Crude D‐(+)‐Glyceraldehyde Obtained from D‐Mannitol‐Diacetonide by Oxidative Cleavage with Sodium Periodate: Its Reactions with Nucleophilic Species

Abstract

The oxidative cleavage of D‐(+)‐mannitol‐diacetonide with sodium periodate lead to a mixture of D‐(+)‐glyceraldehyde, its hydrate and oligomeric derivatives. In spite of the low concentration of free glyceraldehyde (estimated in ∼20%, by NMR), good yields were obtained in nucleophilic additions involving this mixture and a variety of nucleophiles (amines, phosphonates, phosphoranes, nitronates, organometallic compounds).

Keywords:

• D‐(+)‐Mannitol‐diacetonide
• D‐(+)‐Glyceraldehyde
• Oxidative cleavage
• Nucleophilic additions

Acknowledgments

Central Analítica do Núcleo de Pesquisas de Produtos Naturais (NPPN‐UFRJ) and CNPq/CAPES/FAPERJ for the authors' fellowships.

Notes

^aIn NMR ¹H spectra multiple signs are observed between 1.0 to 2.0 ppm (methyl signs) and in ¹³C spectra multiple signs in the region of 110 ppm referent to quaternary carbon of the diacetonide.

^bWe have not made efforts to identify the structure of the major diastereoisomer (syn or anti).