The discovery of proper ligands to simultaneously modulate the reactivity and effectively control the stereoselectivity is a central topic in the field of enantioselective C−H activation. Herein, we reported the synthesis of axially chiral biaryls by Pd‐catalyzed atroposelective C−H olefination. A novel chiral spiro phosphoric acid, STRIP, was identified as a superior ligand for this transformation. A broad range of axially chiral quinoline derivatives were synthesized in good yields with excellent enantioselectivities (up to 98 % ee). Density functional theory was used to gain a theoretical understanding of the enantioselectivities in this reaction.

A simple and ubiquitously present group, free amine, is used as a directing group to synthesize axially chiral biaryl compounds by PdII‐catalyzed atroposelective C−H olefination. A broad range of axially chiral biaryl‐2‐amines can be obtained in good yields with high enantioselectivities (up to 97 % ee). Chiral spiro phosphoric acid (SPA) proved to be an efficient ligand and the loading could be reduced to 1 mol % without erosion of enantiocontrol in gram‐scale synthesis. The resulting axially chiral biaryl‐2‐amines also provide a platform for the synthesis of a set of chiral ligands.

Biaryl atropisomers are of great importance in natural products,p harmaceuticals,a nd asymmteric synthesis. The efficient synthesis of these chiral scaffolds with full enantiocontrol and high diversity remains challenging. Reported herein is aP d-catalyzed atroposelective CÀH allylation with tert-leucine as an efficient catalytic chiral transient auxiliary.Awide range of enantioenriched biaryl aldehydes were prepared in synthetically useful yields with excellent enantioselectivity (up to > 99 %e e) through b-O elimination. The reaction could be carried out on agram scale without erosion of the ee value.Avariety of axially chiral carboxylic acids could be obtained with high enantiopurity. The resulting axially chiral biaryl aldehydes and carboxylic acids might be used in asymmetric synthesis as chiral ligands and/or organocatalysts.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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