314
E. Kaya et al./Chemical Papers 66 (4) 312–315 (2012)
acetylated glucose at laboratory temperature, as indi-
cated in Table 1, almost the same yield (72 %) and
selectivity was obtained. This may be a further ad-
vantage of the method if high temperature deacety-
lation is unfavourable. In all cases, about 15–30 % of
the initial material recovered from the reaction mix-
ture indicated the regioselectivity of deacetylation re-
actions. It should be stated that methyl glycoside by-
products were not detected in the reaction mixtures.
This means that the anomeric deacetylation reaction
could not proceed via the oxacarbenium intermediate.
In addition, as the reaction time increased, multiple
deacetylations were also observed. As a result of these
observations, it can be stated that the reaction pro-
ceeded via transesterification. 1H-NMR was used to
determine the anomeric ratio on the basis of the cou-
pling of H-1 and H-2. The anomeric deacetylation of
Ia and (2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-
(1→4)-O-1,2,3,6-tetra-O-acetyl-D-glucopyranose (Id)
yielded α/β as 4 : 1 and 2 : 1 respectively, where
completely acetylated mannose, rhamnose, and cel-
lobiose yielded only α anomers. The spectral data of
each product corresponded to those in the literature
(Ikeda et al., 2010; Zhang et al., 2011).
Research, 153, 325–329. DOI: 10.1016/s0008-6215(00)90275-
1.
Grynkiewicz, G., Fokt, I., Szeja, W., & Fitak, H. (1989).
Chemoselective deprotection of 1-O-acyl sugar derivatives.
Journal of Chemical Research, Synopses, 5, 152–153.
Hennen, W. J., Sweers, H. M., Wang, Y. F., & Wong, C. H.
(1988). Enzymes in carbohydrate synthesis. Lipase-catalyzed
selective acylation and deacylation of furanose and pyranose
derivatives. Journal of Organic Chemistry, 53, 4939–4945.
DOI: 10.1021/jo00256a008.
Herzig, J., & Nudelman, A. (1986). Regioselective heteroge-
neous O-deacylation of polyacylated sugars. Carbohydrate
Research, 153, 162–167. DOI: 10.1016/s0008-6215(00)90208-
8.
Ikeda, K., Morimoto, T., & Kakiuchi, K. (2010). Utilization
of aldoses as a carbonyl source in cyclocarbonylation of
enynes. Journal of Organic Chemistry, 75, 6279–6282. DOI:
10.1021/jo1012288.
Jiang, J. Q., Biggins, J. B., & Thorson, J. S. (2000). A gen-
eral enzymatic method for the synthesis of natural and
“unnatural” UDP- and TDP-nucleotide sugars. Journal
of the American Chemical Society, 122, 6803–6804. DOI:
10.1021/ja001444y.
Khan, R., Konowicz, P. A., Gardossi, L., Matulova, M., &
Degennaro, S. (1996). Regioselective deacetylation of fully
acetylated mono- and di-saccharides with hydrazine hydrate.
Australian Journal of Chemistry, 49, 293–298.
Knerr, L., Pannecoucke, X., & Luu, B. (1998). Efficient synthe-
sis of hydrophilic phosphodiester derivatives of lipophilic al-
cohols via the glycosyl hydrogenphosphonate method. Tetra-
hedron Letters, 39, 273–274. DOI: 10.1016/s0040-4039(97)
10510-x.
Li, Y. X., Li, Y. W., Wei, Z., & Guan, H. S. (2004). An alter-
native method for anomeric deacetylation of per-acetylated
carbohydrates. Chinese Journal of Chemistry, 22, 117–118.
DOI: 10.1002/cjoc.20040220125.
Mikamo, M. (1989). Facile 1-O-deacylation of per-O-acylaldo-
ses. Carbohydrate Research, 191, 150–153. DOI: 10.1016/
0008-6215(89)85056-6.
