Robert E. Zelle

On the communication of chirality from furanose and pyranose rings to monosaccharide side chains: anomalous results in the glucose series

Abstract The reactions of allyltrimethylsilane with dialdose derivatives occur, under catalysis by boron trifluoride etherale or titanium tetrachloride, with high stercosclectivity, thereby providing simple routes to the corresponding allyl carbinols. The sense of this Sakurai reaction is very dependent on the nature of the Lewis acid. The same aldehydes react with β-trimethylsilylethylidenetriphenylphosphorane to afford 3-trimethylsilylprop-1-ene-1-yl-furanosides and pyranosides. Reactions of these compounds with osmium tetroxide, followed by elimination of trimcthylsilanol, afford the corresponding vinyl carbinols.