On the distribution of the diastereomers of the structural elements in lignins: the steric course of reactions mimicking lignin biosynthesis

Abstract

Stereochemical studies on the formation of the diastereomers of arylglycerol-β-aryl ether structures during lignin biosynthesis have been carried out with model compounds. The addition of water to quinone methides of the β-syringyl ether type gives arylglycerol β-syringyl ethers with a predominance of the erythro isomer when the pH of the medium is low. Since erythro forms of arylglycerol β-syringyl ethers are prevalent in hardwood lignins, this indicates that the pH of the medium in which lignin biosynthesis occurs is lower than has been assumed until now. Equilibration studies with non-phenolic model compounds of the arylglycerolβ-guaiacyl ether and β-syringyl ether types under acidolysis conditions indicate that the erythro predominance observed in the syringyl ethers in lignins does not correspond to equilibrium conditions. A remarkable resistance to acidolysis is observed in the model compounds of etherified syringylglycerol β-syringyl ether type.