Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality ligands and P-stereogenic phosphorus ligands. Most of the reported ligands belong to the former class. Privileged ones such as BINAP and DuPhos are frequently employed in a wide range of catalytic asymmetric transformations. In contrast, the latter class of P-stereogenic phosphorus ligands has remained a small family for many years mainly because of their synthetic difficulty. The late 1990s saw the emergence of novel P-stereogenic phosphorus ligands with their superior enantioinduction ability in Rh-catalyzed asymmetric hydrogenation reactions. Since then, numerous P-stereogenic phosphorus ligands have been synthesized and used in catalytic asymmetric reactions. This Review summarizes P-stereogenic phosphorus ligands reported thus far, including their stereochemical and electronic properties that afford high to excellent enantioselectivities. Examples of reactions that use this class of ligands are described together with their applications in the construction of key intermediates for the synthesis of optically active natural products and therapeutic agents. The literature covered dates back to 1968 up until December 2023, centering on studies published in the late 1990s and later years.

中文翻译：

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不对称催化中的 P-立体磷配体


手性磷配体在有效合成有用的光学活性化合物的不对称催化中发挥着至关重要的作用。它们主要分为两类：主链手性配体和P-立体磷配体。大多数报道的配体属于前一类。 BINAP 和 DuPhos 等特权分子经常用于各种催化不对称转化。相比之下，后一类P-立体磷配体多年来一直是一个小家族，主要是因为它们的合成困难。 20 世纪 90 年代末出现了新型 P-立体磷配体，它们在 Rh 催化的不对称氢化反应中具有优异的对映诱导能力。从那时起，许多P-立体磷配体被合成并用于催化不对称反应。本综述总结了迄今为止报道的 P-立体磷配体，包括它们的立体化学和电子特性，这些特性可提供高至优异的对映选择性。描述了使用此类配体的反应示例及其在构建合成光学活性天然产物和治疗剂的关键中间体中的应用。所涵盖的文献可以追溯到 1968 年至 2023 年 12 月，主要集中在 90 年代末及以后几年发表的研究。