Palladium-Catalyzed Decarboxylative Vinylation of Potassium Nitrophenyl Acetate: Application to the Total Synthesis of (±)-Goniomitine

Merge and divert. (±)-goniomitine was synthesized featuring two key steps: a) fragment coupling to functionalized cyclopentene by a novel palladium-catalyzed decarboxylative vinylation reaction and b) an unprecedented one-pot integrated oxidation/reduction/cyclization (IORC) process to convert the substituted cyclopentene to tetracyclic skeleton of goniomitine. In this IORC process, oxidative scission of one double bond, reduction of azido and nitro groups, formation of three C-N bonds with the concurrent formation of three rings took place with high degree of chemo-, regio- and diastereo-selectivities.