Axially chiral biaryl monophosphorus molecules, exemplified by atropisomeric 1,1′‐biaryl aminophosphines, are significant motifs in numerous chiral ligands/catalysts. Developing efficient methods for preparing phosphorus compounds with these privileged motifs is an important endeavor in synthetic chemistry. Herein, we develop an effective, modular method by a chiral‐phosphonium‐salt‐catalyzed novel cascade between phosphorus‐containing nitroolefins and α,α‐dicyanoolefins, leading to a great diversity of atropisomeric biaryls bearing phosphorus groups in high yields with excellent stereoselectivities. The reaction features include a Thorpe‐type cycloaddition/oxidative hydroxylation/aromatization cascade pathway with a central‐to‐axial chirality transfer process. Insight gained from our studies is expected to advance general efforts towards the catalytic synthesis of atropisomeric biaryl phosphorus compounds, offering a platform for developing new efficient chiral ligands and catalysts.

Axially chiral biaryl monophosphorus molecules, exemplified by atropisomeric 1,1′‐biaryl aminophosphines, are significant motifs in numerous chiral ligands/catalysts. Developing efficient methods for preparing phosphorus compounds with these privileged motifs is an important endeavor in synthetic chemistry. Herein, we develop an effective, modular method by a chiral‐phosphonium‐salt‐catalyzed novel cascade between phosphorus‐containing nitroolefins and α,α‐dicyanoolefins, leading to a great diversity of atropisomeric biaryls bearing phosphorus groups in high yields with excellent stereoselectivities. The reaction features include a Thorpe‐type cycloaddition/oxidative hydroxylation/aromatization cascade pathway with a central‐to‐axial chirality transfer process. Insight gained from our studies is expected to advance general efforts towards the catalytic synthesis of atropisomeric biaryl phosphorus compounds, offering a platform for developing new efficient chiral ligands and catalysts.