Synthesis of 4-C-methyl analogues of glucosylceramide

✍ Scribed by Michael Plewe; Konrad Sandhoff; Richard R. Schmidt

• Book ID: 102998678
• Publisher: Elsevier Science
• Year: 1992
• Tongue: English
• Weight: 889 KB
• Volume: 235
• Category: Article
• ISSN: 0008-6215
• DOI: 10.1016/0008-6215(92)80085-f

✦ Synopsis

Benzyl 2,3,6-tri-O-benzyl-4-deoxy-4-C-methylenea_Dranoside (3) was transformed with 3-chloroperoxybenzoic acid into the epoxides 4 and 5. Reductive opening of the epoxide moiety in 4 furnished benzyl 2,3,6-tri-O-benzyl-4-C-methyl-a-o-glucopyranoside (6); subsequent hydrogenolytic Odebenzylation, per-0-acetylation, selective removal of the anomeric 0-acetyl group, and then treatment with trichloroacetonitrile in the presence of base afforded 2,3,4,6-tetra-O-acetyl-4-C-methyl-p-glucopyranosyl trichloroacetimidate (9). Reaction of 9 with the 3-0-benzoyl-azidosphingosines lOa,b in the presence of BF,.OEt, gave (2S,3R,4E)-2-azido-3-benzoyloxy-1-(2,3,4,6-tetra-O-acetyl-4-C-methyl-B_Dglucopyranosyloxy)~4octadecene (14a) and -4-dodecene (l&r), respectively. Treatment of 14a,b with triphenylphosphine and the carboxylic acid anhydride in the presence of water and then with methanolic sodium methoxide gave the title compounds 16a,b.