The naturally occurring ketene acetal benesudon: total synthesis and assignment of relative and absolute stereochemistry.
The densely functionalized ketene acetal benesudon, which is a bioactive fungal metabolite, was synthesized from D-glucose by a route involving radical cyclization to form the five-membered ring, and oxidative decarboxylation to generate the key central double bond. The originally suggested stereochemistry for the quaternary center C(5) must be revised, as both C(5) epimers were prepared and a comparison with an authentic sample was made. The absolute configuration of benesudon is 4S,5R,6S.
Clive
Derrick L J
DL
Chemistry Department, University of Alberta, Edmonton, Alberta T6G 2G2, Canada. derrick.clive@ualberta.ca
Minaruzzaman
Yang
Haikang
H
D000080:Acetals / Q000737:chemistry*; D000900:Anti-Bacterial Agents / Q000138:chemical synthesis* / Q000494:pharmacology; D000935:Antifungal Agents / Q000138:chemical synthesis* / Q000494:pharmacology; D002264:Carboxylic Acids / Q000737:chemistry; D018360:Crystallography, X-Ray; D003500:Cyclization; D005030:Ethylenes / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D011714:Pyrans / Q000138:chemical synthesis / Q000494:pharmacology; D013237:Stereoisomerism
D000080:Acetals; D000900:Anti-Bacterial Agents; D000935:Antifungal Agents; D002264:Carboxylic Acids; D005030:Ethylenes; D007659:Ketones; D011714:Pyrans; C104991:benesudon; C008223:ketene