Synthesis of 5-C-Methylated d-Mannose, d-Galactose, l-Gulose, and l-Altrose and Their Structural Elucidation by NMR Spectroscopy.

C5/C6-Spirocyclopropanation of exocyclic enol esters followed by alkali ring-opening of the three-membered ring was used for the diastereoselective preparation of 5-C-methylated d-mannose, d-galactose, l-gulose, and l-altrose. Extensive NMR studies demonstrated an increase of furanose form by 5-C-methylation in almost all cases.