Fruiting-body inducers

A myxobacterium Stigmatella aurantiaca uses stigmolone (22) as its fruiting body inducing pheromone. Both the enantiomers of 22 were synthesized by Mori [56] and also byEnders [57], and found to be equally bioactive. Scheme 33 shows Mori s synthesis, and Scheme 34 summarizes that of Enders. Since both (R)- and (S)-22 were bioactive, ( )-22 was synthesized in a very efficient manner by Kulinkovich (Scheme 35) [58]. 

Figure 5.3 Structures of fruiting-body inducers for mushrooms. Reprinted with permission of Shokabo Publishing Co., Ltd...

Figure 5.7 Synthesis of Pen III, a metabolite of Penicillium funiculosum with fruiting-body inducing activity against Schizophyllum commune...

Based on the evidence of positive and negative ion mode FAB MS, the structure of cerebroside (1) was determined to be (4E,8E)-N-2-hydroxyhexadecanoyl-l-0-P-gluco-pyranosyl-9-methyl-Ci8-sphinga-4,8-dienine (Fig. 1), which had been isolated from Schizophyllum commune by Kawai and Ikeda [8] as a fungal fruiting body inducer. 

Enders D, Ridder A. First asymmetric synthesis of stigmolone the fruiting body inducing pheromone of the myxobacte-rium StigmateUa aurantiaca. Synthesis-Stuttgart. 2000 13 1848 1851. 

The fruiting body of the inky cap mushroom Coprinus atramentarius, Bull. (Ba-sidiomycetes) is apparently non-toxic when eaten alone, but induces in humans and in experimental animals an over-sensitivity to ethanol [16]. 

Figure 40 Stigmolone, an inducer of fruiting bodies of myxobacteria. Equilibrium between the hydroxy ketone stigmolone (a) and dihydropyran (b) is shown.

Both (R)- and (S )-stigmolone induced the formation of fruiting bodies of S. aurantiaca at a concentration of 0.4-1.0 nM. A racemic mixture of 110 and 110 was also active. Subsequently, the natural stigmoione was shown to be an enantiomeric mixture.108... 

After completion of the synthesis of Sch II (128) in 1985, we continued our studies on the cerebro-sides inducing the fruiting-body formation in Schizophyllum commune, and the cerebrosides shown in... 

Pen II (130) is another metabolite of P. fumiculosum, and also induces fruiting-body formation of S. commune. For the synthesis of the sphingadienine part C of 130, a new and simpler route was adopted, as shown in Figure 5.8.14 Garner s aldehyde I was employed in this case, too. 

The reason why these cerebrosides induce fruiting-body formation of S. commune is not yet clear. 

In the early 1990s, Azuma, Beppu and their coworkers isolated basidifferquinone C (132, Figure 5.10) from Streptomyces sp. B-412 as an inducer of fruiting-body formation in a mushroom Polyporus arcularius. Its unique structure led us to attempt its synthesis, but we were unable to synthesize it until 2008, when my former student H. Takikawa was successful in synthesizing it, as shown in Figure 5.10.16... 

The glycolipid has the chemical structure of (4E,8E)-N-D-2 -hydroxypalmitoyl-1-0- p-D-glucopyranosyl-9-methyl-4,8-sphingadienine. A similar structure has been reported by Karlsson et al. in the sea anemone Metridium senile (79), This molecule was capable of inducing fruiting body formation when tested on a dikaryotic strain of S.commune. In order to determine the part of the molecule responsible for the activity, the degraded products were tested. 

Oh et al. [188] isolated the principle (3f ,6f )-4-methyl-6-( 1 -methylethyl)-3-phenylmethylperhydro-l, 4-oxazine-2,5-dione from the fruiting bodies of Isaria japonica to study its effects as an apoptosis-inducing agent on human leukemia HL-60 cells. 

Comments F. velutipes tends to form mycelial "pellets" soon after colonizing a substrate. This phenomenon makes liquid cuiture techniques more difficult. Japanese researchers found that the addition of 5% corn starch and 2% malt to a liquid soiution inhibits the formation of these troublesome pellets. Curiously, fruitings on sawdust/bran beds can be precipitated when pieces of a fruit-body are added to this solution. Shiio et al. (1974) found that one could induce the early formation... 

Jelsbak, L. and Sogaard-Andersen, L. (1999). The cell surface-associated intercellular C-signal induces behavioral changes in individual Myxococcus xanthus cells during fruiting body morphogenesis. Proc. Natl. Acad. Sci. U.S.A. 96, 5031-5036. 

Wireman, J.W. and Dworkin, M. (1977). DevelopmentaHy induced autolysis during fruiting body formation by Myxococcus xanthus. J. Bacterial. 129, 796-802. 

P. wortmanni contains the acetylated wortmin in addition to M. The (5)-forms of M., mitorubrinol, and mitorubrinic acid occur in the fruit bodies of Hypoxy-lon fragiforme. Azaphilones (affinity for nitrogen) react with ammonia and amines to form red or dark red compounds. Mitorubrinic acids and lunatic acids formed by Cochliobolus lunatus, belong to the mor-phogenous substances that induce the formation of thick-walled mycelia. All compounds exhibit weak antifungal activities. 

Prod, by Streptomyces sp. B-412. Induces fruiting-body formation of Favolus arcularius. Orange cryst. Mp > 220° dec. 

---