Asymmetric Alkylation of Anthrones, Enantioselective Total Synthesis of (-)- and (+)-Viridicatumtoxins B and Analogues Thereof: Absolute Configuration and Potent Antibacterial Agents.

@article{Nicolaou2017AsymmetricAO,
  title={Asymmetric Alkylation of Anthrones, Enantioselective Total Synthesis of (-)- and (+)-Viridicatumtoxins B and Analogues Thereof: Absolute Configuration and Potent Antibacterial Agents.},
  author={Kyriacos C. Nicolaou and Guodu Liu and Kathryn Beabout and Megan D. McCurry and Yousif Shamoo},
  journal={Journal of the American Chemical Society},
  year={2017},
  volume={139 10},
  pages={
          3736-3746
        },
  url={https://api.semanticscholar.org/CorpusID:3921174}
}
A phase transfer catalyzed asymmetric alkylation of anthrones with cyclic allylic bromides using quinidine- or quinine-derived catalysts was successfully applied to produce enantioselectively (-)- and (+)-viridicatumtoxins B, and thus allowed assignment of the absolute configuration of this naturally occurring antibiotic.
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31 References

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