Photochemical formation of intricarene

Desiree Stichnoth, Patrick Kölle, Thomas J. Kimbrough, Eberhard Riedle, Regina De Vivie-Riedle, Dirk Trauner

Research output: Contribution to journalArticle

Abstract

Sunlight is the ultimate driver of biosynthesis but photochemical steps late in biosynthetic pathways are very rare. They appear to play a role in the formation of certain furanocembranoids isolated from Caribbean corals. One of these compounds, intricarene, has been suspected to arise from an intramolecular 1,3-dipolar cycloaddition involving an oxidopyrylium. Here we show, by a combination of experiments and theory, that the oxidopyrylium forms under photochemical conditions and that its cycloaddition occurs via a triplet state. The formation of a complex by-product can be rationalized by another photochemical step that involves a conical intersection. Our work raises the question whether intricarene is biosynthesized in the natural habitat of the corals or is an artefact formed during workup. It also demonstrates that the determination of exact irradiation spectra, in combination with quantum chemical calculations, enables the rationalization of complex reaction pathways that involve multiple excited states.

Original languageEnglish (US)
Article number5597
JournalNature communications
Volume5
DOIs
StatePublished - Dec 2014

ASJC Scopus subject areas

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

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    Stichnoth, D., Kölle, P., Kimbrough, T. J., Riedle, E., De Vivie-Riedle, R., & Trauner, D. (2014). Photochemical formation of intricarene. Nature communications, 5, [5597]. https://doi.org/10.1038/ncomms6597