Abstract
AbstractCaulerpenyne (1), the most abundant of the ecotoxicologically relevant sesquiterpenoids of the Mediterranean‐adapted tropical green seaweed Caulerpa taxifolia, was found to react with Et3N or pyridine in MeOH by initial deprotection of C(1)HO to give oxytoxin 1 (2a), previously isolated from the sacoglossan mollusc Oxynoe olivacea. With BuNH2, without any precaution to exclude light, 1 gave the series of racemic 3 and 4, and achiral (4E,6E)‐5, (4E,6Z)‐5, (4Z,6E)‐5, and (4Z,6Z)‐5 pyrrole compounds, corresponding to formal C(4) substitution, 4,5‐β‐elimination, and (E/Z)‐isomerization at the C(4)C(5) and C(6)C(7) bonds. Changing to CDCl3 as solvent in the dark, 1 gave cleanly, via 2a as an intermediate, 3 and (4E,6E)‐5. The latter proved to be prone to (E/Z)‐photoisomerization. Under standard acetylation conditions, 3 gave (4E,6E)‐5 via acetamide 7 as an intermediate. Particular notice is warranted by selective deprotection of 1 at C(1), mimicking enzyme reactions, and unprecedented formation of pyrrole compounds from freely‐rotating, protected 1,4‐dialdehyde systems.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
