Catalytic Enantioselective Synthesis of Chiral Tetraphenylenes: Consecutive Inter‐ and Intramolecular Cycloadditions of Two Triynes

Triynes having a phenylene-bridged 1,5-diyne moiety were transformed into substituted tetraphenylenes by the title sequence. A cationic Rh–ligand species catalyzed this highly enantioselective reaction. This protocol is a new and easy approach to the construction of the tetraphenylene skeleton and enables an efficient asymmetric synthesis (see scheme; R=H; Z=NTs, C(CO2Me)2, O).