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At least 397 records · Page 22Linked to original sources
PubMed2005

Macrophomate synthase: QM/MM simulations address the Diels-Alder versus Michael-Aldol reaction mechanism.

Macrophomate synthase (MPS) of the phytopathogenic fungus Macrophoma commelinae catalyzes the transformation of 2-pyrone derivatives to the corresponding benzoate analogues. The transformation proceeds through three separate chemical reactions, including decarboxylation of oxalacetate to produce pyruvate enolate, two C-C bond formations between 2-pyrone and pyruvate enolate that form a bicyclic intermediate, and final decarboxylation with concomitant dehydration. Although some evidence suggests that the second step of the reaction catalyzed by MPS is a Diels-Alder reaction, definite proof that the C-C bond formations occur via a concerted mechanism is still required. An alternative route for formation of the C-C bonds is a stepwise Michael-aldol reaction. In this work, mixed quantum and molecular mechanics (QM/MM) combined with Monte Carlo simulations and free-energy perturbation (FEP) calculations were performed to investigate the relative stabilities of the transition states (TS) for both reaction mechanisms. The key results are that the Diels-Alder TS model is 17.7 and 12.1 kcal/mol less stable than the Michael and aldol TSs in the stepwise route, respectively. Therefore, this work indicates that the Michael-aldol mechanism is the route used by MPS to catalyze the second step of the overall transformation, and that the enzyme is not a natural Diels-Alderase, as claimed by Ose and co-workers (Nature 2003, 422, 185-189; Acta Crystallogr. 2004, D60, 1187-1197). A modified link-atom treatment for the bonds at the QM/MM interface is also presented.

Benzoates↗
PubMed2005

Exploiting the reaction flexibility of a type III polyketide synthase through in vitro pathway manipulation.

A synthetic metabolic pathway has been constructed in vitro consisting of the type III polyketide synthase from Streptomyces coelicolor and peroxidases from soybean and Caldariomyces fumago (chloroperoxidase). This has resulted in the synthesis of the pentaketide flaviolin and its dimeric derivative, and a wide range of pyrones and their coupled derivatives with flaviolin, as well as their halogenated derivatives. The addition of acyl-CoA oxidase to the pathway prior to the polyketide synthase resulted in unsaturated pyrone side chains, further broadening the product spectrum that can be achieved. The approach developed in this work, therefore, provides a new model to exploit biocatalysis in the synthesis of complex natural product derivatives.

Acyl Coenzyme A↗
PubMed2004

Structure-activity relationships of derivatives of fusapyrone, an antifungal metabolite of Fusarium semitectum.

Fusapyrone (1) and deoxyfusapyrone (2) are two 3-substituted-4-hydroxy-6-alkyl-2-pyrones isolated from Fusarium semitectum that have considerable antifungal activity against molds. Because of their low zootoxicity and selective action they are potentially utilizable along with biocontrol yeasts for control of postharvest crop diseases. Seven derivatives of 1 (3 and 5-10) and one derivative of 2 (4) were obtained by chemical modifications of the glycosyl residue, the 2-pyrone ring, the aliphatic chain, or a combination thereof, and a structure-activity correlation study was carried out with regard to their zootoxicity and antifungal activity. Derivatives 7-10, as well as 1, were slightly zootoxic in Artemia salina (brine shrimp) bioassays, whereas pentaacetylation of 1 into 3, 5, and 6 resulted in a strong increase in toxicity. Compound 4, the tetraacetyl derivative of 2, was as toxic as 2. Because the structural changes of 1 that resulted in an increase of biological activity in A. salina bioassay were those that affected mainly the water solubility of the molecule, it appears that toxicity is related to hydrophobicity. Compounds 1 and 2 showed strong antifungal activity toward Botrytis cinerea, Aspergillus parasiticus, and Penicilliun brevi-compactum (minimum inhibitory concentration at 24 h = 0.78-6.25 microg/mL). Among derivatives 3-10, only compounds 7, 9, and 10 retained some activity, limited to B. cinerea and at high concentration (25-50 microg/mL). None of the compounds 1-10 inhibited the growth of the biocontrol yeasts Pichia guilliermondii and Rhodotorula glutinis at the highest concentration tested (50 microg/mL).

