Asymmetric Synthesis of C2‐Symmetric Axially Chiral Biaryls through Rhodium‐Catalyzed and Alkyne‐Controlled Diastereoselective Double [2+2+2] Cycloaddition

The asymmetric synthesis of C2‐symmetric axially chiral biaryls was achieved by the cationic rhodium(I)/1,3‐bis(diphenylphosphino)propane (dppp) complex catalyzed diastereoselective double [2+2+2] cycloaddition of (R)‐3‐butyn‐2‐ol‐derived tetraynes with functionalized monoynes. Interestingly, the use of propiolates afforded biaryls possessing large dihedral angles, and in contrast, the use of propargyl alcohol afforded biaryls possessing small dihedral angles.