Investigations towards the synthesis of dTDP-2,6-dideoxy-D-erythro-3-hexulose — a potential intermediate in the biosynthesis of rare sugars

✍ Scribed by Thomas Müller; Richard R Schmidt

• Publisher: Elsevier Science
• Year: 1997
• Tongue: French
• Weight: 252 KB
• Volume: 38
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(97)01224-0

✦ Synopsis

The synthesis of the target molecule 1 is based on thexyldimethylsilyl 4-O-acetyl-2,3,6-trideoxy-3-Cmethylene-~-D-erythro-hexopyranoside (7) which is readily obtained via two different mutes from tri-O-acetyl-Dglacal (2). Replacement of the anomeric silyl group by the diethylphosphite group, then performing a phosphite/phosphate exchange reaction, and finally removal of all protective groups affccded an o¢l$-mixture of 2,3,6tri-deoxy-3-C-methylene-D-erythro-hexopyranosyl phosphate (8); its ozonolysis furnished the corresponding 3-ulose 10. Treatment of g with dTMP-morpholidate in pyridine led to the 3-C-methylene analogue 9ct of the target molecule; ozonolysis of 9or afforded 1 which -as expected -experienced relatively fast IS--elimination under work-up conditions.