Thermal and photochemical mechanisms for cyclobutane formation in bielschowskysin biosynthesis

Bencan Tang, Robert Simion, Robert S. Paton

Research output: Journal PublicationArticlepeer-review

10 Citations (Scopus)

Abstract

The unique structure of furanocembranoid natural product bielschowskysin has provoked a number of biosynthetic hypotheses: quantum chemical calculations provide a means to assess the feasibility of postulated mechanisms in the construction of this unusual carbon skeleton. Calculations reveal that thermal closure is possible in water via an unusual concerted cyclobutane-forming transition state without the intervention of an enzyme. Photocycloaddition is computed to be extremely efficient, provided enol ether triplet sensitization can be achieved by an appropriate light source. The possible existence of a stable dicarbonyl intermediate presents a challenge for the thermal route, implicating a photochemical pathway in bielschowskysin biosynthesis.

Original languageEnglish
Article number5597
Pages (from-to)501-507
Number of pages7
JournalSynlett
Volume26
Issue number4
DOIs
Publication statusPublished - Mar 2015

Keywords

  • DFT
  • biosynthesis
  • concerted
  • cyclization
  • transition states

ASJC Scopus subject areas

  • Organic Chemistry

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