Synthesis of marmycin A and investigation into its cellular activity

Nat Chem. 2015 Sep;7(9):744-51. doi: 10.1038/nchem.2302. Epub 2015 Jul 20.

Abstract

Anthracyclines such as doxorubicin are used extensively in the treatment of cancers. Anthraquinone-related angucyclines also exhibit antiproliferative properties and have been proposed to operate via similar mechanisms, including direct genome targeting. Here, we report the chemical synthesis of marmycin A and the study of its cellular activity. The aromatic core was constructed by means of a one-pot multistep reaction comprising a regioselective Diels-Alder cycloaddition, and the complex sugar backbone was introduced through a copper-catalysed Ullmann cross-coupling, followed by a challenging Friedel-Crafts cyclization. Remarkably, fluorescence microscopy revealed that marmycin A does not target the nucleus but instead accumulates in lysosomes, thereby promoting cell death independently of genome targeting. Furthermore, a synthetic dimer of marmycin A and the lysosome-targeting agent artesunate exhibited a synergistic activity against the invasive MDA-MB-231 cancer cell line. These findings shed light on the elusive pathways through which anthraquinone derivatives act in cells, pointing towards unanticipated biological and therapeutic applications.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anthraquinones / chemical synthesis*
  • Anthraquinones / chemistry
  • Anthraquinones / toxicity
  • Autophagy / drug effects
  • Catalysis
  • Cell Line, Tumor
  • Copper / chemistry
  • Crystallography, X-Ray
  • Cyclization
  • Cycloaddition Reaction
  • Humans
  • Lysosomes / metabolism
  • Microscopy, Fluorescence
  • Microtubule-Associated Proteins / metabolism
  • Molecular Conformation
  • RNA-Binding Proteins / metabolism
  • Stereoisomerism

Substances

  • Anthraquinones
  • MAP1LC3A protein, human
  • Microtubule-Associated Proteins
  • P62 protein, human
  • RNA-Binding Proteins
  • marmycin A
  • Copper

Associated data

  • PubChem-Substance/251973875
  • PubChem-Substance/251973876
  • PubChem-Substance/251973877
  • PubChem-Substance/251973878
  • PubChem-Substance/251973879
  • PubChem-Substance/251973880
  • PubChem-Substance/251973881
  • PubChem-Substance/251973882
  • PubChem-Substance/251973883
  • PubChem-Substance/251973884
  • PubChem-Substance/251973885
  • PubChem-Substance/251973886
  • PubChem-Substance/251973887
  • PubChem-Substance/251973888
  • PubChem-Substance/251973889
  • PubChem-Substance/251973890
  • PubChem-Substance/251973891
  • PubChem-Substance/251973892
  • PubChem-Substance/251973893
  • PubChem-Substance/251973894
  • PubChem-Substance/251973895
  • PubChem-Substance/251973896
  • PubChem-Substance/251973897
  • PubChem-Substance/251973898
  • PubChem-Substance/251973899
  • PubChem-Substance/251973900
  • PubChem-Substance/251973901
  • PubChem-Substance/251973902
  • PubChem-Substance/251973903