Synthesis of the bicyclic butenolide core of pallamolide A: a biomimetic approach†

Abstract

Pallamolide A is a 7,8-seco-labdane terpenoid possessing a unique bicyclo[2.2.2]octane core and a spiro-butenolide moiety. A biomimetic synthesis of the bicyclic butenolide core over 10 steps is reported, featuring an unexpected autoxidation ring opening, and a vinylogous Mukaiyama aldol reaction which was spontaneously followed by an unusual intramolecular vinylogous aldol reaction to assemble the spiro-butenolide moiety and bicyclic core of pallamolide A.