Fulvene Synthesis by Rhodium(I)‐Catalyzed [2+2+1] Cycloaddition: Synthesis and Catalytic Activity of Tunable Cyclopentadienyl Rhodium(III) Complexes with Pendant Amides

It has been established that a Rh^I+/segphos complex catalyzes the 2+2+1] cycloaddition of 1,6‐diynes with cyclopropylideneacetamides to give substituted fulvenes in good yields. The reductive complexation of the product fulvenes with RhCl₃ in EtOH furnished the corresponding dinuclear cyclopentadienyl Rh^III complexes bearing a pendant amide moiety. These Rh^III complexes were highly active catalysts for oxidative annulation and cyclization through C(sp²)−H and C(sp³)−H functionalization.