Brocaeloids A-C, 4-oxoquinoline and indole alkaloids with C-2 reversed prenylation from the mangrove-derived endophytic fungus Penicillium brocae

Peng Zhang, Ling Hong Meng, Attila Mándi, Tibor Kurtán, Xiao Ming Li, Yang Liu, Xin Li, Chun Shun Li, Bin Gui Wang

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

Three new alkaloids, brocaeloids A-C (1-3), containing C-2 reversed prenylation, were isolated from cultures of Penicillium brocae MA-192, an endophytic fungus obtained from the fresh leaves of the marine mangrove plant Avicennia marina. Their structures were determined on the basis of 1D and 2D NMR spectroscopy as well as by high-resolution mass spectrometry. The absolute configuration of brocaeloid A (1) was established by gas-phase and solution conformational analysis and TDDFT-ECD calculations, which revealed that the fused hetero-ring adopted M-helicity conformation with axial orientation of the C-2 and C-3 substituents. The correct assignment of the hetero-ring conformation was found to be crucial in determining the relative and absolute configuration. Based on ECD calculations, the helicity of the 2,3-dihydroquinoline-4(1H)-one chromophore was correlated with the characteristic ECD transitions, and the resultant helicity rule was found to coincide with that of the chroman-4-one chromophore. X-ray single-crystal analysis of 1 by Cu-Kα radiation also confirmed the result of the stereochemical analysis obtained from ECD calculations. Brocaeloid B (2) showed lethality against brine shrimp (Artemia salina) with an LD50 value of 36.7 μM. Brocaeloids A-C (1-3), having reversed prenylation in their structures, were isolated from the mangrove-derived endophytic fungus Penicillium brocae, and their structures were determined by NMR and HRMS analysis. The absolute configuration of 1 was established, and the results revealed the importance of the conformation of the hetero-ring in determining the relative and absolute configuration.

Original languageEnglish
Pages (from-to)4029-4036
Number of pages8
JournalEuropean Journal of Organic Chemistry
Volume2014
Issue number19
DOIs
Publication statusPublished - Jul 2014

Keywords

  • Alkaloids
  • Circular dichroism
  • Density functional calculations
  • Natural products

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

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