Synthesis and Structure of 4-O,6-O-Glycosylidene Glycosides

Abstract

Interglycosidic spiro ortho esters (9-20) were efficiently prepared from methyl 2,6-di-O-benzylgluco- or galactopyranoside and various sugar lactones in the presence of methoxytrimethylsilane and a catalytic amount of trimethylsilyl triflate. All of the prepared sugar ortho esters possess perhydrospiro[2H-pyran-2,2'-pyrano[3,2-d][1,3]dioxin] ring systems commonly in their molecules and, remarkably, were afforded as single isomers. The configurations of the spiro centers in their molecules were determined or estimated by X-ray single crystallographic analysis and molecular modeling studies. By comparing the conformations of prepared ortho esters, we revealed that the difference in the stability between two possible isomers was principally caused from that between the spiro ring systems in their molecules in each case.