Ruthenium-Catalyzed Cross-Coupling of 7-Azabenzonorbornadienes with Alkynes. An Entry to 3a,9b-Dihydrobenzo[g]indoles

Electron-rich half-sandwich ruthenium complex CpRuI(PPh₃)₂, generated in situ, catalyzed the coupling reaction of 7-azabenzonorbornadienes with alkynes to form 3a,9b-dihydrobenzo[g]indoles. This transformation involves the cleavage of one C−N bond of the bicyclic alkene and formation of two (C−C and C−N) bonds at the acetylenic carbons. The scope and limitations of the reaction are addressed according to the substitution patterns of the alkyne and of the substituent at the nitrogen atom of the azabenzonorbornadiene.