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For further characterisation, 18a was prepared by
conventional O-acetylation employing acetic anhydride
20
in pyridine to give crystalline acetate: ½aꢀD +5.3 (c
0.85, CH2Cl2), mp 98–102 ꢁC; 1H NMR (CDCl3): d
5.16 (d, 1H, J3,4 4.2 Hz, H-4), 4.36 (d, 1H, J1a,1b
9.0 Hz, H-1a), 4.27 (dd, 1H, J5,6a 1.5 Hz, J6a,6b
10.2 Hz, H-6a), 4.22 (d, 1H, H-3), 4.13 (dd, 1H, J5,6b
1.5 Hz, H-6b), 4.05 (br s, 1H, H-5), 3.95 (d, 1H, H-
1b); 13C NMR: d 170.6 (C@O), 99.2 (C-2), 83.7, 77.0,
71.3, 71.1, 66.9 (C-1, C-3, C-4, C-5, C-6), 21.2 (COMe).
Anal. Calcd for C11H16O6: C, 54.09; H, 6.60. Found: C,
54.03; H, 6.66.
´
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A soln of compound 18 (10 g, 49.5 mmol) in aq acetic
acid (80%, 30 mL) was stirred at 65 ꢁC for 15 min and
the solvent was removed under diminished pressure.
The residue was dissolved in dry MeOH (50 mL) and
the soln was slowly added to cold ether (1000 mL)
under vigorous stirring. The resulting suspension was
stirred at 0 ꢁC for 2 h and filtered. The precipitate was
washed with dry ether (300 mL) and dried under dimin-
ished pressure to give known final product to give 1 (8 g,
94%) as a hygroscopic white powder. The product
showed a 13C NMR spectrum identical with that of an
authentical sample of 1 provided by Danisco (Copen-
hagen) and prepared according to Refs. 12 and 14: 13C
NMR (1 hydrate, D2O): d 92.8 (C-2), 80.8, 77.1, 71.9,
69.1, 61.4 (C-1, C-3, C-4, C-5, C-6); for comparative
data, see Refs. 17 and 18.
19. Andersen, S. M.; Lundt, I.; Marcussen, J.; Yu, S.
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22. Elsser, D.; Morgan, J. A.; Thomas, L. V.; Yu, S. PCT, Int.
Appl. WO 02/26060, 2002; AN 2002, 256006.
23. Elsser, D.; Morgan, J. A.; Thomas, L. V.; Yu, S. PCT, Int.
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26. Muroya, M.; Fujisue, M.; Matsuda, T. Japanese Patent
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Acknowledgment
27. Hizukuri, S.; Abe, J.; Junichi, Y.; Muroya, K.; Yoshinaga,
K.; Fujisue, M.; Ishiba, H. PTC Int. Appl. WO
2001072124, 2001; AN 2001, 730498.
A.E.S. thanks the Technical University of Denmark
(DTU) for a guest professorship in March 2005.
28. Hisaku, S.; Abe, J.; Muroya, M.; Yoshinaga, K. Japanese
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