Oxidative decarboxylation as a route to ketene acetals: assignment of relative and absolute stereochemistry to the fungal metabolite benesudon by total synthesis.
The unusual 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 possibilities 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, Canada T6G 2G2. derrick.clive@ualberta.ca
Minaruzzaman
D000080:Acetals / Q000737:chemistry*; D001203:Ascomycota / Q000737:chemistry* / Q000378:metabolism*; D002125:Calcium Gluconate / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry*; D005030:Ethylenes / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011714:Pyrans / Q000138:chemical synthesis / Q000737:chemistry / Q000378:metabolism; D013237:Stereoisomerism
D000080:Acetals; D002264:Carboxylic Acids; D005030:Ethylenes; D007659:Ketones; D011714:Pyrans; C104991:benesudon; C008223:ketene; D002125:Calcium Gluconate