Pd(0)-catalyzed intramolecular C–H alkenylation was achieved with excellent yields and enantioselectivity for the construction of planar chiral ferrocenes. It is compatible with a broad range of substrates and various functional groups. Notably, the enantioselective and diastereoselective synthesis of planar chiral ferrocenes was realized by cascade C–H arylation and alkenylation reaction for the first time. Additionally, the product was easily converted into a N,O-bidentate ligand, showing promising chiral induction in asymmetric alkynylation of 1-naphthaldehyde.

A highly efficient synthesis of planar chiral ferrocenylpyridine derivatives via Pd-catalyzed intramolecular C–H arylation was developed, and quantitative yields and excellent enantioselectivity were obtained for a wide range of substrates. Notably, the catalyst loading could be lowered to 0.2 mol %, which represents the highest catalytic efficiency found for asymmetric C–H bond activation (TON up to 495). These compounds could be easily transformed to pyridine N-oxides, displaying promising catalytic reactivity in the asymmetric opening of meso-epoxide. Moreover, computational investigations were conducted to clarify the origin of the excellent enantioselectivity. The compatibility of large-scale synthesis and low catalyst loading should enhance the practicality of the synthetic application of the current method.

A highly efficient synthesis of planar chiral ferrocenes by enantioselective Pd(0)-catalyzed direct C–H arylation from readily available starting materials under mild reaction conditions was developed (up to 99% yield, 99% ee). The products can be easily transformed to the highly efficient planar ferrocene ligands, which have demonstrated high efficiency in Pd-catalyzed asymmetric allylic alkylation and amination reactions.

An efficient protocol to synthesize axially chiral compounds via kinetic resolution by Pd(II)-catalyzed direct C–H iodination was realized (up to s = 27). The iodide product could be easily transformed to aryl-substituted pyridine N-oxides via the Suzuki–Miyaura coupling, which proved to be a suitable catalyst in asymmetric allylation of benzaldehyde with allyltrichlorosilane.Keywords: axial chirality; iodination; kinetic resolution; N-oxide; Pd(II)-catalyzed

Enantioselective Pd(II)-catalyzed direct coupling of aminomethylferrocene derivatives with boronic acids was realized. With commercially available Boc-l-Val-OH as a ligand, planar-chiral ferrocenes could be synthesized in yields of 14–81% with up to 99% ee under mild conditions.