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 - 2014

Fingerprint

Anthozoa
Cycloaddition
Cycloaddition Reaction
cycloaddition
biosynthesis
habitats
Sunlight
Biosynthesis
Biosynthetic Pathways
sunlight
Excited states
Artifacts
intersections
atomic energy levels
Ecosystem
Byproducts
artifacts
Irradiation
irradiation
excitation

ASJC Scopus subject areas

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

Cite this

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

Photochemical formation of intricarene. / Stichnoth, Desiree; Kölle, Patrick; Kimbrough, Thomas J.; Riedle, Eberhard; De Vivie-Riedle, Regina; Trauner, Dirk.

In: Nature Communications, Vol. 5, 5597, 2014.

Research output: Contribution to journalArticle

Stichnoth, D, Kölle, P, Kimbrough, TJ, Riedle, E, De Vivie-Riedle, R & Trauner, D 2014, 'Photochemical formation of intricarene', Nature Communications, vol. 5, 5597. https://doi.org/10.1038/ncomms6597
Stichnoth D, Kölle P, Kimbrough TJ, Riedle E, De Vivie-Riedle R, Trauner D. Photochemical formation of intricarene. Nature Communications. 2014;5. 5597. https://doi.org/10.1038/ncomms6597
Stichnoth, Desiree ; Kölle, Patrick ; Kimbrough, Thomas J. ; Riedle, Eberhard ; De Vivie-Riedle, Regina ; Trauner, Dirk. / Photochemical formation of intricarene. In: Nature Communications. 2014 ; Vol. 5.
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