Studies on the biosynthesis of cyclitols, XXXI. Further investigations on the biosynthesis of laminitol (1D-4-c-methyl-myo-inositol) in Porphyridium sp.
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To elucidate the biosynthetic pathway of platenomycin (PLM), biosynthetic relationships of platenolides I (PL-I) and II (PL-II), 3-O-propionyl-5-O-mycaminosyl platenolides I (PPL-I-MC) and II (PPL-UU-MC), 9-dehydro demycarosyl platenomycin (DDM-PLM) were examined with growing cultures or the washed mycelium of blocked mutants of Streptomyces platensis subsp. malvinus MCRL0388, a platenomycin-producing organism. As a result, it was revealed that PLM was biosynthesized from PL-I via DM-PLM and DA-PLM along the pathways shown in Chart 1. 4''-Isovaleroyl unit of PLM-A and 4''-propionyl unit of PLM-B were respectively derived from L-leucine and L-isoleucine.
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An aclacinomycin-negative mutant strain KE303 which required aklavinone aglycone for the production of anthracycline antibiotics was derived from Streptomyces galilaeus, and employed for the glycosidation of various anthracyclinones. epsilon- gamma- and beta-Rhodomycinones, epsilon-isorhodomycinone, epsilon- and beta-pyrromycinones and chemically modified aklavinones were found to be glycosidated to the biologically active anthracyclines, when they were fed to the growing culture. However, the feeding of daunomycinone, 13-deoxydaunomycinone, adriamycinone and steffimycinone did not yield any glycoside. The bioconversion of presumptive precursor glycosides revealed that aclacinomycin A is biosynthesized by the step-wise glycosidation from aklavinone vai aklavin and MA144 S1.
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Ten metabolites produced by 4 mutants derived from Actinomadura verrucosospora subsp. neohibisca E-40, a high pradimicins producer, were isolated and their structures were determined. Strain JN-219 produced 3 novel analogs of the pradimicin A aglycone, i.e. 11-O-demethyl-7-methoxypradinone II and 11-O-demethylpradinones I and II together with a known aglycone analog, pradinone I, while the metabolites from strain JN-47 were determined to be 2 new aglycone analogs, 11-O-demethylpradimicinone I and 11-O-demethyl-7-methoxypradimicinone II and a known aglycone analog, 11-O-demethylpradimicinone II (11dM-PMN II). Products of strain JN-207 were identified as 11-O-demethyl-6-deoxypradinone I and 11dM-PMN II. Interestingly, a new pradimicin analog, 7-hydroxypradimicin A was isolated from strain JN-58 together with a new aglycone analog, pradimicinone II and 11dM-PMN II. None of these metabolites showed antifungal activity.
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