Facile synthesis of alpha-D-Araf-(1-5)-D-Galf, the linker unit of the arabinan to the galactan in Mycobacterium tuberculosis

LUCíA, GANDOLFI-DONADíO; CAROLA, GALLO-RODRíGUEZ; ROSA, M. DE LEDERKREMER

CANADIAN JOURNAL OF CHEMISTRY

National Research Council of Canada

Lugar: Ottawa; Año: 2006 vol. 84 p. 486 - 491

0008-4042

The arabinogalactan is a crucial constituent of the cell wall of mycobacteria. Both monosaccharides (arabinose and galactose) are found in the furanose configuration, absent in mammals. An efficient synthesis of á-DAraf-(1-5)-D-Galf, the linker unit of the arabinan to the galactan, is described. The strategy relies on the use of a conveniently substituted D-galactono-1,4-lactone as a precursor of the reducing furanose ring. The glycosylation step was performed by the tin(IV) chloride promoted method using 1,2,3,5-tetra-O-benzoyl-á,b-D-arabinofuranose. The arabinosedonor was obtained in a crystalline state in one step by benzoylation of arabinose in hot pyridine. Selective glycosylation of the exocyclic OH-5 was obtained in 75% yield to give 2,3,5-tri-O-benzoyl-á-D-arabinofuranosyl-(1-5)-2,6-di-O-pivaloyl-D-galactono-1,4-lactone. Reduction with disiamylborane gave the disaccharide synthon, useful for further glycosylations. Dec-9-enyl á-D-Araf-(1-5)-b-D-Galf, a convenient substrate for arabinofuranosyl transferases studies, was obtained by the trichloroacetimidate method of glycosylation.á-DAraf-(1-5)-D-Galf, the linker unit of the arabinan to the galactan, is described. The strategy relies on the use of a conveniently substituted D-galactono-1,4-lactone as a precursor of the reducing furanose ring. The glycosylation step was performed by the tin(IV) chloride promoted method using 1,2,3,5-tetra-O-benzoyl-á,b-D-arabinofuranose. The arabinosedonor was obtained in a crystalline state in one step by benzoylation of arabinose in hot pyridine. Selective glycosylation of the exocyclic OH-5 was obtained in 75% yield to give 2,3,5-tri-O-benzoyl-á-D-arabinofuranosyl-(1-5)-2,6-di-O-pivaloyl-D-galactono-1,4-lactone. Reduction with disiamylborane gave the disaccharide synthon, useful for further glycosylations. Dec-9-enyl á-D-Araf-(1-5)-b-D-Galf, a convenient substrate for arabinofuranosyl transferases studies, was obtained by the trichloroacetimidate method of glycosylation.