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Peniciadametizine A, a Dithiodiketopiperazine with a Unique Spiro[furan-2,7'-pyrazino[1,2-b][1,2]oxazine] Skeleton, and a Related Analogue, Peniciadametizine B, from the Marine Sponge-Derived Fungus Penicillium adametzioides.

Liu Y, Mándi A, Li XM, Meng LH, Kurtán T, Wang BG - Mar Drugs (2015)

Bottom Line: Peniciadametizine A (1); a new dithiodiketopiperazine derivative possessing a unique spiro[furan-2,7'-pyrazino[1,2-b][1,2]oxazine] skeleton, together with a highly oxygenated new analogue, peniciadametizine B (2); as well as two known compounds, brasiliamide A (3); and viridicatumtoxin (4), were isolated and identified from Penicillium adametzioides AS-53, a fungus obtained from an unidentified marine sponge.The spiro[furan-2,7'-pyrazino[1,2-b][1,2]oxazine] skeleton of 1 has not been reported yet among natural products and the biosynthetic pathway for 1 and 2 was discussed.Compounds 1 and 2 showed inhibitory activity against the pathogenic fungus Alternaria brassicae.

View Article: PubMed Central - PubMed

Affiliation: Key Laboratory of Experimental Marine Biology, Institute of Oceanology, Chinese Academy of Sciences, Nanhai Road 7, Qingdao 266071, China. buckuper@163.com.

ABSTRACT
Peniciadametizine A (1); a new dithiodiketopiperazine derivative possessing a unique spiro[furan-2,7'-pyrazino[1,2-b][1,2]oxazine] skeleton, together with a highly oxygenated new analogue, peniciadametizine B (2); as well as two known compounds, brasiliamide A (3); and viridicatumtoxin (4), were isolated and identified from Penicillium adametzioides AS-53, a fungus obtained from an unidentified marine sponge. The unambiguous assignment of the relative and absolute configuration for the spiro center C-2 of compound 1 was solved by the combination of NMR and ECD measurements with Density-Functional Theory (DFT) conformational analysis and Time-Dependent Density-Functional Theory-Electronic Circular Dichroism (TDDFT-ECD) calculations. The spiro[furan-2,7'-pyrazino[1,2-b][1,2]oxazine] skeleton of 1 has not been reported yet among natural products and the biosynthetic pathway for 1 and 2 was discussed. Compounds 1 and 2 showed inhibitory activity against the pathogenic fungus Alternaria brassicae.

No MeSH data available.


Experimental ECD (black) spectrum of 1 compared with BH & HLYP/TZVP ECD spectra (blue) of (2R,4R,10R,11R,12R)-1 computed for the B97D/TZVP conformers (PCM/MeCN). Bars represent the computed rotational strengths of the lowest-energy conformer.
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marinedrugs-13-03640-f005: Experimental ECD (black) spectrum of 1 compared with BH & HLYP/TZVP ECD spectra (blue) of (2R,4R,10R,11R,12R)-1 computed for the B97D/TZVP conformers (PCM/MeCN). Bars represent the computed rotational strengths of the lowest-energy conformer.

Mentions: In order to determine the absolute configuration of 1, Time-Dependent Density Functional Theory-Electronic Circular Dichroism (TDDFT-ECD) calculations were carried out on the B97D/TZVP conformers of (2R,4R,10R,11R,12R)-1 with functionals (B3LYP, BH & HLYP, PBE0) and TZVP basis set (Figure 4). The ECD spectrum of 1 showed a broad negative transition (CE) at 269 nm and positive Cotton effects (CEs) at 237, 226, and 205 nm. The computed TDDFT-ECD spectra of (2R,4R,10R,11R,12R)-1 reproduced well the experimental curve with the BH & HLYP/TZVP method giving the best agreement (Figure 5), which allowed determining the absolute configuration as (−)-(2R,4R,10R,11R,12R) for 1.


