Convenient synthesis of 3-deoxy-d-ribo-hexose and 3-deoxy-d-arabino-hexose

✍ Scribed by Patricia M. Scensny; Susan G. Hirschhorn; James R. Rasmussen

• Publisher: Elsevier Science
• Year: 1983
• Tongue: English
• Weight: 365 KB
• Volume: 112
• Category: Article
• ISSN: 0008-6215
• DOI: 10.1016/0008-6215(83)88295-0

✦ Synopsis

As part of a study of the effects of sugar analogs on glycoprotein biosynthesis'V2, it was necessary to prepare 3-deoxy-D-ribo-hexose (4) and 3-deoxy-D-arabino-hexose (5). Several satisfactory syntheses of these deoxy sugars have been reported3-7. For example, 3-deoxy-D-Cbo-hexose may be obtained by reduction of an appropriate t~ocarbonyl derivative of 1,2 : 5,6-di-0-isopropylidene-~-D-glucofuranose by tributylstannane . 4-6 Reduction of methyl 2,3-anhydro-4,6-O-benzylidene-~-D-mannopyranoside by lithium aluminum hydride leads to 3-deoxy-D-arabiizo-hexose'. Wood and Fletcher prepared compounds 4 and 5 by a Kiliani-Fischer synthesis that involved addition of cyanide to %deoxy-D-erythro-pentose (2-deoxy-D-ribose) followed by successive separation of the calcium salts of the epimeric aldonic acids, lactonization, and reduction by sodium amalgam'.

Improvements have been made by several investigators in the original Kiliani-Fischer procedure. Kuhn and co-workers were able to isolate the initial cyanohydrin intermediates by treating an aldose with anhydrous hydrogen cyanide in nonaqueous solvents. The cyanohydrins were catalytically reduced directly to the chain-extended products in aqueous solution at low pH 9-11 Although this procedure was employed .