De Novo Asymmetric Approach to Aspergillide‐C: Synthesis of 4‐epi‐seco‐Aspergillide‐C

Abstract An asymmetric approach toward the synthesis of marine natural product aspergillide‐C has been developed. The convergent uses two Noyori transfer hydrogenations to enantioselectively prepare key fragments, a C ‐1 ‐7 pyranone fragment and ‐8 ‐14 β ‐keto‐sulfone fragment. absolute stereochemistry was established by reduction ‐furylketoester form furyl alcohol. Achmatowicz rearrangement used stereoselectively convert alcohol in an ynone propargyl alkyne zipper isomerization stereospecifically Finally, Pd‐catalyzed ‐glycosylation diastereoselectively couple which when combined with Julia‐Kocienski type elimination formed protected variant 4‐ epi ‐seco‐acid aspergillide‐C.