306
A. Falshaw et al. / Carbohydrate Research 329 (2000) 301–308
wise, with stirring, to Ph3P (858.7 mg, 3.3
mmol) and diethyl azodicarboxylate (515.5
mL, 3.3 mmol) in dry toluene (3 mL). After 7
days with stirring at rt the reaction mixture
was fractionated directly by FC (1:5 EtOAc–
hexanes) to give the anhydride 12 (353 mg,
62%) as a white solid. Recrystallisation (1:1
MeOH–water) gave white needles; mp 106–
H-2, H-5 or H-3, H-4), 3.53 (m, 2 H, H-3, H-4
or H-2, H-5); 13C NMR (CD3OD): l 136.9
(CH2ꢀCH), 117.7 (CH2ꢀCH), 79.1 (C-1 and
C-6), 75.3 (C-2, C-5 or C-3, C-4), 73.9
(CH2ꢁO), 73.0 (C-3, C-4 or C-2, C-5); FAB+-
MS (MeOH–glycerol): Calcd for C12H21O6
[M+H+]: m/z 261.1338. Found: 261.1335.
Tetraol 9 (1.14 g, 4.4 mmol) was dissolved
in dry DMF (30 mL) and treated with NaH
(0.42 g, 60% w/w in oil, 10.5 mmol) at 0 °C,
followed by BnBr (1.8 g, 10.5 mmol) under
argon. The mixture was stirred at rt overnight
and a second portion of NaH (0.42 g, 60%
w/w in oil, 10.5 mmol) was added followed by
another portion of BnBr (1.8 g, 10.5 mmol) at
0 °C. After 24 h at rt with stirring, the reac-
tion was quenched with EtOH (100 mL) and
the mixture was poured into water (150 mL).
The resulting soln was extracted with EtOAc
(3×75 mL) and the combined EtOAc extract
was washed with water (50 mL), dried
(MgSO4), filtered and the solvent removed in
vacuo to yield crude 10 as a yellow oil con-
taminated with parafin oil (3.26 g). To 3.0 g of
this oil, p-toluenesulfonic acid monohydrate
(1.0 g, 5.3 mmol) and Pd–C (1.5 g of 10%
w/w) were added, followed by water (10 mL)
and MeOH (45 mL) and the mixture was
heated under reflux for 2.25 h [21]. The mix-
ture was cooled and the catalyst removed by
filtration through Celite pre-washed with
MeOH. The filtrate was concd and partitioned
between CHCl3 (100 mL) and water (75 mL).
The organic phase was washed with water (75
mL), dried (MgSO4), filtered and the filtrate
was taken to dryness. FC of the residue (3:2
1
107 °C; [h]2D0 −34° (c 0.72, CHCl3); H NMR
(CDCl3): 7.50–7.20 (m, 20 H, Ar), 4.80–4.70
(m, 8 H, CH2), 3.90 (dd, 1 H, J 8.5, B2 Hz,
H-3 or H-6), 3.89 (d, 1 H, J 8.7 Hz, B2 Hz,
H-6 or H-3), 3.62 (dd, 1 H, J 10.3, 8.7 Hz,
H-4 or H-5), 3.47 (dd, 1 H, J 10.3, 8.7 Hz,
H-5 or H-4), 3.32 (br d, 1 H, J 3.6, B2 Hz,
H-1 or H-2), 3.19 (d, 1 H, J 3.8 Hz, H-2 or
H-1); 13C NMR (CDCl3): 83.9 (C-4 or C-5),
79.8 and 79.7 (C-6 and C-3), 79.5 (C-5 or
C-4), 76.4, 75.9, 73.7, 73.5 (CH2), 55.6 and
55.4 (C-1 and C-2); FAB+-MS: Calcd for
C34H33O5 [M−H+]: m/z 521.2328. Found:
521.2324; Anal. Calcd for C34H34O5: C, 78.14;
H, 6.56. Found: C, 77.90; H, 6.61.
1
L
-1,2-Anhydro-myo-inositol [1 -conduritol
L
B epoxide] (1).—Palladium-on-carbon catalyst
(90 mg of 10% w/w) was added to compound
12 (250 mg, 0.48 mmol) in 5:1 MeOH–EtOAc
(55 mL) and shaken under hydrogen at atmo-
spheric pressure overnight at rt. The catalyst
was removed by filtration through Celite and
FC (1:3 MeOH–CHCl3) of the concentrate
yielded anhydride 1 (71.3 mg, 94%) as a white
solid. Recrystallisation (EtOH) gave white cu-
bic crystals; mp 158–159 °C, lit. 160 °C [5];
1
[h]2D0 −65° (c 0.99, water), lit. −70° [5]; H
NMR (D2O): 3.94 (m, 1 H, H-3 or H-6), 3.80
(m, 1 H, H-6 or H-3), 3.49 (dd, 1 H, J 1.9, 1.6
Hz, H-1 or H-2), 3.33–3.28 (m, 3 H, H-2 or
hexanes–EtOAc) gave 1 -2,3,4,5-tetra-O-ben-
L
zyl-chiro-inositol (11) (0.95 g, 40% from 9) as
1
13
a clear, colourless oil; H NMR (CDCl3): l
H-1 and H-4 and H-5); C NMR (D2O): 75.2
7.55–7.22 (m, 20 H, Ar), 4.84 (s, 4 H, CH2),
4.81–4.56 (m, 4 H, H-2, H-5 and H-3, H-4),
4.11 (s, 2 H, H-1 and H-6), 3.83 (m, 4 H,
CH2), 2.68 (br s, 2 H, OH×2); 13C NMR
(CDCl3): l 139.0, 138.2, 128.6, 128.4, 128.0,
127.7, 127.6, 127.0, Ar), 81.6 (C-3 and C-4),
80.3 (C-2 and C-5), 75.9, 73.3 (CH2), 69.1 (C-1
and C-6); FAB+-MS (MeOH–NBA): Calcd
for C34H35O6 [M−H+]: m/z 539.2434. Found:
539.2441.
(C-4 or C-5), 71.8 (C-3 or C-6), 71.0 (C-6 or
C-3), 70.8 (C-5 or C-4), 57.7 (C-1 or C-2), 57.0
(C-2 or C-1); Anal. Calcd for C6H10O5: C,
44.45; H, 6.22. Found: C, 44.47; H 6.33.
1
D
-1,2-Anhydro-3,4,5,6-tetra-O-benzyl-myo-
inositol (17).—Demethylation of 1 -pinitol
(5) was performed as previously reported [22]
D
to give 1 -chiro-inositol 3 (77%) as off-white
D
1
crystals; H and 13C NMR data (D2O) were
identical to those of compound 6.
The tetraether 11 (590 mg, 1.1 mmol) in dry
toluene (3 mL) was added under argon drop-
1 -chiro-Inositol (3) (8.0 g, 44 mmol) was
D
dissolved in dry DMF (80 mL) and acetone