Unravelling Photochemical Relationships among Natural Products from Aplysia dactylomela

Bryan S. Matsuura, Patrick Kölle, Dirk Trauner, Regina De Vivie-Riedle, Robin Meier

Research output: Contribution to journalArticle

Abstract

Aplydactone (1) is a brominated ladderane sesquiterpenoid that was isolated from the sea hare Aplysia dactylomela together with the chamigranes dactylone (2) and 10-epi-dactylone (3). Given the habitat of A. dactylomela, it seems likely that 1 is formed from 2 through a photochemical [2 + 2] cycloaddition. Here, we disclose a concise synthesis of 1, 2, and 3 that was guided by excited state theory and relied on several highly stereoselective transformations. Our experiments and calculations confirm the photochemical origin of 1 and explain why it is formed as the sole isomer. Irradiation of 3 with long wavelength UV light resulted in a [2 + 2] cycloaddition that proceeded with opposite regioselectivity. On the basis of this finding, it seems likely that the resulting regioisomer, termed "8-epi-isoaplydactone", could also be found in A. dactylomela.

Original languageEnglish (US)
Pages (from-to)39-46
Number of pages8
JournalACS Central Science
Volume3
Issue number1
DOIs
StatePublished - Jan 25 2017

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Cycloaddition
Biological Products
Regioselectivity
Excited states
Ultraviolet radiation
Isomers
Irradiation
Wavelength
Experiments

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Matsuura, B. S., Kölle, P., Trauner, D., De Vivie-Riedle, R., & Meier, R. (2017). Unravelling Photochemical Relationships among Natural Products from Aplysia dactylomela. ACS Central Science, 3(1), 39-46. https://doi.org/10.1021/acscentsci.6b00293

Unravelling Photochemical Relationships among Natural Products from Aplysia dactylomela. / Matsuura, Bryan S.; Kölle, Patrick; Trauner, Dirk; De Vivie-Riedle, Regina; Meier, Robin.

In: ACS Central Science, Vol. 3, No. 1, 25.01.2017, p. 39-46.

Research output: Contribution to journalArticle

Matsuura, BS, Kölle, P, Trauner, D, De Vivie-Riedle, R & Meier, R 2017, 'Unravelling Photochemical Relationships among Natural Products from Aplysia dactylomela', ACS Central Science, vol. 3, no. 1, pp. 39-46. https://doi.org/10.1021/acscentsci.6b00293
Matsuura, Bryan S. ; Kölle, Patrick ; Trauner, Dirk ; De Vivie-Riedle, Regina ; Meier, Robin. / Unravelling Photochemical Relationships among Natural Products from Aplysia dactylomela. In: ACS Central Science. 2017 ; Vol. 3, No. 1. pp. 39-46.
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