Chemical interaction between the aglycon and the allyl group of 6-O-allylhexopyranoside derivatives

✍ Scribed by Robert J. Ferrier; David W. Hall; Paul M. Petersen

• Book ID: 102992859
• Publisher: Elsevier Science
• Year: 1993
• Tongue: English
• Weight: 786 KB
• Volume: 239
• Category: Article
• ISSN: 0008-6215
• DOI: 10.1016/0008-6215(93)84210-w

✦ Synopsis

The free radical derived from l-O-allyl-2,6-anhydro-3,4,7,9-tet~d~~-8~-pheno~thi~ar~nyl-~ambrim-non-3-en-5-ulose. ethylene acetal (4), in the presence of tributyhin hydride, gave the direct product of reduction ( 13) and also products (15), derived following tandem cyclisation, which are structurally related to the trichothecenes. In addition, evidence was found which indicated that the initial radical reacted intramolecularly with the ally1 group. To establish whether radicals in aglycons can react with the alkene groups of 6-ally1 ethers of hexopyranosides, 2bromoethyl2,3,4-tri-O-ace@-6-0-dlyl-fi-o-glucopyranoside (19) was treated with tributyltin hydride and a radical initiator. The ll-membered ring product 5'-hydroxypentyl 2,3,4-tri-O-acetyl-6,5'-anhydro-~-o-glucopyranoside (21) was isolated (IS%, unoptimised) as well as the product of direct reductive debromination.