Unravelling Photochemical Relationships Among Natural Products from Aplysia dactylomela
| Autor: | Regina de Vivie-Riedle, Dirk Trauner, Patrick Kölle, Robin Meier, Bryan S. Matsuura |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
biology
010405 organic chemistry Stereochemistry Chemistry General Chemical Engineering Regioselectivity General Chemistry 010402 general chemistry Photochemistry Aplysia dactylomela biology.organism_classification 01 natural sciences Cycloaddition 0104 chemical sciences lcsh:Chemistry Long wavelength lcsh:QD1-999 Structural isomer Ladderane Research Article |
| Zdroj: | ACS Central Science ACS Central Science, Vol 3, Iss 1, Pp 39-46 (2016) |
| ISSN: | 2374-7951 2374-7943 |
| DOI: | 10.1021/acscentsci.6b00293 |
| Popis: | 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. We report the photochemistry, supported by excited state theory, of the brominated chamigranes dactylone and 10-epi-dactylone in the biomimetic synthesis of aplydactone and its isomer, which we anticipate is a natural product. |
| Databáze: | OpenAIRE |
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