A Formal [3+3+1] Reaction of Enyne‐Methylenecyclopropanes through Au(I)‐Catalyzed Enyne Cycloisomerization and Rh(I)‐Catalyzed [6+1] Reaction of Vinylspiropentanes and CO

Abstract A formal [3+3+1] reaction through gold(I)‐catalyzed enyne cycloisomerization of enyne‐methylenecyclopropanes and rhodium(I)‐catalyzed [6+1] reaction of vinylspiropentanes and CO has been developed to synthesize aza‐6/7 bicyclic compounds, hexahydrocyclohepta[ c ]pyridinones. DFT calculations reveal that four steps are involved in the [6+1] cycloaddition of vinylspiropentanes and CO, including oxidative addition of cyclopropane to Rh, β−C elimination, CO insertion and reductive elimination.