The vastly increasing application of chiral Cp ligands in asymmetric catalysis results in growing demand for novel chiral Cp ligands. Herein, we report a new class of chiral Cp ligands based on 1,1'-spirobiindane, a privileged scaffold for chiral ligands and catalysts. The corresponding Rh complexes are shown to be excellent catalysts in asymmetric oxidative coupling reactions, providing axially chiral biaryls in 19-97% yields with up to 98:2 er.

Enantioselective construction of axially chiral biaryls by direct C-H bond functionalization reactions has been realized. Novel axially chiral biaryls were synthesized by the direct C-H bond olefination of biaryl compounds, using a chiral [Cp*Rh(III)] catalyst, in good to excellent yields and enantioselectivities. The obtained axially chiral biaryls were found as suitable ligands for rhodium-catalyzed asymmetric conjugate additions.

A Rh-catalyzed enantioselective dearomatization of 1-aryl-2-naphthols with internal alkynes via C-H functionalization reaction was achieved. In the presence of a chiral Cp/Rh catalyst and combined oxidants of Cu(OAc)2 and air (oxygen), various highly enantioenriched spirocyclic enones bearing an all-carbon quaternary stereogenic center could be synthesized in 33-98% yields with up to 97:3 er.