First total synthesis of concavine.

ABSTRACT

The synthesis of the unusual alkaloid concavine, isolated from Clitocybe concava (Basidiomycetae), has been accomplished. The synthetic route features regio- and stereoselective manipulation of polycyclic imide intermediates via enolate substitution and Grignard addition, along with a key bridge-forming step involving a new method for sulfenylative radical cyclisation. The NMR data for synthetic concavine demonstrate that the original data reported for the natural product refer to the derived acetic acid salt, probably formed as an artefact of isolation or purification.