Synthesis of axially chiral biaryl compounds by asymmetric catalytic reactions with transition metals

•A review on the synthesis of axially chiral biaryls by asymmetric catalysis.•Exhaustive description of chiral ligands used in the palladium-catalyzed Suzuki–Miyaura cross-coupling reaction.•Emerging reactions such as asymmetric direct CH functionalization are presented.•Asymmetric [2+2+2] cycloadditions catalyzed by group 9 transition metals are included. Axially chiral biaryl structures are unique systems encountered in various synthetic compounds such as BINAP and BINOL, polymers, but also in natural products presenting a pharmaceutical interest such as Vancomycin, Steganacin or Korupensamine. The axial chirality of these products, so-called atropisomerism, is induced by the restricted rotation around the aryl–aryl bond. This review will summarize the different strategies imagined by chemists to control such chirality, focusing on asymmetric catalytic processes with transition metals. Only transition metal complexes bearing chiral ligands will be considered and the core of this review will consist of the enantioselective coupling of two achiral substrates.