Abstract

Abstract This article focuses on the design and development of novel phosphite, phosphoramidite, and diphosphonite ligands with fine‐tuning capability and their successful applications to catalytic asymmetric synthesis. A library of chiral biphenol‐based phosphorus ligands have been designed, synthesized and applied to a wide range of transition metal‐catalyzed asymmetric catalytic reactions. These reactions include asymmetric hydrogenation, hydroformylation, conjugate addition, allylic amination, allylic alkylation, and allylic etherification. These reactions have also provided enantioselective routes to the syntheses of key intermediates in the total syntheses of bioactive natural products. The fine‐tuning capability of these ligands is proven critical in achieving excellent enantioselectivity and catalytic activity for specific reactions and processes.

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