Graduate School of Science, Chiba University.
Proc Jpn Acad Ser B Phys Biol Sci. 2021;97(9):520-542. doi: 10.2183/pjab.97.026.
Metal-catalyzed asymmetric synthesis is one of the most important methods for the economical and environmentally benign production of useful optically active compounds. The success of the asymmetric transformations is significantly dependent on the structure and electronic properties of the chiral ligands coordinating to the center metals, and hence the development of highly efficient ligands, especially chiral phosphine ligands, has long been an important research subject in this field. This review article describes the synthesis and applications of P-chiral phosphine ligands possessing chiral centers at the phosphorus atoms. Rationally designed P-chiral phosphine ligands are synthesized by the use of phosphine-boranes as the intermediates. Conformationally rigid and electron-rich P-chiral phosphine ligands exhibit excellent enantioselectivity and high catalytic activity in various transition-metal-catalyzed asymmetric reactions. Recent mechanistic studies of rhodium-catalyzed asymmetric hydrogenation are also described.
金属催化的不对称合成是经济且环境友好地生产有用的光学活性化合物的最重要方法之一。不对称转化的成功在很大程度上取决于与中心金属配位的手性配体的结构和电子性质，因此，高效配体的开发，特别是手性膦配体的开发，一直是该领域的重要研究课题。本文综述了具有磷原子手性中心的 P-手性膦配体的合成与应用。通过使用膦-硼烷作为中间体，合理设计了 P-手性膦配体。构象刚性和富电子的 P-手性膦配体在各种过渡金属催化的不对称反应中表现出优异的对映选择性和高催化活性。还描述了最近对铑催化不对称氢化反应的机理研究。
