One‐Pot Two‐Step Synthesis of Optically Active α‐Amino Phosphonates by Palladium‐Catalyzed Hydrogenation/Hydrogenolysis of α‐Hydrazono Phosphonates. Issue 1 (9th December 2016)

• Record Type: Journal Article
• Authors: Goulioukina, Nataliya S.; Shergold, Ilya A.; Rybakov, Victor B.; Beletskaya, Irina P.
• Is Part Of: Advanced synthesis & catalysis. Volume 359:Issue 1(2017)
• Page Start: 153
• Page End: 162
• Publication Date: 2016-12-09
• Subjects: α-amino phosphonates -- asymmetric catalysis -- α-hydrazono phosphonates -- hydrogenation -- palladium; Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201600945
• Languages: English
• ISSNs: 1615-4150

Abstract

Abstract: An efficient and convenient one‐pot procedure for the stereoselective catalytic synthesis of ring‐substituted [amino(phenyl)methyl]phosphonates has been developed. The enantioselective hydrogenation of easily available diisopropyl ( Z )‐[aryl(phenylhydrazono)methyl]phosphonates using palladium(II) acetate as a precatalyst, ( R )‐2, 2′‐bis(diphenylphosphino)‐5, 5′‐dichloro‐6, 6′‐dimethoxy‐1, 1′‐biphenyl [( R )‐Cl–MeO‐BIPHEP] as a ligand, and (1 S )‐(+)‐10‐camphorsulfonic acid as an activator in a mixture of 2, 2, 2‐trifluoroethanol and methylene chloride at ambient temperature results in the formation of corresponding [aryl(2‐phenylhydrazino)methyl]phosphonates. The subsequent cleavage of the N−N bond has been accomplished with molecular hydrogen after the addition of palladium on carbon and methanol into crude reaction mixture to afford the optically active [amino(aryl)methyl]phosphonates. The method is operationally simple and provides an appreciable enantioselectivity up to 98 % ee . Abstract :