Synthesis of D-Allose Fatty Acid Esters
835
13C-NMR ꢃ (CD3OD): 14.4, 23.7, 26.0, 30.1, 32.8, 34.9,
65.4, 69.0, 72.8, 72.9, 73.4, 95.4, 175.5. Anal. Found: C,
54.61; H, 8.41%. Calcd. for C14H26O7: C, 54.89; H,
8.55%.
2) Bhuiyan, S. H., Itami, Y., Rokui, Y., Katayama, T., and
Izumori, K., D-Allose production from D-psicose using
immobilized L-rhamnose isomerase. J. Ferment. Bioeng.,
85, 539–541 (1998).
3) Arnold, E. C., and Silady, P. J., U.S. Patent 5620960
(Apr. 15, 1997).
4) Hossain, M. A., Izuishi, K., and Maeta, H., Protective
effects of D-allose against ischemia reperfusion injury of
the rat liver. J. Hepatobiliary Pancreat. Surg., 10, 218–
225 (2003).
5) Hossain, M. A., Wakabayashi, H., Goda, F., Kobayashi,
S., Maeta, T., and Maeta, H., Effect of the immunosup-
pressants FK506 and D-allose on allogenic orthotopic
liver transplantation in rats. Transplant. Proc., 32, 2021–
2023 (2000).
6) Murata, A., Sekiya, K., Watanabe, Y., Yamaguchi, F.,
Hatano, N., Izumori, K., and Tokuda, M., A novel
inhibitory effect of D-allose on production of reactive
oxygen species from neutrophils. J. Biosci. Bioeng., 96,
89–91 (2003).
7) Rees, W. D., and Holman, G. D., Hydrogen bonding
reguirements for the insulin-sensitive sugar transport
system of rat adipocytes. Biochim. Biophys. Acta, 646,
251–260 (1981).
8) Ogino, K., Research and development of novel surfac-
tants. J. Jpn. Oil Chem. Soc., 45, 921–932 (1996).
9) Fujii, T., Biosurfactants. J. Jpn. Oil Chem. Soc., 45,
1013–1022 (1996).
10) Baker, I. J. A., Willing, R. I., Furlong, D. N., Grieser, F.,
and Drummond, C. J., Sugar fatty acid esters surfactants:
biodegradation pathways. J. Surf. Det., 3, 13–27 (2000).
11) Therisod, M., and Klibanov, A. M., Facile enzymatic
preparation of monoacylated sugars in pyridine. J. Am.
Chem. Soc., 108, 5638–5640 (1986).
Synthesis of D-allose 6-caprate (5). 73% yield, mp
25
109–110 ꢀC; ½ꢁꢁD +10.0 ꢀ (c 1.0, CH3OH); IR ꢂmax
(KBr) cmꢂ1: 3442, 2922, 1736, 1108; 1H-NMR ꢃ
(CD3OD): 0.90 (3H, t, J ¼ 6:8 Hz), 1.30 (12H, m),
1.61 (2H, m), 2.33 (2H, t, J ¼ 7:6 Hz), 3.24 (1H, dd,
J ¼ 3:0, 8.1 Hz), 3.49 (1H, dd, J ¼ 3:1, 9.8 Hz), 3.89
(1H, ddd, J ¼ 2:2, 6.1, 9.8 Hz), 4.05 (1H, t, J ¼ 3:0 Hz),
4.14 (1H, dd, J ¼ 6:1, 11.7 Hz), 4.37 (1H, dd, J ¼ 2:2,
11.7 Hz), 4.82 (1H, d, J ¼ 8:1 Hz); 13C-NMR
ꢃ
(CD3OD): 14.4, 23.7, 26.0, 30.2, 30.4, 30.6, 33.0,
34.9, 65.4, 69.1, 72.8, 72.9, 73.5, 95.5, 175.5. Anal.
Found: C, 57.15; H, 9.01%. Calcd. for C16H30O7: C,
57.47; H, 9.04%.
Synthesis of D-allose 6-laurate (6). 56% yield, mp
25
101–102 ꢀC; ½ꢁꢁD +6.0 ꢀ (c 1.0, CH3OH); IR ꢂmax
(KBr) cmꢂ1: 3409, 2920, 1736, 1108; 1H-NMR ꢃ
(CD3OD): 0.90 (3H, t, J ¼ 7:1 Hz), 1.29 (16H, m),
1.61 (2H, m), 2.33 (2H, t, J ¼ 7:6 Hz), 3.24 (1H, dd,
J ¼ 2:9, 8.0 Hz), 3.49 (1H, dd, J ¼ 2:9, 10.0 Hz), 3.89
(1H, ddd, J ¼ 1:9, 6.1, 10.0 Hz), 4.05 (1H, t, J ¼ 2:9
Hz), 4.14 (1H, dd, J ¼ 6:1, 12.0 Hz), 4.36 (1H, dd,
J ¼ 1:9, 12.0 Hz), 4.82 (1H, d, J ¼ 8:0 Hz); 13C-NMR ꢃ
(CD3OD): 14.4, 23.7, 26.0, 30.2, 30.4, 30.5, 30.6, 30.7,
33.1, 34.9, 65.4, 69.1, 72.8, 72.9, 73.4, 95.5, 175.5. Anal.
Found: C, 59.34; H, 9.36%. Calcd. for C18H34O7: C,
59.65; H, 9.45%.
Acknowledgments
12) Acros, J. A., Bernabe, M., and Otero, C., Quantitative
enzymatic production of 6-O-acyl-glucose esters. Bio-
technol. Bioeng., 57, 505–509 (1998).
13) Pulido, R., Ortiz, F. L., and Gotor, V., Enzymatic
regioselective acylation of hexoses and pentoses using
oxime esters. J. Chem. Soc., Perkin Trans. 1, 2891–2898
(1992).
The authors thank Amano Enzyme Inc. and Novo
Nordisk for respectively providing lipase PS and AK,
and Novozym 435.
14) Wang, Y.-F., Lalonde, J. J., Momongan, M., Bergbreiter,
D. E., and Wong, C.-H., Lipase-catalyzed irreversible
transesterification using enol ester as acylating reagents:
preparative enantio- and regioselective synthesis of
alcohols, glycerol derivatives, sugars, and organometal-
lics. J. Am. Chem. Soc., 110, 7200–7205 (1988).
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