An effective alternative method for the selective
anomeric deacetylation of carbohydrates has been de-
veloped. The mild reaction conditions, experimental
simplicity, low cost, acceptable yields, and the envi-
ronmentally benign nature are some of the advantages
of the method. This method is especially valuable
when the basic reagents are unfavourable for anomeric
deacetylation.
Acknowledgements. This work was financially supported by
the Sakarya University Scientific Research Project (07-02-04-
005).
Mohankumar, P., Ilango, K., Santhanakrishan, V. P., Radhakr-
ishnan, V., & Narasimhan, S. (2010). Ethylenediamine: an
effective reagent for deacetylation of natural products. Jour-
nal of Asian Natural Products Research, 12, 851–858. DOI:
10.1080/10286020.2010.507545.
Nudelman, A., Herzig, J., Gottlieb, H. E., Keinan, E., & Ster-
ling, J. (1987). Selective deacetylation of anomeric sugar ac-
etates with tin alkoxides. Carbohydrate Research, 162, 145–
152. DOI: 10.1016/0008-6215(87)80209-4.
Rowell, R. M., & Feather, M. S. (1967). Synthesis and properties
of anomerically unsubstituted hepta-O-acetyl disaccharides.
Carbohydrate Research, 4, 486–491. DOI: 10.1016/s0008-
6215(00)81840-6.
References
Baba, T., Kobayashi, A., Kawanami, Y., Inazu, K., Ishikawa,
A., Echizenn, T., Murai, K., Aso, S.,
& Inomata, M.
(2005). Characteristics of methoxycarbonylation of aromatic
diamine with dimethyl carbonate to dicarbamate using a
zinc acetate catalyst. Green Chemistry, 7, 159–165. DOI:
10.1039/b413334j.
Boger, D. L., Teramoto, S., & Zhou, J. (1995). Key syn-
thetic analogs of bleomycin A2 that directly address the
effect and role of the disaccharide: Demannosylbleomycin
A2 and α-D-mannopyranosyldeglycobleomycin A2. Journal
of the American Chemical Society, 117, 7344–7356. DOI:
10.1021/ja00133a008.
Chittenden, G. J. F. (1988). A simplified synthesis of α-
D-galactopyranose 1,3,4,6-tetraacetate. Carbohydrate Re-
search, 183, 140–143. DOI: 10.1016/0008-6215(88)80055-7.
Excoffier, G., Gagnaire, D., & Utille, J. P. (1975). Coupure
sélective par l’hydrazine des groupements acétyles anom`eres
de résidus glycosyles acétylés. Carbohydrate Research, 39,
368–373. DOI: 10.1016/s0008-6215(00)86150-9.
Sambaiah, T., Fanwick, P. E., & Cushman, M. (2001). Regiose-
lective 1-O-acyl hydrolysis of peracylated glycopyranoses by
mercuric chloride and mercuric oxide. Synthesis, 2001, 1450–
1452. DOI: 10.1055/s-2001-16084.
Schmidt, R. R., & Kinzy, W. (1994). Anomeric-oxygen ac-
tivation for glycoside synthesis: The trichloroacetimidate
method. Advances in Carbohydrate Chemistry and Biochem-
istry, 50, 21–123. DOI: 10.1016/s0065-2318(08)60150-x.
Sim, M. M., Kondo, H., & Wong, C. H. (1993). Synthesis of
dibenzyl glycosyl phosphites using N,N-diethylphosphorami-
dite as phosphorylating reagent: an effective route to gly-
cosyl phosphates, nucleotides, and glycosides. Journal of
the American Chemical Society, 115, 2260–2267. DOI:
10.1021/ja00059a023.
Fiandor, J., & De Las Heras, F. G. (1986). Selective ben-
zoylation of 2-deoxy-D-arabino-hexose: synthesis of 3,6-di-
O-benzoyl-2,4-dideoxy-D-threo-hexopyranose. Carbohydrate
Tiwari, P.,
& Misra, A. K. (2006). Selective removal of
anomeric O-acetate groups in carbohydrates using HClO4–