Four new diketopiperazines including spirobrocazines A-C (1-3) and brocazine G (4) were characterized from the mangrove-derived Penicillium brocae MA-231. Compounds 1 and 2 had a 6/5/6/5/6 cyclic system with a rare spirocyclic center at C-2. Their structures and absolute configurations were determined by spectroscopic analysis, TDDFT-ECD calculations, and X-ray diffraction. Compound 4 exhibited potent cytotoxicity against both sensitive and cisplatin-resistant human ovarian cancer cells and strong antimicrobial activity against pathogenic Staphylococcus aureus.

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.

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