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    1978, SETO - Coarctatin

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    Mayra Fonseca
    This document reports on a study investigating the biosynthetic pathway of the fungal metabolite coarctatin through 13C NMR spectroscopy. The key findings are: 1) 13C NMR analysis including chemical shifts, coupling patterns, and selective decoupling experiments were used to assign all 11 carbon signals of coarctatin. 2) Incorporation of 13C-labeled precursors such as sodium acetate, sodium propionate, and sodium bicarbonate showed that coarctatin is biosynthesized from four acetate units and three chloride ions, supporting the proposed biosynthetic pathway. 3) This confirms that coarctatin shares a similar biosynthetic pathway with other fungal metabolites formed from

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    1978, SETO - Coarctatin

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    Mayra Fonseca
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    This document reports on a study investigating the biosynthetic pathway of the fungal metabolite coarctatin through 13C NMR spectroscopy. The key findings are: 1) 13C NMR analysis including chemical shifts, coupling patterns, and selective decoupling experiments were used to assign all 11 carbon signals of coarctatin. 2) Incorporation of 13C-labeled precursors such as sodium acetate, sodium propionate, and sodium bicarbonate showed that coarctatin is biosynthesized from four acetate units and three chloride ions, supporting the proposed biosynthetic pathway. 3) This confirms that coarctatin shares a similar biosynthetic pathway with other fungal metabolites formed from

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    This document reports on a study investigating the biosynthetic pathway of the fungal metabolite coarctatin through 13C NMR spectroscopy. The key findings are: 1) 13C NMR analysis including chemical shifts, coupling patterns, and selective decoupling experiments were used to assign all 11 carbon signals of coarctatin. 2) Incorporation of 13C-labeled precursors such as sodium acetate, sodium propionate, and sodium bicarbonate showed that coarctatin is biosynthesized from four acetate units and three chloride ions, supporting the proposed biosynthetic pathway. 3) This confirms that coarctatin shares a similar biosynthetic pathway with other fungal metabolites formed from

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    4 views3 pages

    1978, SETO - Coarctatin

    Uploaded by

    Mayra Fonseca
    This document reports on a study investigating the biosynthetic pathway of the fungal metabolite coarctatin through 13C NMR spectroscopy. The key findings are: 1) 13C NMR analysis including chemical shifts, coupling patterns, and selective decoupling experiments were used to assign all 11 carbon signals of coarctatin. 2) Incorporation of 13C-labeled precursors such as sodium acetate, sodium propionate, and sodium bicarbonate showed that coarctatin is biosynthesized from four acetate units and three chloride ions, supporting the proposed biosynthetic pathway. 3) This confirms that coarctatin shares a similar biosynthetic pathway with other fungal metabolites formed from

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    of 3

    926 THE JOURNAL OF ANTIBIOTICS SEPT.

    1978

    Communications to the editor

    UTILIZATION OF 13C-13C COUPLING IN spectrum, chemical shifts and selective proton


    STRUCTURAL AND BIOSYNTHETIC decoupling experiments. In view of the difference
    STUDIES. XI.' BIOSYNTHETIC of solvents used*, the result is in agreement with
    STUDIES OF COARCTATIN that reported by TURNER et al.21 However, the
    assignments of the remaining quaternary sp2
    Sir: carbons were not so straightforward. Of these,
    Coarctatin (1)2) is a metabolite of the fungus four at 169.9, 164.3, 163.5 and 162.6 ppm**
    Chaetonrum coarctatum. Notwithstanding its were assigned to sp2 carbons bearing oxygen and
    structural similarity to radicinin, which is formed therefore, the rest two at 99.2 and 119.8 ppm were
    by the condensation of only acetic acid mole- due to those unsubstituted by oxygen.
    cules," a somewhat different biosynthetic path- In the a-pyron system with oxygen substi-
    way (four acetic units plus two Cl units) for the tuents at /3- and s-positions, carbonyl carbons
    main framework of I has been proposed by and the oxygenated ones absorb at the same
    TURNER et al.2' However, another pathway region in the 13C-nmr spectra.',', Therefore,
    involving, for example, the incorporation of the differentiation of these carbons from each
    propionic acid molecules into C'-9, 6 and 5, and other was made by long range selective proton
    C-10, 4 and 3, may operate in the formation of 1. decoupling (LSPD) experiments" and by use of
    "C -"C coupling patterns observed in I labeled
    A recent report on the incorporation of pro-
    pionic acid into a fungal metabolite aurovertin" with "CH313COONa.
    prompted us to investigate the biosynthesis of Irradiation at H-2(d 5.95) collapsed a signal
    I by 13C-nmr spectroscopy. at 164.3 ppm to a sharp singlet which appeared
    The required 13C assignments for I was made as a broad peak in the proton coupled spectrum.
    as follows and the chemical shifts are listed in Likewise, the unresolved resonance at 169.9 ppm
    Table 1. The assignments of protonated reso- was perturbed by the irradiation at CHaO (1S„
    nances due to C-2, 7, 8 and 9 were obtained easily 4.10). Thus, these signals were assigned to C-1
    based on splitting patterns in the off-resonance and C-3, respectively. Saturation of H-9 (S„
    5.25) led to an inconclusive result, since it elimi-
    nated long range couplings from both the signals
    Table L °'C-Nmr chemical shifts and coupling at 162.6 and 163.5 ppm. In the 13C-nmr spectrum
    constants of coarctatin.
    of 13CH.313000Na enriched 1, (Fig. 1) two pairs
    Carbon Jc(ppm)h) Je-c(Hz)

