Bioinspired Synthesis of (−)-PF-1018

Hugo Quintela-Varela, Cooper S. Jamieson, Qianzhen Shao, K. N. Houk, Dirk Trauner

Research output: Contribution to journalArticle

Abstract

The combination of electrocyclizations and cycloadditions accounts for the formation of a range of fascinating natural products. Cascades consisting of 8π electrocyclizations followed by a 6π electrocyclization and a cycloaddition are relatively common. We now report the synthesis of the tetramic acid PF-1018 through an 8π electrocyclization, the product of which is immediately intercepted by a Diels–Alder cycloaddition. The success of this pericyclic cascade was critically dependent on the substitution pattern of the starting polyene and could be rationalized through DFT calculations. The completion of the synthesis required the instalment of a trisubstituted double bond by radical deoxygenation. An unexpected side product formed through 4-exo-trig radical cyclization could be recycled through an unprecedented triflation/fragmentation.

Original languageEnglish (US)
Pages (from-to)5263-5267
Number of pages5
JournalAngewandte Chemie - International Edition
Volume59
Issue number13
DOIs
StatePublished - Mar 23 2020

Keywords

  • Diels–Alder cycloaddition
  • biomimetic synthesis
  • electrocyclization
  • tetramic acids
  • total synthesis

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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  • Cite this

    Quintela-Varela, H., Jamieson, C. S., Shao, Q., Houk, K. N., & Trauner, D. (2020). Bioinspired Synthesis of (−)-PF-1018. Angewandte Chemie - International Edition, 59(13), 5263-5267. https://doi.org/10.1002/anie.201912452