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Ir(I)-catalyzed atroposelective hydroarylation of alkynes with 1-arylisoquinolines through C–H functionalization was realized. In the presence of 5 mol% of [Ir(cod)Cl]2 and 10 mol% of QUINOX-P, a wide range of axially chiral alkenylated biaryls were obtained in up to 98% yield and 97% ee. Notably, only one equivalent of the alkyne was required to guarantee a high efficiency of this C–H functionalization process. This reaction exhibits excellent functional-group tolerance under mild conditions.

Chiral cyclopentadienyl rhodium (CpRh) complex-catalyzed asymmetric C-H functionalization reactions have witnessed a significant progress in organic synthesis. In sharp contrast, the reported chiral Cp ligands are limited to C-linked Cp and are often synthetically challenging. To address these issues, we have developed a novel class of tunable chiral cyclopentadienyl ligands bearing oxygen linkers, which were efficient catalysts for C-H arylation of benzo[h]quinolines with 1-diazonaphthoquinones, affording axially chiral heterobiaryls in excellent yields and enantioselectivity (up to 99 % yield, 98.5:1.5 er). Mechanistic studies suggest that the reaction is likely to proceed by electrophilic C-H activation, and followed by coupling of the cyclometalated rhodium(III) complex with 1-diazonaphthoquinones.

CpxM(III)-catalyzed enantioselective C–H functionalization reactions have progressed rapidly using either chiral cyclopentadienyl ligands or appropriate chiral carboxylic acids. In this context, highly reactive carbene and nitrene precursors can serve as effective C–H coupling partners, providing a straightforward and efficient approach to access chiral molecules. In this review, we highlight the developments in CpxM(III)-catalyzed enantioselective C–H functionalization reactions through migratory insertion of metal–carbenes/nitrenes by employing chiral CpxM(III) complexes or achiral CpxM(III) complexes combined with chiral carboxylic acids.

The Rh(III)-catalyzed highly enantioselective C2-arylation of indole derivatives with 1-diazonaphthoquinones is reported. In the presence of 2.5 mol % SCpRh complex and 20 mol % AgNO

Cp

Transition-metal-catalyzed enantioselective C-H functionalization has become a powerful strategy for the formation of C-C or C-X bonds, enabling the highly asymmetric synthesis of a wide range of enantioenriched compounds. Atropisomers are widely found in natural products and pharmaceutically relevant molecules, and have also found applications as privileged frameworks for chiral ligands and catalysts. Thus, research into asymmetric routes for the synthesis of atropisomers has garnered great interest in recent years. In this regard, transition-metal-catalyzed enantioselective C-H functionalization has emerged as an atom-economic and efficient strategy toward their synthesis. In this Perspective, the approaches for the synthesis of atropisomers by transition-metal-catalyzed asymmetric C-H functionalization reactions are summarized. The main focus here is on asymmetric catalysis via Pd, Rh, and Ir complexes, which have been the most frequently utilized catalysts among reported enantioselective C-H functionalization reactions. Finally, we discuss limitations on available protocols and give an outlook on possible future avenues of research.