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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. [ABSTRACT FROM AUTHOR]

A practical and efficient strategy using a Pd‐catalyzed intramolecular Buchwald‐Hartwig amination was reported. A broad range of atropisomeric arylamines were obtained with excellent diastereoselectivities and yields. Even the N‐alkyl substrates were synthesized smoothly. The reaction scale‐up and further transformations of selected arylamines also demonstrated the synthetic utility of this protocol. [ABSTRACT FROM AUTHOR]

Front Cover: Efficient Construction of Atropisomeric Arylamines through a Diastereoselective Buchwald-Hartwig Amination (Asian J. Org. Keywords: amines; amination; atroposelective synthesis; C-N axial chirality; central-to-axial chirality transfer Amines, amination, atroposelective synthesis, C-N axial chirality, central-to-axial chirality transfer. [Extracted from the article]