Animals↗
PubMed2002

First total syntheses of the phytotoxins solanapyrones D and E via the domino Michael protocol.

The phytotoxins solanapyrones D (1) and E (2) have been synthesized from the decalone prepared by the domino Michael reaction of the kinetic enolate of optically pure acetylcyclohexene with methyl crotonate. The decalone was transformed into a solanapyrone core by equilibration into thermodynamically stable trans-decalone (11), dehydroxylation, and dehydration. Condensation of a methyl acetoacetate equivalent followed by cyclization installed a pyrone moiety. Introduction of a formyl or hydroxymethyl unit into the pyrone ring via Pummerer related reactions furnished solanapyrones D (1) and E (2).

Alternaria↗
PubMed2000

Biological characterization of fusapyrone and deoxyfusapyrone, two bioactive secondary metabolites of Fusarium semitectum.

Fusapyrone (1) and deoxyfusapyrone (2), two alpha-pyrones originally isolated from rice cultures of Fusarium semitectum, were tested in several biological assays. Compounds 1 and 2 showed considerable antifungal activity against several plant pathogenic and/or mycotoxigenic filamentous fungi, although they were inactive toward yeasts isolated from plants and the Gram-positive bacterium Bacillus megaterium in disk diffusion assays. Compound 1 was consistently more active than 2. Among the tested fungi, Fusarium species were the least sensitive to the two pyrones, while Alternaria alternata, Ascochyta rabiei, Aspergillusflavus, Botrytis cinerea, Cladosporium cucumerinum, Phoma tracheiphila, and Penicillium verrucosum were the most sensitive. Compounds 1 and 2 also showed good inhibitory activity toward agents of human mycoses. Aspergilli were the most sensitive, while some species-specific variability was found among the Candida spp. In an Artemia salina larvae bioassay, 1 was not toxic at the highest concentration tested (500 microM), whereas the LC(50) of 2 was 37.1 microM (21.8 microg/mL). Neither 1 nor 2 was phytotoxic in a panel of assays that monitored plant-cell toxicity, as well as wilt-, chlorosis-, and necrosis-inducing activity. Moreover, 2 stimulated the root elongation of tomato seedlings at doses of 10 and 100 microM. In consideration of the biological activities evidenced in this study, 1 and 2 appear to be potential candidates for biotechnological applications, as well as good models for studies on mechanism(s) of action and structure-activity relationships.

Animals↗
PubMed2003

Annularins A-H: new polyketide metabolites from the freshwater aquatic fungus Annulatascus triseptatus.

Eight new polyketide metabolites, annularins A-H (1-8), along with the known compound (-)-(S)-p-hydroxyphenyllactic acid, were isolated from the organic extracts of the freshwater fungus Annulatascus triseptatus. Compounds 1-6 are 3,4,5-trisubstituted alpha-pyrones, and the fused bicyclic pyrone-furanone system in annularin F (6) has not been reported previously among natural products. Compounds 7 and 8 are 3,4-disubstituted alpha,beta-unsaturated gamma-lactones. Annularins A (1), B (2), C (3), and F (6) exhibited antibacterial activity.

Anti-Infective Agents↗
PubMed2005

Photochemical relationships in Sacoglossan polypropionates.

Cyercene A has been synthesized and converted to placidene A and isoplacidene A through photoisomerization with sunlight. Hydroperoxide, isolated form Placida dendritica, was synthesized both by singlet oxygenation of cyercene A using Rose Bengal and through the irradiation of cyercene A alone in aerobic solution. The observation that hydroperoxide could be made by singlet oxygenation of cyercene A and that this occurs when cyercene A alone is irradiated supported the hypothesis that gamma-pyrones may act as triplet sensitizers. This was confirmed using cyercene A and a model gamma-pyrone to sensitize the photooxidation of n-butyl sulfide. The biosynthetic implications of these observations for Sacoglossan polypropionates are discussed.

