Sulfur participation in methanolysis and acetolysis of 5-deoxy-5-thio-D-glucose derivatives

✍ Scribed by Hironobu Hashimoto; Hideya Yuasa

• Publisher: Elsevier Science
• Year: 1988
• Tongue: French
• Weight: 254 KB
• Volume: 29
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)82084-5

✦ Synopsis

Acid methanolysis of 5-deoxy-5-thio-D-glucose derivatives gave the $-O-methyl glycoside 4 and the 4,6-di-0-methylated dimethyl acetal 1, indicating transannular participation of the sulfur atom. Similarly, acetolysis of the corresponding per-O-alkylated glucosides gave the 1,4diacetates, 13 and 17. --Nucleophilic substitutions of 2-and 4-0-sulfonates of 5-thiopyranoside derivatives were found to proceed via transannular sulfur participation, giving substituted products with retention of configuration or ring-contracted products'. A similar ring contraction was suggested for the formation of 5bromomethyl-2-formylthiophene on the hydrobrominolysis2 of methyl 2,3,4,6-