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The first direct synthesis of (+)-lysergic acid (2a) suitable for scale-up has been achieved by the following reaction sequence. Bromoketones 4d or 4g were allowed to react with amine 5 followed by deprotection, and the resulting diketone 6c was transformed into the unsaturated ketone (+/-)-7 by the LiBr/Et(3)N system. Resolution afforded (+)-7, which was further transformed by Schöllkopf's method into the mixture of esters 2e and 2f. Upon hydrolysis the latter mixture afforded (+)-2a. The peptide part of alpha-ergocryptine (1) was prepared according to the Sandoz method; the stereoefficiency, however, has been significantly improved by applying a new resolution method and recycling the undesired enantiomer. Coupling the peptide part with lysergic acid afforded 1. Having synthetic (+)-7 in hand, we can claim the total synthesis of all the alkaloids which were prepared earlier from (+)-7 that had been obtained through degradation of natural lysergic acid.

Griseochelin, C3,H;;QO" isolated from an asporogenous strain of Streptonryces griseus represents a novel carboxylic acid antibiotic. The metabolite, which is active against Grarnpositive bacteria, forms water-insoluble salts with mono-and divalent cations and binds alkaline-earth metal ions specifically in 2: 1 (X_M) stoichiometry.Detailed spectral (IR, MS and NMR) studies provide full characterization of its constitution featuring a carboxylic acid function, a substituted tetrahydropyran ring, an allylic OH group which are accomodated within a tetrahydroxylated-octamethyl-C" diene backbone.Griseochelin was isolated in the course of our investigations into the biochemistry of streptomycinnon-producing Amy-mutants derived from high-yielding streptomycin-producing strains of Strepto- StrainThe griseochelin-producing strain, S. griseus ZIMET 43681, was taken from the strain collection of the Central Institute of Microbiology and Experimental Therapy, Jena. It represents a stable prototropic Amy-Str-mutant of the high-yielding, streptomycin-producing (Amy+ Str+) S. griseus HP strain". Derived from the parent strain via glycerol-limited chemostat cultivation, this mutant exhibits a number of modified biochemical properties. In particular, it excels in its capability to produce griseochelin under submerged cultivation in enhanced yields that may exceed those of the parent strain by a factor of 10 to 303). FermentationLyophilized stock mycelia" were first propagated in agar slant cultures at 27°C for 8 days. The medium consisted of baker's yeast 1.5 %, maize starch 1 %, NaCI 0.5 %, peptone (Difco 0.1 %) and agar 2Y. and had a pH 7.0. Samples of the slant cultures were then used to inoculate the growth medium

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Hydroxyindolones (1-6, 15-16) were transformed into isatinylidenes (7, 9-13, 17-19) by dehydration with 4-toluenesulfonic acid. The dimer-type compounds (14, 20) were also isolated in a few cases. The obtained isatinylidenes were transformed into 3-spiro-cyclopropane-oxindoles (21-32) with dimethyloxosulfonium methylide. Compound 22 shows protective effects against hypobaric hypoxia and triethyltin induced brain edema.

In einer vorangehenden Mitteilung beschrieben wir die Synthese der Dibenzo-a-pyrone Autumnariol und Autumnariniol I), Inhaltsstoffe von Eucomis autumnalis (Liliaceae). Hier beschreiben wir die Synthese zweier Stoffwechselprodukte aus Mikroorganismen, von Alternariol (1) und seines 9-Monomethylethers (2), die 1953 erstmals von Raistrick et aL4) aus Alternaria tenuis und spater auch aus verschiedenen anderen AlternariaArten ') isoliert wurden.Das Grundgeriist von 1 und 2 wurde durch eine von Raistrick et al.4' ausgefuhrte Synthese des Trimethylethers 3 bewiesen, doch konnte diese die relative Lage der Methyl-und Hydroxylgruppe an C-1 bzw. -3 nicht eindeutig belegen. Eine der Biogenese ahnelnde Entstehungsweise des Alternariols aus 7-(4-0rcinyl)-3,5,7-trioxoheptansaure beschrieben Hay und Harris6'. Tamm und Mitarbb. konnten aufgrund des nuclearen Ouerhnuser-Effektes die Methylgruppe in 1 und einer Reihe von natiirlichen und durch Hurtley-Kondensation hergestellten synthetischen ') I. Mitteil.: L. Farkas, F. Sdti, M. Incze und M. Ndgrcidi, Chem. Ber. 107, 3874 (1974).

Organic chemistry Z 0200 Synthetic Route to Ergot Alkaloids -[37 refs.]. -(MOLDVAI, I.; TEMESVARI-MAJOR, E.; INCZE, M.; DOERNYEI, G.; SZENTIRMAY, E.; SZANTAY*, C.; Helv. Chim. Acta 88 (2005) 6, 1344-1356; Chem. Res. Cent., Hung. Acad. Sci., H-1525 Budapest, Hung.; Eng.) -S. Adam 40-257