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

    Fingerprint

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(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