The Hofer-Moest decarboxylation of D-glucuronic acid and D-glucuronosides.
Research was undertaken to effect the oxidative decarboxylation of glycuronosides. Experiments with free D-glucuronic acid and aldonic acids were also executed. Both anodic decarboxylation and variants of the Ruff degradation reaction were investigated. Anodic decarboxylation was found to be the only successful method for the decarboxylation of glucuronosides. It was, therefore, proposed that glycuronosides can only undergo a one-electron oxidation to form an acyloxy radical, which decomposes to form carbon dioxide and a C-5 radical, that is, a Hofer-Moest decarboxylation. The radical is subsequently oxidized to a cation by means of a second one-electron oxidation. The cation undergoes nucleophilic attack from the solvent (water), whose product (a hemiacetal) undergoes a spontaneous hydrolysis to yield a dialdose (xylo-pentodialdose from D-glucuronosides).
Stapley
Jonathan A
JA
Whistler Center for Carbohydrate Research, Purdue University, 745 Agriculture Mall Drive, West Lafayette, IN 47906-2009, USA.
Bemiller
James N
JN
D003653:Decarboxylation; D020723:Glucuronic Acid / Q000737:chemistry*; D020719:Glucuronides / Q000737:chemistry*; D008956:Models, Chemical
D020719:Glucuronides; D020723:Glucuronic Acid