Isolation and structure determination of TMC-151s: Novel polyketide antibiotics from Gliocladium catenulatum Gilman &amp; Abbott TC 1280

Kohno, Jun; Nishio, Maki; Sakurai, Masaaki; Kawano, Kimio; Hiramatsu, Hidenori; Kameda, Noriaki; Kishi, Noboru; Yamashita, Toyoharu; Okuda, Tôru; Komatsubara, Saburo

doi:10.1016/s0040-4020(99)00408-1

Cited by 50 publications

(55 citation statements)

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“…The majority of natural products in this subfamily contain a single deoxypropionate stereotriad. Natural products that contain multiple deoxypropionate units are comparatively fewer and are generally characterized by an all-syn orientation of methyl groups on an acyclic framework, as in the structures of lardolure (7), siphonarienal (6), siphonarienolone (8), pectinatone (9,10), TMC-151 (11), and branched alkanoic acids isolated from the preen-gland wax of the domestic goose (12). A major cuticular hydrocarbon from a cane beetle species was reported recently to have an unprecedented three sets of anti-disposed deoxypropionates (13).…”

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confidence: 99%

Total synthesis of the cytotoxic cyclodepsipeptide (-)-doliculide: The “ester” effect in acyclic 1,3-induction of deoxypropionates

Hanessian

Mascitti

Giroux

2004

Proc. Natl. Acad. Sci. U.S.A.

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The total synthesis of the marine cyclodepsipeptide (؊)-doliculide is described. An acyclic (2S,4S,6R)-trimethyl alkanoic acid precursor to the ''hydrocarbon'' portion of doliculide was synthesized starting with L-ascorbic acid based on a stereocontrolled iterative conjugate addition of lithium dimethylcuprate to acyclic ␦-Cmethyl ␣,␤-unsaturated ester derivatives. syn͞syn selectivity was achieved by relying on 1,3-induction in preferred folded conformations that avoid 1,5-syn-pentane interactions in the transition states. The nature of the ester moiety seems to play an important role in determining the syn͞anti ratios of C-methyl adducts. The 1-methyl-1-cyclopentyl ester group was found to confer the best syn selectivity to the cuprate addition products, especially in seven-carbon enoates.

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confidence: 99%

Total synthesis of the cytotoxic cyclodepsipeptide (-)-doliculide: The “ester” effect in acyclic 1,3-induction of deoxypropionates

Hanessian

Mascitti

Giroux

2004

Proc. Natl. Acad. Sci. U.S.A.

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“…The geometry of both of the disubstituted double bonds was assigned as E based on J H8-H9 and J H12-H13 values of 15 Hz. Upfield chemical shifts for olefinic methyl carbons 4-CH 3 (d 11.1) and 16-CH 3 (d 13.1) allowed assignment of the E-geometry of both trisubstituted double bonds [7]. The relative configurations of the stereocenters in the ring were proposed by analysis of relevant vicinal coupling constants and NOESY correlations.…”

Section: Resultsmentioning

confidence: 99%

“…A similar conclusion was derived for the C14ϳC15 stereocenters based on a similar coupling constant between H-14 and H-15 (8.8 Hz) and analogous NOESY correlations between 14-CH 3 and 16-CH 3 . However, the corresponding 3 J-values at other, structurally similar sites in the molecule were considered less definitive (e.g., 7 Hz values for J H6-H7 and J H10-H11 ), so relative configurations at these positions were not proposed.…”

Section: Resultsmentioning

confidence: 99%

“…The trisubstituted double bond was also assigned the E-geometry on the basis of the carbon chemical shift for the 16-CH 3 (d 13.1) [7]. The relative stereochemistry of the ring in 2, and the stereocenters at C2ϳC3 and C14ϳC15 was presumed to be the same as that in 1 on the basis of close similarities in the NMR data.…”

Section: Resultsmentioning

confidence: 99%

“…Most of the compounds of this class have either pentitol or hexitol units incorporated into their structures via ester linkages at one of the termini, and cyclic sugars that form ether bonds with one of the open-chain hydroxy groups. Representative examples include roselipins [10], TMC-151 AϳF [7], and cladionol A [6]. Cameronic acid, cubensic acid, berteric acid, and malaysic acid, isolated from Xylaria spp.…”

