J. Spreitz et al. / Carbohydrate Research 337 (2002) 183–186
185
again dissolved in hot 2-propanol and allowed to crys-
tallise to remove residual triphenylphosphane oxide.
Ketose 4 was thus obtained as colourless crystalline
was obtained by conventional processing of the mother
liquor. Physical data and spectra of 8 were identical
4
with the data from previously prepared material.
20
material (54.6 g, 89%): mp 112–113 °C; [h] +37.4° (c
D
8 20
3 D
1
.2, CHCl ). [Lit. : mp 114 °C; [h] +44°, (c 1.0,
CHCl )]. H NMR (CDCl ): l 5.64 (1 H, dd, J 2.0,
1
3
3
3,4
Acknowledgements
J4,5 8.8 Hz, H-4), 5.46 (1 H, d, H-3), 5.24 (1 H, m, H-5),
4
3
.90 (1 H, d, J1a,1b 17.4 Hz, H-1a), 4.68 (1 H, d, H-1b),
.59 (1 H, dd, J5,6a 3.4, J 11.4 Hz, H-6a), 3.43 (1 H,
Financial support by the Austrian Fonds zur
F o¨ rderung der Wissenschaflichen Forschung (FWF),
Vienna, Project P 13593 CHE is appreciated. T.M.W.
thanks the FWF for a Hertha-Firnberg-Grant (T-18
CHE).
6a,6b
1
3
dd, J5,6b 5.7 Hz), H-6b); C NMR: l 198.0 (C-2), 74.2,
0.3, 69.0, 67.0 (C-1, C-3, C-4, C-5), 31.2 (C-6).
Preparation of 6-bromo-6-deoxy-h,i- -fructofura-
7
D
nose (7).—To a 3% methanolic solution of bromod-
eoxyketose 4 (49.4 g, 120.1 mmol), 1 M methanolic
sodium methoxide was added slowly at 0 °C until pH 8
was reached. The reaction was found to be completed
References
after 5 h. Acidic ion-exchange resin (Amberlite IR 120
+
1. (a) Moremen, K. W. In Carbohydrates in Chemistry and
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VCH: Weinheim, 2000; Vol. 3, pp. 81–117;
[H ]) was washed with MeOH and added to the reac-
tion mixture until neutral. After filtration, the solution
was concentrated under reduced pressure, and the re-
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(
b) Elbein, A. D.; Molyneux, R. J. In Iminosugars as
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0
13
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slightly yellow syrup: [h] +1.9° (c 1.8, MeOH);
C
D
NMR (D O): l 104.8, 101.9 (C-2, a/b), 82.1, 80.2, 79.6,
2
7
(
8.4, 77.0, 75.4 (C-3 a/b, C-4 a/b, C-5 a/b), 62.9, 62.8
C-1 a/b), 33.9, 32.7 (C-6 a/b). Anal. Calcd for
C H BrO : C, 29.65; H, 4.56. Found: C, 29.61; H,
2
. Spiro, R. G. In Carbohydrates in Chemistry and Biology,
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6
11
5
4
.59.
Preparation of 6-azido-6-deoxy-h,i-
6).—To a 3% solution of bromodeoxysugar 7 (19.1 g,
5.7 mmol) in N,N-dimethylformamide (DMF),
D
-fructofuranose
(
1
3. (a) Schweden, J.; Legler, G.; Bause, E. Eur. J. Biochem.
986, 157, 563–570;
b) Hamagashira, N.; Oku, H.; Mega, T.; Hase, T. J.
1
sodium azide (94 g, 18.4 equiv) was added, and the
mixture was stirred at ambient temperature for 7 days.
Dichloromethane (1300 mL) was added, and the precip-
itate was removed by filtration. Concentration of the
filtrate under reduced pressure furnished a yellow mate-
rial that was purified on silica gel to give free azido-
deoxyketose 6 (10.6 g, 66%) identical with previously
(
Biochem. 1996, 119, 998–1003.
4
. de Raadt, A.; St u¨ tz, A. E. Tetrahedron Lett. 1992, 33,
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1
(
4
20
D
13
prepared material; [h] +42.1° (c 1.3, MeOH);
C
(
c) Zou, W.; Szarek, W. A. Carbohydr. Res. 1994, 254,
NMR (D O): l 102.5, 99.6 (C-2 a/b), 79.6, 77.6, 76.8,
2
25–33;
7
4.8, 72.8, 72.7 (C-3 a/b, C-4 a/b, C-5 a/b), 60.6, 60.3
(d) Park, K. H.; Yoon, Y. J.; Lee, S. G. J. Chem. Soc.,
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(
C-1 a/b), 50.3, 49.3 (C-6 a/b).
(
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deoxymannojirimycin, 8).—A 2.5% methanolic solution
of azidodeoxyfructose 6 (5.2 g, 25.3 mmol) was stirred
with Pd–C (5%, 0.5 g) under an atmosphere of hydro-
gen at ambient temperature. The reaction was found
completed after 4 h. The catalyst was removed by
filtration and the filtrate was concentrated under re-
duced pressure. The remaining crude product was dis-
solved in water, and treated with basic ion-exchange
resin (Merck III). After filtration and removal of the
water under reduced pressure, MeOH was added to the
yellow residue, and the solution was seeded to induce
crystallisation. Slightly yellow product 8 was isolated
by filtration (2.5–2.9 g; 60–70%). Additional product
(
C.; Bolte, J. Tetrahedron: Asymmetry 1995, 6, 67–70;
(g) Xu, Y.-M.; Zhou, W.-S. Tetrahedron Lett. 1996, 37,
1
461–1462;
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19–533;
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Chem. Commun. (Cambridge) 1999, 41–42;
(
5
(
(
1
(
(