Biosynthesis and Identification of Volatiles Released by the Myxobacterium Stigmatella aurantiaca

Abstract

The volatiles released by agar plate cultures of two strains of the myxobacterium Stigmatella aurantiaca (strains Sg a15 and DW4/3-1) were collected in a closed-loop stripping apparatus (CLSA) and analyzed by GC-MS. Large numbers of substances from different compound classes (ketones, esters, lactones, terpenes, and sulfur and nitrogen compounds) were identified; several of them are reported from natural sources for the first time. The volatiles 2-methyltridecan-4-one (17), its isomer 3-methyltridecan-4-one (20), and the higher homologue 2-methyltetradecan-4-one (18) were identified in the extracts of both strains and were synthesized. In addition, strain Sg a15 produced 2,12-dimethyltridecan-4-one (19), 2-methyltridec-2-en-4-one (23), and a series of phenyl ketones, among them 1-phenyldecan-1-one (14) and 9-methyl-1-phenyldecan-1-one (16), whereas strain DW4/3-1 emitted traces of 10-methylundecan-2-one (21). The biosynthesis of 14 and 16 was examined in feeding experiments with deuterated precursors carried out on agar plate cultures. The leucine-derived starter unit isovalerate was shown to be incorporated into 16, as was phenylalanine-derived benzoic acid into both 14 and 16. The results point to formation both of the phenyl ketones and of the structurally related aliphatic ketones through an unusual head-to-head coupling between a starter unit such as benzoyl-CoA and a fatty acyl-CoA, followed by decarboxylation.

Terpene synthases are widely distributed in bacteria

“…In addition to determining the structure of Berthelot's geosmin, shown to be a C 12 degraded sesquiterpene alcohol (and giving it its name, which means earth odor) (2, 3), Gerber (4) also isolated and determined the structures of the methylated monoterpene 2-methylisoborneol as well as several other cyclic sesquiterpenes produced by streptomycetes (5-7). In subsequent years, numerous volatile terpenes have been detected in streptomycetes (8)(9)(10)(11)(12)(13)(14)(15)(16). The three most commonly detected streptomycetes terpenoids, geosmin, and 2-methylisoborneol and the tricyclic α,β-unsaturated ketone albaflavenone (Fig.…”

Isoprenoids Are Essential for Fruiting Body Formation in Myxococcus xanthus

“…We also described the genes required for the degradation pathway of leucine and subsequently also those involved in the transformation of IV-CoA to HMG-CoA (4). In myxobacteria leucine is an important precursor for isoprenoid biosynthesis, as was already shown elsewhere for the biosynthesis of steroids (7) and prenylated secondary metabolites like aurachin (22) or leupyrrins (6), as well as volatiles like geosmin or germacradienol in M. xanthus and S. aurantiaca (11,13). The interconnection of iso-FAs and isoprenoid biosynthesis made it difficult to assign functions to these compound classes during fruiting body formation in M. xanthus because it cannot be excluded that reduced leucine degradation also impairs isoprenoid biosynthesis.…”

Geosmin Biosynthesis in Streptomyces avermitilis. Molecular Cloning, Expression, and Mechanistic Study of the Germacradienol/Geosmin Synthase

“…Since that time, germacradienol has frequently been observed as a cometabolite of geosmin in streptomycetes, myxobacteria, and liverworts, often accompanied by germacrene D (4) [5,6,22]. Consistent with the demonstration that S. coelicolor A3(2) harbors a germacradienol synthase encoded by the SCO6073 gene, and that this gene is essential for geosmin production, we and others originally proposed a variety of multistep biosynthetic pathways involving both oxidative and reductive transformations to account for the evident conversion of germacradienol to geosmin [4,13,20,23].…”