916
C. Chakraborty, D. D. Dhavale / Carbohydrate Research 341 (2006) 912–917
J2,3 = 2.8 Hz, H-3), 4.50 (d, 1H, J1,2 = 3.3 Hz, H-2),
5.10 (s, 2H, OCH2Ph), 5.46–5.58 (br s, 1H exchanges
with D2O, OH/NH), 5.95 (d, 1H, J1,2 = 3.3 Hz, H-1),
7.30–7.42 (m, 5H, Ar-H); 13C NMR (75 MHz, CDCl3)
d 26.2, 26.8, 44.9, 67.1, 70.3, 76.3, 79.9, 85.3, 104.8,
111.8, 128.0, 128.1, 128.4, 135.9, 157.2. Anal. Calcd for
C17H23NO7: C, 57.79; H, 6.55. Found: C, 57.90; H, 6.77.
ity. We are thankful to Professor M. S. Wadia for help-
ful suggestions.
References
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1.9. (2S,3R,4R,5R)-Tetrahydroxyazepane (1a)
A solution of 4a (0.10 g, 0.28 mmol) in TFA-H2O
(3 mL, 2:1) was stirred at 25 ꢁC for 2.5 h. The TFA
was then co-evaporated with benzene to furnish a thick
liquid. To a solution of the above product in CH3OH/
HCl (5 mL, 9:1) was added 10% Pd/C (0.05 g). The solu-
tion was hydrogenated at 80 psi for 24 h. The catalyst
was filtered through Celite and washed with CH3OH.
The filtrate was concentrated to obtain a semi-solid.
The sticky solid was washed with CHCl3 and loaded
on DOWEX–H+ resin. Elution with 5% ammonia–
CH3OH and evaporation of the CH3OH afforded 1a
(0.04 g, 81%) as a sticky solid. Rf 0.11 (2:8, CH3OH/
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CHCl3); IR (neat) 3555–3340, 1592, 1194 cmꢀ1
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1H
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M.; Krajcik, J. Tetrahedron 2000, 56, 5465–5472.
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NMR (300 MHz, D2O) 2.65–2.87 (m, 4H,
d
H2CNHCH2), 3.40–3.52 (m, 1H), 3.53–3.65 (m, 2H),
3.78–3.88 (m, 1H); 13C NMR (75 MHz, D2O) d 49.3,
49.6, 71.2, 73.3, 74.7, 75.2. Anal. Calcd for C6H13NO4Æ2-
H2O: C, 36.18; H, 8.59. Found: C, 36.47; H, 8.90. A
solution of 1a (0.1 g) in CH3OH (5 mL) and two drops
of concentrated HCl was stirred at rt for 24 h. The solu-
tion was concentrated and the residue was dissolved in
water (10 mL) and extracted with ether (2 · 10 mL).
The aqueous layer was concentrated and the residue
washed with CH3OH–Et2O to give a white gummy solid
(0.08 g, 70%); [a]D ꢀ18.2 (c 0.6, H2O); lit.13m,14a [a]D
ꢀ15.0 (c 1.0, H2O) and [a]D ꢀ19.5 (c 0.6, H2O).
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1.10. (2S,3R,4R,5S)-Tetrahydroxyazepane (1b)
Reaction of 4b (0.2 g, 0.56 mmol) with TFA–H2O as de-
scribed for 4a, followed by hydrogenation with 10% Pd/
C in CH3OH gave 1b (0.06 g 65%) as a thick liquid. [a]D
18.8 (c 0.1, H2O); lit.13e,14a [a]D 19.9 (c 2.0, H2O) and
[a]D 20.1 (c 0.2, H2O); Rf 0.15 (1:4, CH3OH/CHCl3);
IR (neat) 3560–3367, 1577, 1179 cmꢀ1
;
1H NMR
(300 MHz, D2O) d 2.95–3.07 (dd, 2H, J = 8.2, 13.8 Hz,
H2CNHCH2), 3.12–3.24 (dd, 2H, J = 1.9, 13.8 Hz,
H2CNHCH2), 3.46–3.55 (m, 2H, H-2 and H-5), 3.84–
3.96 (m, 2H, H-3 and H-4); 13C NMR (75 MHz, D2O)
d 47.0, 67.8, 76.7. Anal. Calcd for C6H13NO4Æ2H2O:
C, 36.18; H, 8.59. Found: C, 36.43; H, 8.77.
Acknowledgements
11. (a) Fellows, L. E.; Fleet, G. W. J. Natural Product
Isolation; Elsevier: Amsterdam, 1998, p 538; (b) Winches-
ter, B.; Fleet, G. W. J. Glycobiology 1992, 2, 199–210; (c)
We gratefully acknowledge UGC, New Delhi, for the
grant to purchase the high-field (300 MHz) NMR facil-