard for 1H in CDCl3, DOH (4.65 ppm) for 1H
in D2O, and 1,4-dioxane (67.4 ppm) for 13C in D2O.
Solutions of SmI2 were titrated with I2 prior to use.
1,2,3,4-Tetra-O-benzyl-d-chiro-inositol (5).ÐDue
to the low ozone ¯ux of the ozonator 400 mg
(0.75 mmol) of 4 were ozonolyzed in eight portions.
In each case a solution containing 50 mg of 4 and
20 ꢂL of pyridine in 3 mL of CH2Cl2 was treated
with ozone at 78 ꢀC until TLC (8:2 hexane±
EtOAc) showed complete disappearance of the
starting material (Rf 0.6), at which point 200 ꢂL of
Me2S were added. All eight solutions were kept at
rt for 5 h, pooled and treated with water (15 mL).
After the separation of the organic layer the aqu-
eous phase was extracted with additional CH2Cl2
(15 mL). The combined organic layers were dried
(MgSO4) and evaporated to dryness. The residue
was diluted with t-butanol (0.22 mL, 2.25 mmol) in
THF (25 mL) and added dropwise over a period of
30 min to a cold ( 78 ꢀC) solution of SmI2
(5.1 mmol) in THF (85 mL). The mixture was stir-
red for 3 h at 78 ꢀC and then overnight at rt. Sat.
NaHCO3 solution (30 mL) was added and the
white slurry was extracted with EtOAc (2Â50 mL).
The organic layer was washed with 10% Na2S2O3
(50 mL), sat. NaCl (50 mL), and dried (MgSO4).
Evaporation of the solvent and ¯ash chromato-
graphy (7:3 hexane±EtOAc) aorded pure 5
(160 mg, 40% yield); 1H NMR (CDCl3): ꢃ 7.4±7.22
(m, 20 H, aromatic), 5.02, 4.81 (2d, 2 H, Jgem
11.3 Hz, CH2Ph), 4.99, 4.65 (2d, 2 H, Jgem 10.5 Hz,
CH2Ph), 4.81, 4.65 (2d, 2 H, Jgem 10.7 Hz, CH2Ph),
4.72, 4.61 (2d, 2 H, Jgem 11.7 Hz, CH2Ph), 4.07±
3.86 (m, 5 H, CH-OR), 3.64 ( t, 1 H, J3,4 9.1 Hz,
H-3 or H-4), 2.31, 2.32 (2 br d, 2 OH); FAB
HRMS (NBA/NaI) m/z 563.2434, M+Na+ calcd
for C34H36O6 563.2411. A sample of 5 (5 mg) was
treated with Ac2O (10 ꢂL) and pyridine (0.2 mL)
for 2 h at rt. After aqueous work-up, 5 mg of
1
ether) gave 18.7 mg of 6 (77% yield); H NMR
(CDCl3): ꢃ 7.35±7.2 (m, 22 H, aromatic), 6.85±6.78
(d, 2 H, aromatic), 4.94±4.47 (m, 10 H, CH2Ar),
3.94 (dd, 1 H, J 9.3, 8.8 Hz, H-3 or H-4), 3.95±3.90
(m, 2 H, CHOR), 3.85 (dd, 1 H, J 10.3, 2.6 Hz, H-2
or H-5), 3.80±3.72 (m, 2 H, CHOR), 3.79 (s, 3 H,
OCH3), 2.41 (br s, 1 H, OH); Anal calcd for
C42H44O7: C, 76.34; H, 6.71. Found: C, 75.98; H,
6.84. A solution of 6 (3.3 mg, 5 ꢂmol) in pyridine
(192 ꢂL), was treated with Ac2O (3.3 ꢂL, 35 ꢂmol).
After aqueous work-up, 2.7 mg of acetylated prod-
uct was obtained; 1H NMR (CDCl3, inositol
numbering is the same as in 6): ꢃ 7.35±7.2 (m, 22 H,
aromatic), 6.85±6.78 (d, 2 H, aromatic), 5.32 ( t, 1
H, J6,1 and J5,6 3.4 Hz, H-6), 4.93±4.40 (m, 10 H,
CH2Ar), 3.97±3.85 (m, 2 H, CHOR), 3.77 (s, 3 H,
OCH3), 3.78±3.68 (m, 4 H, CHOR), 2.0 (s, 3 H,
OAc).
1,2,3,4,6-Penta-O-benzyl-d-chiro-inositol (7).ÐA
solution of 6 (14.2 mg, 21.5 ꢂmol) in DMF
(190 ꢂL) at 0 ꢀC was treated with NaH (3.4 mg of a
60% oil dispersion, 86 ꢂmol). After 0.5 h, the mix-
ture was treated with benzyl bromide (7.7 ꢂL,
65ꢂmol) and allowed to warm to room temperature.