Ni-Catalyzed Asymmetric Hydrophosphination of Unactivated Alkynes

• Published in: Journal of the American Chemical Society Vol. 143; no. 30; pp. 11309 - 11316
• Main Authors: Liu, Xu-Teng, Han, Xue-Yu, Wu, Yue, Sun, Ying-Ying, Gao, Li, Huang, Zhuo, Zhang, Qing-Wei
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 04.08.2021; Amer Chemical Soc
• Subjects: alkynes; catalytic activity; Chemistry; Chemistry, Multidisciplinary; enantioselectivity; ligands; nickel; organocatalysts; phosphine; Physical Sciences; Science & Technology; toxicity; ENANTIOSELECTIVE SYNTHESIS; CHIRAL PHOSPHORUS LIGANDS; KINETIC RESOLUTION; ALKYLATION; ARYLATION; SECONDARY; OXIDES; P-STEREOGENIC PHOSPHINAMIDES; ACCESS; DESYMMETRIZATION
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.1c05649

The practical synthesis of P-stereogenic tertiary phosphines, which have wide applications in asymmetric catalysis, materials, and pharmaceutical chemistry, represents a significant challenge. A regio- and enantioselective hydrophosphination using cheap and ubiquitous alkynes catalyzed by a nickel complex was designed, in which the toxic and air-sensitive secondary phosphines were prepared in situ from bench-stable secondary phosphine oxides. This methodology has been demonstrated with unprecedented substrate scope and functional group compatibility to afford electronically and structurally diversified P­(III) compounds. The products could be easily converted into various precursors of bidentate ligands and organocatalysts, as well as a variety of transition-metal complexes containing both P- and metal-stereogenic centers.