Total Syntheses of Malettinins C and E

The total syntheses of tropolone-containing natural products malettinins C and E were accomplished. A nitro compound and a chiral enone were prepared by using palladium-mediated nitromethylation and an organocatalyst-mediated asymmetric aldol reaction, respectively, and were connected via a Michael reaction. Oxidative dearomatization of a phenol having a cyclic acetal moiety produced a spirocyclic dienone, which could be converted into a tropolone via a base-mediated ring-expansion reaction, with elimination of the nitro group, providing entry to malettinins C and E.