A practical access to glucose- and allose-based (5+5) 3-spiropseudonucleosides from a common intermediate

• Multigram syntheses of carbohydrate-based spirooxazolidinones are developed.
• Novel 3-spiropseudonucleosides are characterized by X-ray diffraction analysis.
• User-friendly diacetone-α-d-glucose oxidation is elaborated and validated.

A practical access to glucose-based and allose-based spirooxazolidinones is reported. The synthetic sequence consisting of TEMPO-catalyzed oxidation of 1,2:5,6-di-O-isopropylidene-α-d-glucofuranose, Henry reaction, and reduction provides amino alcohol with allo-configuration on a multigram scale. Alternatively, water elimination from Henry products followed by a rehydration gives an access to diastereomerically pure glucose-based nitro alcohol which upon reduction provides complementary amino alcohol with gluco-configuration. The latter amino alcohols are transformed into spirooxazolidinones (3-spiropseudonucleosides) via their N-Cbz or N-phenylcarbamate derivatives. The title compounds easily undergo N-derivatization and give highly crystalline materials. Two of the newly obtained (5+5) 3-spiropseudonucleosides are characterized by X-ray crystallography.

Figure optionsDownload as PowerPoint slide