Animals↗
PubMed2001

The first total synthesis of (-)-solanapyrone E based on domino Michael strategy.

[figure: see text] A phytotoxin, solanapyrone E, has been synthesized from the decalone prepared by the domino Michael reaction of the kinetic enolate of optically pure acetylcyclohexene with methyl crotonate. After several transformations on the decalone ring, condensation of a methyl acetoacetate equivalent installed a pyrone moiety and introduction of a hydroxymethyl unit into the pyrone ring furnished solanapyrone E.

Alternaria↗
PubMed2001

Stereoselective trans- and cis-dihydroxylations of 2H-pyranyl and dihydropyridinyl heterocycles synthesized from formal [3 + 3]-cycloaddition reactions of alpha,beta-unsaturated iminium ions with 1,3-dicarbonyl equivalents.

[reaction: see text]We describe here an inherent problem in direct epoxidation of the endocyclic olefin in 2H-pyrans fused to 2-pyrones. Such difficulties led to the development of highly stereoselective trans- and cis-dihydroxylations of these olefinic systems in both 2H-pyrans and dihydropyridines fused to a 2-pyrones or a 2-cyclohexenone. Protocols for the removal of the activated allylic hydroxyl group are also reported.

Alkaloids↗
PubMed2002

Enantioenriched dihydropyrones from beta-lactone templates.

[reaction: see text] Optically active 4-substituted 2-oxetanones provide conduits for preparing 2,3-dihydro-4H-pyrone heterocycles. Enantioenriched beta-lactones are prepared by asymmetric catalytic acyl halide-aldehyde cyclocondensation reactions. Hydrazone anion-mediated beta-lactone ring opening and ensuing cyclization-dehydroamination of the derived beta-ketohydrazone afford the desired dihydropyrones (68-81%). Optimized lactone ring-opening-cyclization reaction conditions render a variety of optically active 4-substituted-2-oxetanones as effective precursors to enantioenriched 2,3-dihydro-4H-pyrones.

Cyclization↗
PubMed2005

Stereoselective synthesis of cyercene A and the placidenes.

Members of a family of alpha-methoxy-gamma-pyrone-containing polypropionate natural products have been stereoselectively synthesized. Two key iodovinyl pyrone building blocks were coupled to appropriately selected vinyl stannanes to assemble the highly substituted polyene side chains of the natural products. [structure: see text]

Biological Products↗
PubMed2005

Synthesis of an analogue of the marine polypropionate tridachiahydropyrone.

[reaction: see text] A novel approach to the formation of the unusual pyrone-containing ring systems as found in polypropionate metabolites from the Tridachia family of marine molluscs has been developed. This approach includes an intramolecular cyclization of a beta-keto acid onto a cyclohexenone ring to afford a fused, bicyclic pyrone.

Animals↗
PubMed1990

The antinociceptive actions of kava components in mice.

1. The antinociceptive properties of the aqueous extract of the intoxicating beverage kava, and of the lipid soluble extract (kava resin) were tested in mice, by the tail immersion and abdominal constriction methods. Both extracts showed analgesic effects in both tests. 2. Eight purified pyrones from the lipid soluble extract were also tested for activity in the tail immersion test, and kawain, dihydrokawain, methysticin and dihydromethysticin were found to be very effective in producing analgesia. Using the tail immersion test the time course of action of the extracts of the four effective pyrones of kava were studied. 3. Naloxone, in doses which inhibited morphine-induced analgesia in both tests, was completely ineffective in reversing the antinociceptive activities of the kava extracts, showing that analgesia produced by kava occurs via non-opiate pathways.

Analgesics↗
PubMed1995

Isolation of some immunosuppressive components from an ascomycete, Gelasinospora multiforis.

