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Matsuura, Bryan S.; Kölle, Patrick; Trauner, Dirk; Vivie-Riedle, Regina de; Meier, Robin (2017): Unravelling Photochemical Relationships Among Natural Products from Aplysia dactylomela. In: ACS Central Science, Vol. 3, No. 1: pp. 39-46
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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.