Synthesis and determination of the absolute configuration of fugomycin and desoxyfugomycin: CD spectroscopy and fungicidal activity of butenolides

Chemistry : a European Journal
Manfred BraunStefan Grimme

Abstract

The dibromoalkenes (S)-3 and (R)- and (S)-4 are intermediates in the syntheses of the naturally occurring fungicidal butenolides fugomycin (1) and desoxyfugomycin (2), respectively. The stereoselective bromine-lithium exchange that leads to the carbenoid 12 and the vinyllithium reagent 17 a on the one hand, and palladium-catalyzed coupling reactions of the dibromoalkene 3 and the bromolactone 22 on the other are key steps en route to the butenolides 1 and 2. The chiral building blocks (S)-3, (R)-4, and (S)-4 are readily available from (R)-isopropylideneglyceraldehyde 5, isobutyl (R)-lactate 6 a, and ethyl (S)-lactate 6 b, respectively. The synthetic procedure adopted here permits the absolute configuration of the natural products fugomycin (1) and desoxyfugomycin (2) to be assigned by comparison of their chiroptical properties with those of the synthetic products. The CD spectra of the bromolactone 22, calculated by two different density functional methods (TDDFT, DFT/MRCI), are found to be in good agreement with the measured spectra. On the basis of these calculations, the two CD bands observed could be assigned to n-pi* and pi-pi* transitions, respectively. Fugomycin (1) and the synthetic butenolide 20 displayed high fungicid...Continue Reading

Citations

Jul 27, 2010·Analytical and Bioanalytical Chemistry·Carlo BertucciAngela De Simone
Jan 17, 2015·Fitoterapia·Jie-Feng TianXin-Sheng Yao
Sep 6, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Renso VisbalM Concepción Gimeno
Feb 23, 2019·Organic & Biomolecular Chemistry·Mengchen YangShurong Ban
Apr 15, 2010·Chemistry : a European Journal·Yolanda ArroyoJosé Luis García Ruano
Jan 13, 2011·Organic & Biomolecular Chemistry·Jingyu YangYanzhong Li
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Sep 20, 2012·The Journal of Physical Chemistry. a·Wanyi JiangAngela K Wilson
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