4 含硫ペプチド抗生物貭シオマイシンおよびチオストレプトンの化学構造と^<13>C NMRスペクトル

概要

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Sulfur-containing peptide antibiotics, siomycins (SIM) A, B, and C isolated from Streptomyces sioyaensis are known to have structures quite similar to that of thiostrepton (TST) isolated from S. azureus. The 25-MHz ^<13>C FT NMR and 220-MHz ^1H NMR spectra of TST and SIM's were determined in CDCl_3-CD_3OD (8: 2) at various temperatures to obtain structural relationships between these antibiotics. ^<13>C signals were tentatively assigned by ^1H noise decoupling, single-frequency and noise off-resonance decouplings, and partially-relaxed FT techniques and using known chemical-shift rules, the chemical shifts of amino acids reported, and those observed for thiostreptine and a quinaldic acid derivative. Their ^<13>C spectra quite similar to each other revealed the numbers of carbon atoms and dehydroalanine (Deala) residues. It was found that (1) the signals of the Val-Deala residues in SIM's are changed to those of the Ile-Ala residue in TST, that (2) SIM-B lacks of the terminal Deala-Deala residue in the long side-chain, and that (3) SIM-C has an unknown amino-acid residue instead of the terminal Deala. On the basis of the above spectral and other chemical studies, and a tentative structure (Ia) proposed for TST by an X-ray crystallographic analysis, the structures Ib, II, and III were concluded to be assigned to TST, and SIM-A and -B, respectively.
天然有機化合物討論会の論文
1976-09-20