Section: Resultsmentioning

confidence: 99%

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Sporminarins A and B: Antifungal Metabolites from a Fungicolous Isolate of Sporormiella minimoides

2006

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Cultures of a fungicolous isolate of Sporormiella minimoides afforded two new polyketide metabolites which we have named sporminarins A (1) and B (2). The planar structures of 1 and 2 were elucidated by analysis of NMR and MS data, and by chemical methods. 1 exhibited significant antifungal activity against Aspergillus flavus. Keywords sporminarins, antifungal, Sporormiella minimoides IntroductionOur ongoing studies of mycoparasitic and fungicolous fungi have shown them to be excellent sources of new biologically active natural products [1ϳ4]. In the course of this ongoing project, we examined cultures of a fungicolous isolate of Sporormiella minimoides Ahmed & Cain (Sporormiaceae; NRRL 37629) that was obtained from a basidioma of Trametes hirsutum collected from a dead hardwood branch in a subalpine dry forest in Hawaii. The ethyl acetate extract obtained from solid-state fermentation cultures of S. minimoides exhibited antifungal activity against Aspergillus flavus. The extract was fractionated using silica gel column chromatography, and the resulting fractions were subjected to reversed-phase HPLC to yield two new metabolites, which we have named sporminarins A (1) and B (2). The known compound brocaenol A was also obtained, and was identified by comparison of NMR and MS data with literature values [5]. Details of the isolation, structure elucidation, and bioactivities of 1 and 2 are presented here. Results and DiscussionSporminarin A (1) was assigned a molecular formula of C 36 H 62 O 8 (six degrees of unsaturation) on the basis of NMR (Table 1) and HRESIMS data. 1 H NMR analysis of 1 in CDCl 3 gave poor spectra, with considerable overlap and broad signals, but spectra recorded in CD 3 OD were of much better quality. 1 H, 13 C NMR, and DEPT data for 1 revealed the presence of six olefinic protons, five oxymethines, six non-oxygenated methines, three nonoxygenated methylenes, and 11 methyl groups. These units accounted for 56 protons, indicating that the remaining six protons must be exchangeable. The methyl group 1 H NMR signals consisted of two olefinic methyl resonances lacking vicinal coupling, two aliphatic methyl singlets, six CH 3 -CH doublets, and one CH 3 -CH 2 triplet. The 13 C NMR spectrum of 1 revealed 35 discrete signals, one short of the expected count, suggesting that two of the signals were coincident. Only seven signals were distinguishable in the olefinic region of the 13 C NMR spectrum of 1, and the DEPT spectrum contained six of those signals, indicating that the overlapped signal must correspond to one of two nonprotonated olefinic carbons. also revealed the presence of two oxygenated quaternary sp 3 carbons, and an oxycarbonyl carbon (d C 179.9) that was presumed to be a carboxylic acid group, although chemical shift alone could not definitively rule out an ester unit [6]. Treatment of 1 with trimethylsilyldiazomethane yielded the corresponding methyl ester (COOCH 3 methyl signal at d H 3.69), thereby confirming the presence of the carboxylic acid group. Of the six degrees of uns...

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The Aldol Condensation

Sierra

Torre²,

Cossío

2013

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Isolation and structure determination of TMC-151s: Novel polyketide antibiotics from Gliocladium catenulatum Gilman & Abbott TC 1280

Cited by 50 publications

References 14 publications

Total synthesis of the cytotoxic cyclodepsipeptide (-)-doliculide: The “ester” effect in acyclic 1,3-induction of deoxypropionates

Total synthesis of the cytotoxic cyclodepsipeptide (-)-doliculide: The “ester” effect in acyclic 1,3-induction of deoxypropionates

Sporminarins A and B: Antifungal Metabolites from a Fungicolous Isolate of Sporormiella minimoides

The Aldol Condensation

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