Total Synthesis of Ulodione A via a Double-Alkylation and DABCO Promoted Ring-Expansion Rearrangement Sequence.

Abstract

First total synthesis of ulodione A has been achieved via the key-step reactions of DIPEA-promoted dialkytion of 1,3-cyclopentadione with a bromonitroolefin and DABCO promoted/catalytic semipinacol-like ring-expansion rearrangement, with regioselective transformation of the nitrocyclohexane intermediates to their cyclopentenone counterparts via a sequence of reactions in a one-pot operation. Structures of six products were unequivocally established by X-ray crystallography.