NMR strategy for unraveling structures of bioactive sponge-derived oxy-polyhalogenated diphenyl ethers

J Nat Prod. 2009 Mar 27;72(3):443-9. doi: 10.1021/np800737z.

Abstract

The overexpression of the Mcl-1 protein in cancerous cells results in the sequestering of Bak, a key component in the regulation of normal cell apoptosis. Our investigation of the ability of marine-derived small-molecule natural products to inhibit this protein-protein interaction led to the isolation of several bioactive oxy-polyhalogenated diphenyl ethers. A semipure extract, previously obtained from Dysidea (Lamellodysidea) herbacea and preserved in our repository, along with an untouched Dysidea granulosa marine sponge afforded 13 distinct oxy-polyhalogenated diphenyl ethers. Among these isolates were four new compounds, 5, 6, 10, and 12. The structure elucidation of these molecules was complicated by the plethora of structural variants that exist in the literature. During dereplication, we established a systematic method for analyzing this class of compounds. The strategy is governed by trends in the (1)H and (13)C NMR shifts of the aromatic rings, and the success of the strategy was checked by X-ray crystal structure analysis.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Animals
  • Antineoplastic Agents* / chemistry
  • Antineoplastic Agents* / isolation & purification
  • Antineoplastic Agents* / pharmacology
  • Apoptosis / drug effects
  • Crystallography, X-Ray
  • Drug Screening Assays, Antitumor
  • Dysidea / chemistry*
  • Halogenated Diphenyl Ethers* / chemistry
  • Halogenated Diphenyl Ethers* / isolation & purification
  • Halogenated Diphenyl Ethers* / pharmacology
  • Molecular Conformation
  • Molecular Structure
  • Myeloid Cell Leukemia Sequence 1 Protein
  • Nuclear Magnetic Resonance, Biomolecular
  • Proto-Oncogene Proteins c-bcl-2 / drug effects
  • Proto-Oncogene Proteins c-bcl-2 / metabolism*

Substances

  • Antineoplastic Agents
  • Halogenated Diphenyl Ethers
  • Myeloid Cell Leukemia Sequence 1 Protein
  • Proto-Oncogene Proteins c-bcl-2