    8q') 14.6 42
    II q 57.6
    9t 64.9
    2d 89.3 80
    4s 99.2 67
    6s 119.8 63
    Coorctatin (I) Radicinin
    7d 138.7 42
    lOs 162.6
    5s 163.5 64
    * In the structural studies on I , a mixed solvent
    Is 164.3 81
    (CDCI• supplemented with CF3CO2H) was used for
    3s 169.9 67
    the measurements of 13C-nmr spectra.21 In our ex-
    Determined on a JEOL FX-100 spectrometer at periments, however, CF3CO_H was replaced by
    25.05 MHz spectral width; 5 KHz, pulse angle; CC13CO2H (CCI3C02H - CDCI3, 1 : 1) to eliminate
    - 70', data points; 16 K. strong quartet peaks due to CF3C02H.
    ** 13C-Nmr spectra were obtained as reported
    multiplicity of off-resonance decoupling.
    s; singlet, d; doublet, t; triplet, q; quartet. previously') and the chemical shifts are expressed in
    ppm downfield from internal TMS. ppm from internal TMS.
    VOL. XXXI NO. 9 THE JOURNAL OF ANTIBIOTICS 927

    Fig. 1. Proton noise-decoupled 13C-nmr spectrum of 13CH313C02H enriched coarctatin (I).


    Two strong signals at 88.6 and 166.6 ppm are due to CC13C02H.

    of 13C-13C couplings were observed between Fig. 2. Biosynthetic pathway of coarctatin (I).
    quaternary sp2 carbons. Among these, a peak
    at 99.2 ppm coupling to C-3 (169.9 ppm) with
    J,•_,•= 67 Hz was unambiguously assigned to C-4.
    The remaining pair of resonances at 163.5 and
    99.2 ppm was therefore due to C-6 and 5. C-10
    was assigned to a peak at 162.6 ppm by elimina-
    tion to give the total 11C assignments of I.
    13C-Labeled samples of I were prepared by
    separate additions of each ca. 90% enriched Thus, it has been proved that coarctatin is
    CHs13COONa, '3CH3000Na, 13CH3I3COONa biosynthesized from four acetates and three
    (diluted three fold with unlabeled sodium acetate) CI-units (Fig. 2) in the same manner as most
    and H13COONa at the level of 15 mg/50 ml fungal metabolites.
    fermentation broth on 10, 11 and 12 days after
    HARUO SETO
    inoculation. At the end of the fermentation,
    13C-enriched I was isolated as reported pre- MARIKO SHIBAMIYA
    HIROSHI YONEHARA
    viously.,)
    In the 13C-nmr spectrum of the CH313COONa Institute of Applied Microbiology
    enriched I, the signal intensities of C-1, 3, 5 and 7 The University of Tokyo
    were increased by 8 times, whereas the resonances Bunkyo-ku, Tokyo, Japan
    due to C-2, 4, 6 and 8 were enriched in the 13C- (Received May 12, 1978)
    nmr spectrum of I labeled with 13CH3COONa.
    The label of HIVCOONa was also efficiently References
    incorporated into C-9, C-10, and C-11. Several
    1) For Part X see, SETO, H.; Y. MIYAZAKI, K.
    attempts to label I with CD3CD2000Na
    FUJITA & N. OTAKE: Studies on the iono-
    (checked by mass spectrometry), however, were phorous antibiotics. X. The assignments of
    unsuccessful. In the 13C-nmr spectrum of I label- 13C-nmr spectrum of salinomycin . Tetrahed.
    ed with 11CH3113COONa,two pairs of 13C-13C Lett. 1977: 2417-2420, 1977
    couplings, C-1,2 (J= 81 Hz), and C-7,8 (J=42 Hz) 2) BURROW, B. F.; W. B. TURNER & E. R. H.
    were observed in addition to those explained WALKER: 8-Ethylidene-7,8-dihydro-4-methoxy-
    previously. pyrano[4,3-b]pyran-2,5-dione (coarctatin), a
    928 THE JOURNAL OF ANTIBIOTICS SEPT. 1978

    metabolite of Chaetomium coarctatum. J. Chem. cultural Chemical Society of Japan, p. 153,


    Soc. Perkin 1. 1975: 999 - 1000, 1975 Yokohama, 1977
    3) SETO,H. & S. URANO: Revised assignment of 5) TORT, K.: Carbon-13 nmr spectral studies of
    the 13C-nmr spectrum of radicinin. Agr. Biol. aloenin and its derivatives. Carbon-13 signal
    Chem. 39: 915-916, 1975 assignment problem of 4-methoxy-2-pyrons.
    TANABE,M.; H. SETO& L. F. JOHNSON: Bio- Tetrahed. Lett. 1976: 1311 - 1314, 1976
    synthetic studies with carbon-13. Carbon-13 6) TAKEUCHI, S.; J. UZAWA, H. SETO & H. YONE-
    nuclear magnetic resonance spectra of radicinin. HARA: New 13C-nmr techniques applied to
    J. Am. Chem. Soc. 92: 2157-2158, 1970 pentalenolactone structure. Tetrahed. Lett.
    4) URAMOTO,M.; L. W. CARY & M. TANABE: 1977: 2943-2946, 1977
    Abstract of the Annual Meeting of The Agri-

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