Novel autoxidation and Michael addition of a butenolide-containing sugar leading to a C-branched-chain glucopyranosidulose, and X-ray structure of intermediates.
A butenolide-containing sugar available from the aldol condensation of methyl 4,6-O-benzylidene-alpha-D-glucopyranosid-2-ulose with diethyl malonate is autoxidized at the C-3 position into the corresponding alpha,beta-unsaturated gamma-lactone sugar by air, which subsequently undergoes 1,4-conjugate (Michael) addition of hydroxide ion (or water) leading to a C-branched-chain glucopyranosidulose. The autoxidations are also performed in weakly basic, neutral and weakly acidic medium, respectively.
Liu
Hong-Min
HM
Department of Chemistry, Zhengzhou University, Daxue Road, Zhengzhou 450052, PR China. liuhm@zzu.edu.cn
Zhang
Fuyi
F
Zhang
Jianye
J
Li
Shi
S
D015107:4-Butyrolactone / Q000031:analogs & derivatives; D002236:Carbohydrate Conformation; D018360:Crystallography, X-Ray; D005663:Furans / Q000737:chemistry*; D005947:Glucose / Q000737:chemistry; D006027:Glycosides / Q000138:chemical synthesis*; D006860:Hydrogen Bonding; D007661:Ketoses / Q000737:chemistry; D008314:Malonates / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013237:Stereoisomerism
D005663:Furans; D006027:Glycosides; D007661:Ketoses; D008314:Malonates; C004511:butenolide; D005947:Glucose; D015107:4-Butyrolactone; C030978:diethylmalonic acid