J. Cheng et al. / Carbohydrate Research 344 (2009) 2093–2095
2095
aqueous solution of NaHCO3 until pH 8. The organic layer was then
washed with brine, dried (Na2SO4), and concentrated. The residue
was purified by chromatography on silica gel (EtOAc–petroleum
ether, 1:8) to afford 4 (1.0 g, 53%) as a yellow syrup: 1H NMR
(300 MHz, CDCl3), d: 2.65 (br, 2.65, 1H, 2-OH), 3.68–3.73 (m, 2H),
3.84–3.89 (m, 3H), 4.07 (dd, 1H, J = 3.3, 7.1 Hz), 4.27 (dd, 1H,
J = 5.7, 11.7 Hz), 4.34–4.45 (m, 4H), 4.70–4.76 (m, 6H), 5.69 (s,
1H), 7.21–7.48 (m, 25H, Ph); 13C NMR (75 MHz, CDCl3), d: 62.3,
69.3, 72.3, 73.5, 73.7, 75.1, 76.9, 78.3, 78.7, 78.7, 79.9, 103.3,
127.1–129.8 (25C), 137.4-138.8 (5C); ESI-MS: m/z = 683.28
[M+Na]+, 699.27 [M+K]+; HRMS calcd for C42H45O7 [M+H]+
661.31598. Found: 661.31490.
(0.53 g, 85%) as a white solid: mp 148–150 °C, lit.15 mp 151 °C;
= +29.0 (c 1.0, H2O), lit15 = +29.1 (c 1.0, H2O); 13C NMR
(75 MHz, CDCl3), d: 63.6, 66.6, 69.4, 72.5, 73.4, 75.5, 100.3 (C-2);
ESI-MS: m/z = 211.06 [M+H]+; the purity of 1 as checked by RP-
HPLC was 99.5%.
½
a 2D0
ꢃ
½ ꢃ
a 2D0
Supplementary data
Supplementary data associated with this article can be found, in
References
1.4. 3,4,5,6,7-Penta-O-benzyl-D
-mannoheptulose (40)
1. Xu, L. Z.; Weber, I. T.; Harrison, R. W.; Gidh-Jain, M.; Pilkis, S. J. Biochemistry
1995, 34, 6083–6092.
2. Ferrer, J.; Gomis, R.; Fernandez Alvarez, J.; Casamitjana, R.; Vilardell, E. Diabetes
1993, 42, 1273–1280.
3. Board, M.; Colquhoun, A.; Newsholme, E. A. Cancer Res. 1995, 55, 3278–3285.
4. Li, X. F.; Zhang, D. H.; Lee, U.; Li, X. G.; Cheng, J. G.; Zhu, W. L.; Jung, J. H.; Choi,
H. D.; Son, B. W. J. Nat. Prod. 2007, 70, 307–309.
5. Taatjes, D. J.; Gaudiano, G.; Resing, K.; Koch, T. H. J. Med. Chem. 1997, 40, 1276–
1286.
6. (a) Johnson, R. A.; Sharpless, K. B. In Catalytic Asymmetric Synthesis; Ojima, I.,
A suspension of 4 (1.0 g, 1.5 mmol) and 3 M hydrochloric acid
(10 mL) in acetone (10 mL) was stirred at rt for 3 h. The mixture
was diluted and extracted with CHCl3 (2 ꢁ 100 mL), the organic
layers were washed with a saturated aqueous solution of NaHCO3,
dried (Na2SO4), and concentrated. The residue was purified by
chromatography on silica gel (EtOAc–petroleum ether, 1:8) to af-
ford 4’ (0.95 g, 95%) as a yellow syrup: 1H NMR (300 MHz, CDCl3),
d:3.66–3.73 (m, 2H), 3.74–3.76 (m, 2H), 3.81–3.83 (m, 2H), 3.85–
3.88 (m, 2H), 4.12–4.68 (m, 10H, PhCH2), 7.20–7.41 (m, 25H, Ph);
13C NMR (75 MHz, CDCl3), d: 60.3, 63.9, 69.5, 72.2, 72.5, 73.1,
73.4, 73.7, 78.4, 78.8, 79.5, 127.6–128.9 (25C), 137.6–138.0 (5C),
206.5 (C-2); HRMS calcd for C42H45O7 [M+H]+ 661.31598. Found:
661.32470.
Ed.; 2nd ed.; Wiley: New York, Weinheim, 2000;
p 357; (b) Bolm, C.;
Hildebrand, J. P.; Muniz, K. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.,
2nd ed.; Wiley: New York, Weinheim, 2000; p 399.
7. (a) Johnson, R. A.; Sharpless, K. B. In Catalytic Asymmetric Synthesis; Ojima, I.,
Ed., 2nd ed.; Wiley: New York, Weinheim, 2000; p 231; (b) Katsuki, T. In
Catalytic Asymmetric Synthesis; Ojima, I., Ed., 2nd ed.; Wiley: New York,
Weinheim, 2000; p 287; (c) Jacobsen, E. N.; Wu, M. H.. In Comprehensive
Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer:
Berlin, Heidelberg, 1999; Vol. II, p 649.
8. (a) Lohray, B. B.; Bhushan, V.; Kumar, R. K. J. Org. Chem. 1994, 59, 1375–1380;
(b) Sharpless, K. B.; Akashi, K. J. Am. Chem. Soc. 1976, 98, 1986–1987.
9. Srinivasan, N. S.; Lee, D. G. Synthesis 1979, 520.
1.5. D-Mannoheptulose (1)
10. Baskaran, S.; Das, S. J.; Chandrasekaran, S. J. Org. Chem. 1989, 54, 5182–5184.
11. Takai, T.; Yamada, T.; Mukaiyama, T. Chem. Lett. 1991, 1499.
12. (a) Plietker, B. Eur. J. Org. Chem. 2005, 1919–1929; (b) Plietker, B. Org. Lett.
2004, 6, 289–291; (c) Plietker, B. J. Org. Chem. 2004, 69, 8287–8296; (d)
Plietker, B.; Niggemann, M. Org. Biomol. Chem. 2004, 2, 2403–2407; (e) Plietker,
A suspension of 4 (2.0 g, 3.0 mmol) and 10% Pd–C (1.5 g) in
EtOAc–EtOH (1:1, 20 mL) was stirred at rt under 1–2 atm H2 for
48 h. After removing the Pd–C by filtration, the filtrate was concen-
trated and then dissolved in 0.5 M sulfuric acid (30 mL), and the
mixture was maintained at 60 °C for 12 h, neutralized with barium
carbonate until pH 7, filtered, and concentrated to dryness. The
residue was purified by chromatography on silica gel (MeOH–
Et3N–H2O, 6:2:1) and then crystallized from methanol to afford 1
B. J. Org. Chem. 2003, 68,
7123–7125.
13. López-Herrera, F. J.; Sarabia-Garcia, F. Tetrahedron 1997, 53, 3325–3346.
14. (a) Bonini, C.; Chiummiento, L.; Funicello, M.; Lupattelli, P.; Pullez, M. Eur. J.
Org. Chem. 2006, 80–83; (b) Bonini, C.; Chiummiento, L.; Pullez, M.; Solladié, G.;
Colobert, F. J. Org. Chem. 2004, 69, 5015–5022.
15. Kampf, A.; Dimant, E. Carbohydr. Res. 1974, 32, 380–382.