Enantioselective Synthesis of Atropisomeric Biaryl Phosphorus Compounds by Chiral‐Phosphonium‐Salt‐Enabled Cascade Arene Formation
Lixiang Zhu, Heling Peng, Yan Guo, Jixing Che, Jia‐Hong Wu, Zhishan Su, Tianli Wang
Abstract
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.