Synthetic Studies on the Cladiellins (Eunicellins): Unexpected Selenoxide ­Displacement with Concomitant Alcohol Oxidation During Attempted ­Selenoxide Elimination

Abstract

In the course of studies directed towards the total synthesis of the marine diterpene natural product litophynin E, unexpected nucleophilic displacement of a selenoxide was observed upon ­oxidation of a selenide using MCPBA and heating the resulting ­selenoxide. An unusual fused tricyclic ketone was obtained as a crystalline solid in high yield and its structure was fully elucidated by X-ray crystallography.

target synthesis - cyclization - fused ring systems - oxidation - selenium

References and Notes

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Crystallographic data (excluding structure factors) have been deposited with the Cambridge Crystallographic Data Centre (9: CCDC 601472, 12: CCDC 601473, 14: CCDC 601474, 15: CCDC 601475). Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK [fax: [phone], e-mail: [e-mail]].

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