Five new components, named multiforisins A, B, C, D, and E, with immunosuppressive activity were isolated from an Ascomycete, Gelasinospora multiforis. Multiforisin A, the main immunosuppressive principle of this fungus, was deduced to be 5-formyl-3-(hydroxymethyl)-4-methoxy-6-(1E-propenyl)-alpha-pyrone. Multiforisins B, C, D, and E were also deduced to be alpha-pyrone derivatives related to multiforisin A. The IC50 values of multiforisins A, B, C, D, E, and dihydro multiforisin A were evaluated against proliferation of mouse spleen lymphocytes stimulated with concanavalin A and lipopolysaccharide.

Ascomycota↗
PubMed1990

The kapurimycins, new antitumor antibiotics produced by Streptomyces. Physico-chemical properties and structure determination.

The kapurimycins A1, A2 and A3 were revealed to be new antitumor antibiotics with molecular formula of C27H26O9, C26H24O9 and C27H24O9, respectively. The structures of the kapurimycins were determined by NMR spectroscopic analysis. The kapurimycins are new class of polycyclic microbial metabolites having the tetrahydroanthra-gamma-pyrone skeleton and the beta, gamma-unsaturated delta-keto carboxylic acid structure. The individual components of the kapurimycins differ from one another in the side chain at the pyrone ring of the molecule.

Anthracenes↗
PubMed1993

Dactylfungins, novel antifungal antibiotics produced by Dactylaria parvispora.

Novel antifungal antibiotics, designated as dactylfungins A (1) and B (3), were isolated from the culture broth of Dactylaria parvispora D500. Dactylfungins A and B were found to be new substances containing an alpha-pyrone and a gamma-pyrone ring, respectively, which conjoined with a polyalcohol moiety and a long side chain, based on NMR spectral analyses. The antibiotics were active against Candida pseudotropicalis and other fungi, with an MIC value at less than 10 micrograms/ml.

Antifungal Agents↗
PubMed1998

[The chemical constituents of Goniothalamus howii Merr].

Two new compounds were isolated from the chloroform soluble fraction of ethanolic extract of bark of Goniothalamus howii Merr. On the basis of their chemical properties and spectral data (MS, UV, IR, 1H and 13CNMR) they were identified as 6S (1R-hydroxy-2R-cinnamyloxyphenethyl) 5, 6-dihydro-5S-hydroxy-2-pyrone named Howiinol A and 6S-(1S, 2R-epoxyphenethyl-5S-cinnamyloxy) 5, 6-dihydro-2-pyrone named Howiinin A. Howiinol A showed significant antitumor activities toward human tumor cell in vitro and in vivo and less toxic.

Animals↗
PubMed2000

Enzymatic formation of unnatural aromatic polyketides by chalcone synthase.

Substrate specificity of recombinant chalcone synthase (CHS) from Scutellaria baicalensis (Labiatae) was investigated using chemically synthesized aromatic and aliphatic CoA esters. It was demonstrated for the first time that CHS converted benzoyl-CoA to phlorobenzophenone (2,4,6-trihydroxybenzophenone) along with pyrone by-products. On the other hand, phenylacetyl-CoA was enzymatically converted to an unnatural aromatic polyketide, phlorobenzylketone (2, 4,6-trihydroxyphenylbenzylketone), whose structure was finally confirmed by chemical synthesis. Furthermore, in agreement with earlier reports, S. baicalensis CHS also accepted aliphatic CoA esters, isovaleryl-CoA and isobutyryl-CoA, to produce phloroacylphenones. In contrast, hexanoyl-CoA only afforded pyrone derivatives without formation of a new aromatic ring. It was noteworthy that both aromatic and aliphatic CoA esters were accepted in the active site of the enzyme as a starter substrate for the complex condensation reaction. The low substrate specificity of CHS thus provided further insight into the structure and function of the enzyme.

Acyltransferases↗