Synthesis and applications of high-performance P-chiral phosphine ligands

• Published in: Proceedings of the Japan Academy, Series B Vol. 97; no. 9; pp. 520 - 542
• Main Author: IMAMOTO, Tsuneo
• Format: Journal Article
• Language: English
• Published: Japan The Japan Academy 11.11.2021
• Subjects: Appointments & personnel changes; asymmetric hydrogenation; Asymmetric synthesis; Asymmetry; Atomic properties; Boron; Catalysis; Catalytic activity; catalytic asymmetric synthesis; Chemical reactions; Chemical synthesis; Enantiomers; enantioselection mechanism; Fluorides; Heavy metals; Hydrogenation; Intermediates; Ligands; Metals; Optical activity; Organic chemistry; P-chiral phosphine ligand; Phosphine; Phosphines; Phosphines - chemistry; phosphine–borane; Phosphorus; Reagents; Review; Rhodium; Transition metals; enantioselection mechanism; P-chiral phosphine ligand; catalytic asymmetric synthesis; asymmetric hydrogenation; phosphine–borane
• ISSN: 0386-2208; 1349-2896; 1349-2896
• 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.