Structure of the corynetoxins, metabolites of Corynebacterium rathayi responsible for toxicity of annual ryegrass (Lolium rigidum) pastures

Abstract

The corynetoxins, toxic metabolities of Corynebacterium rathayi formed in galled seed-heads of infected annual ryegrass, Lolium rigidum, are shown to be new members of the tunicamycin group of antibiotics. They consist of N-acetylglucosaminyl-tunicaminyl-uracil in amide linkage with fatty acids which differ in certain respects from those present in the tunicamycins. The corynetoxin acids are of slightly longer chain length, C₁₅-C₁₉, occur in a β-hydroxy as well as saturated and α,β-un-saturated series, and have anteiso, iso and normal chain terminations. β-Hydroxy acids have not been observed previously in the tunicamycin group and anteiso chains were reported only recently in the streptovirudin subgroup.

Stereochemical identity of the C₁₁-aminosugar in the corynetoxins with the tunicamine part of the tunicamycins is demonstrated by formation of a common hydrolysis product, di(N-trifluoro- acetyl)glucosaminyl-tunicaminyl-uracil. Analysis of the carbon-13 and proton n.m.r. spectra of the main components, corynetoxins H17a and U17a, confirms the stereochemistry proposed for tunicamine except that the glycosidic linkages are changed to α-galactosamine, β-glucosamine.