80 ヌノサラシ科魚の脂溶性皮膚毒の化学構造(ポスター発表の部)

概要

論文の詳細を見る
A lipophilic ichthyotoxin from the defensive mucous skin secretion of soapfishes Diploprion bifasciatum and Aulacocephalus temmincki (the family Grammistidae), named lipogrammistin-A, was isolated and chemically characterized. Its ^<13>C NMR spectrum showed many sets of four weak temperature-dependent signals, each of which was attributed to one carbon on the basis of CH-COSY. Despite of the complexity of the NMR spectra due to four interchanging conformers in solution, the planar structure was successfully deduced by intensive analysis of 2D-NMR spectra as an 18-membered polyamine lactam with a C-11 aliphatic side chain (1). Stereochemistry of its two 2-methylbutyroyl moieties were deduced both S by mild acid hydrolysis to yield (S)-2-methylbutyric acid, as identified in the form of (S)-1-(1-naphthyl)ethylamide. Lipogrammistin-A is not only differs in its chemical type from the other defense substances of fish ever known, but also is the first example of a macrocyclic polyamine lactam found in the animal kingdom. It shows toxicity to medaka fish and to mice, and hemolytic activity to rabbit erythrocytes. For further chemical and biological investigation on this compound, synthetic study is being performed with a route shown in Scheme 1 and 2.
天然有機化合物討論会の論文
1993-09-10