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Synlett 2011(15): 2242-2244  
DOI: 10.1055/s-0030-1261189
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Isotopically Labeled Fusarium Mycotoxin ¹³C2-Moniliformin [1-Hydroxycyclobut-1-ene-3,4-dione]

Lilia Lohreya, Takeshi Muratab, Daisuke Uemurab,c, Hans-Ulrich Humpf*a
a Institut für Lebensmittelchemie, Westfälische Wilhelms-Universität Münster, Corrensstr. 45, 48149 Münster, Germany
Fax: +49(251)8333396; e-Mail: humpf@uni-muenster.de;
b Department of Chemistry, Graduate School of Science, , Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan
c Department of Biosciences and Informatics, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi,Yokohama 223-8655, Japan
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Publication History

Received 13 June 2011
Publication Date:
12 August 2011 (online)

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Abstract

The total synthesis of isotopically labeled [¹³C2]-1-hydroxycyclobut-1-ene-3,4-dione (moniliformin) a fungal toxic secondary metabolite to be used as internal standard for mycotoxin analysis is described. The synthesis proceeds in four steps starting from 1,4-dioxane, which was converted to 2,3-dihydro-1,4-dioxine followed by a [2+2]-cycloaddition with trichloroacetyl chloride-1,2-¹³C2 as ¹³C source. The ¹³C2-labeled cyclobutanone precursor was transformed to [¹³C2]-moniliformin by acid-catalyzed hydrolysis. The successful incorporation of two ¹³C atoms was proven by detailed NMR and mass spectrometric studies of labeled moniliformin and its precursor.

Key words

Fusarium - moniliformin - [2+2] cycloaddition - stable isotope dilution analysis - HPLC-MS/MS

17

Compound 3 never distilled over separately neither at atmospheric nor at reduced pressure. Distillation was only possible as azeotropic mixture after the addition of H2O.

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Purification by continuous liquid-liquid extraction with Et2O did not give moniliformin in sufficiently pure grade (NMR).