Two new metabolites, (4S)-(+)-ascochin (1a) and (S,S)-(+)-ascodiketone (3), together with the known compounds (3R,4R)-(–)-4-hydroxymellein (2), ent-α-cyperone (4) and (3S,4R)-(–)-dihydroxy-(6S)-undecyl-α-pyranone (5) were isolated from cultures of the of the endophytic fungus Ascochyta sp. The biologically active isocoumarin derivative, (4S)-(+)-ascochin (1a), has an unusual substitution pattern which was confirmed by X-ray diffraction. Its absolute configuration was determined by our solid-state TDDFT CD methodology using the X-ray coordinates as input for the calculation. By catalytic hydrogenation, (4S)-(+)-ascochin was converted into the corresponding (3S,4S)-dihydroisocoumarin derivative 1b. The measured and TDDFT calculated CD spectra enabled studies on the correlation between absolute configuration and n-π* transition Cotton effect.

Bioactive Natural Products from the Endophytic Fungus Ascochyta sp. From Meliotus dentatus – Configurational Assignment by Solid-State CD and TDDFT Calculations

PESCITELLI, GENNARO;
2007-01-01

Abstract

Two new metabolites, (4S)-(+)-ascochin (1a) and (S,S)-(+)-ascodiketone (3), together with the known compounds (3R,4R)-(–)-4-hydroxymellein (2), ent-α-cyperone (4) and (3S,4R)-(–)-dihydroxy-(6S)-undecyl-α-pyranone (5) were isolated from cultures of the of the endophytic fungus Ascochyta sp. The biologically active isocoumarin derivative, (4S)-(+)-ascochin (1a), has an unusual substitution pattern which was confirmed by X-ray diffraction. Its absolute configuration was determined by our solid-state TDDFT CD methodology using the X-ray coordinates as input for the calculation. By catalytic hydrogenation, (4S)-(+)-ascochin was converted into the corresponding (3S,4S)-dihydroisocoumarin derivative 1b. The measured and TDDFT calculated CD spectra enabled studies on the correlation between absolute configuration and n-π* transition Cotton effect.
2007
Krohn, K; Kock, I; Elssser, B; Floerke, U; Schulz, B; Draeger, S; Pescitelli, Gennaro; Antus, S; Kurtan, T.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11568/116913
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