Peniciadametizine A, a Dithiodiketopiperazine with a Unique Spiro[furan-2,7'-pyrazino[1,2-b][1,2]oxazine] Skeleton, and a Related Analogue, Peniciadametizine B, from the Marine Sponge-Derived Fungus Penicillium adametzioides.

Liu Y, Mándi A, Li XM, Meng LH, Kurtán T, Wang BG - Mar Drugs (2015)

Experimental ECD (black) spectrum of 1 compared with BH & HLYP/TZVP ECD spectra (blue) of (2R,4R,10R,11R,12R)-1 computed for the B97D/TZVP conformers (PCM/MeCN). Bars represent the computed rotational strengths of the lowest-energy conformer.
© Copyright Policy
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4483649&req=5

marinedrugs-13-03640-f005: Experimental ECD (black) spectrum of 1 compared with BH & HLYP/TZVP ECD spectra (blue) of (2R,4R,10R,11R,12R)-1 computed for the B97D/TZVP conformers (PCM/MeCN). Bars represent the computed rotational strengths of the lowest-energy conformer.
Mentions: In order to determine the absolute configuration of 1, Time-Dependent Density Functional Theory-Electronic Circular Dichroism (TDDFT-ECD) calculations were carried out on the B97D/TZVP conformers of (2R,4R,10R,11R,12R)-1 with functionals (B3LYP, BH & HLYP, PBE0) and TZVP basis set (Figure 4). The ECD spectrum of 1 showed a broad negative transition (CE) at 269 nm and positive Cotton effects (CEs) at 237, 226, and 205 nm. The computed TDDFT-ECD spectra of (2R,4R,10R,11R,12R)-1 reproduced well the experimental curve with the BH & HLYP/TZVP method giving the best agreement (Figure 5), which allowed determining the absolute configuration as (−)-(2R,4R,10R,11R,12R) for 1.

Bottom Line: Peniciadametizine A (1); a new dithiodiketopiperazine derivative possessing a unique spiro[furan-2,7'-pyrazino[1,2-b][1,2]oxazine] skeleton, together with a highly oxygenated new analogue, peniciadametizine B (2); as well as two known compounds, brasiliamide A (3); and viridicatumtoxin (4), were isolated and identified from Penicillium adametzioides AS-53, a fungus obtained from an unidentified marine sponge.The spiro[furan-2,7'-pyrazino[1,2-b][1,2]oxazine] skeleton of 1 has not been reported yet among natural products and the biosynthetic pathway for 1 and 2 was discussed.Compounds 1 and 2 showed inhibitory activity against the pathogenic fungus Alternaria brassicae.

View Article: PubMed Central - PubMed

Affiliation: Key Laboratory of Experimental Marine Biology, Institute of Oceanology, Chinese Academy of Sciences, Nanhai Road 7, Qingdao 266071, China. buckuper@163.com.

ABSTRACT
Peniciadametizine A (1); a new dithiodiketopiperazine derivative possessing a unique spiro[furan-2,7'-pyrazino[1,2-b][1,2]oxazine] skeleton, together with a highly oxygenated new analogue, peniciadametizine B (2); as well as two known compounds, brasiliamide A (3); and viridicatumtoxin (4), were isolated and identified from Penicillium adametzioides AS-53, a fungus obtained from an unidentified marine sponge. The unambiguous assignment of the relative and absolute configuration for the spiro center C-2 of compound 1 was solved by the combination of NMR and ECD measurements with Density-Functional Theory (DFT) conformational analysis and Time-Dependent Density-Functional Theory-Electronic Circular Dichroism (TDDFT-ECD) calculations. The spiro[furan-2,7'-pyrazino[1,2-b][1,2]oxazine] skeleton of 1 has not been reported yet among natural products and the biosynthetic pathway for 1 and 2 was discussed. Compounds 1 and 2 showed inhibitory activity against the pathogenic fungus Alternaria brassicae.

No MeSH data available.