Atroposelective synthesis of axially chiral biaryls by palladium-catalyzed C-H olefination, using tert-leucine as an inexpensive, catalytic, and transient chiral auxiliary, has been realized. This strategy provides a highly efficient and straightforward access to a broad range of enantioenriched biaryls in good yields (up to 98 %) with excellent enantioselectivities (95 to >99 % ee). Kinetic resolution of trisubstituted biaryls bearing sterically more demanding substituents is also operative, thus furnishing the optically active olefinated products with excellent selectivity (95 to >99 % ee, s-factor up to 600).

Recent advances in the synthesis of axially chiral biarylsviatransition metal-catalysed asymmetric C–H functionalization are reported.

Chiral aldehyde catalysis opens new avenues for the activation of simple amines. However, the lack of easy access to structurally diverse chiral aldehyde catalysts has hampered the development of this cutting‐edge field. Herein, we report a Pd‐catalyzed atroposelective C−H naphthylation with 7‐oxabenzonorbornadienes for the preparation of axially chiral biaryls with excellent enantioselectivities (up to >99 % ee). This reaction is scalable and robust, which serves as a key step to provide a rapid access to axially chiral aldehyde catalysts through a three‐step C−H functionalization sequence. These chiral aldehydes exhibit better activities and enantioselectivities than the previously reported organocatalysts in the asymmetric activation of glycine derived amides and dipeptides. Moreover, preliminary investigation also discloses that the aldehyde catalyst can effectively override the intrinsic facial selectivity of chiral dipeptide substrates, showcasing the strong chiral induction ability of this type of novel aldehyde catalysts.

Due to the lower rotational barriers, the catalytic asymmetric construction of atropisomeric species featuring a five-membered ring remains a formidable challenge. Herein, we describe a Pd-catalyzed atroposelective C−H alkynylation to synthesize such atropisomers. A wide range of atropisomers displaying either a stereogenic C−N or C−C bond featuring one or even two five-membered rings were obtained (up to 98% yield and up to >99% ee). Various five-membered heteroarenes, including pyrroles, thiophenes, benzothiophenes, and benzofurans were compatible with this protocol. Notably, this strategy offers the catalytic asymmetric synthesis of axially chiral 3,3′-bisbenzothiophene with good ee (93% ee). Computational studies revealed the key structural elements that differentiate the rotational barriers of benzothiophene and benzofuran moieties.

Cp*Cobalt­(III)-catalyzed enantioselective C–H amidation of ferrocenes using monoprotected amino acids (MPAAs) as chiral ligands was developed. The reaction was performed under mild conditions in high yields (up to 97%) with moderate enantioselectivity (up to 77.5:22.5 er), providing a promising strategy to create planar chirality via base-metal-catalyzed enantioselective C–H activation.