Direct asymmetric ruthenium-catalyzed reductive amination of alkyl-aryl ketones with ammonia and hydrogen

• Verfasst von: Gallardo-Donaire, Joan [VerfasserIn]
• Verfasst von: Hermsen, Marko [VerfasserIn]
• Verfasst von: Wysocki, Jędrzej [VerfasserIn]
• Verfasst von: Rominger, Frank [VerfasserIn]
• Verfasst von: Trapp, Oliver [VerfasserIn]
• Verfasst von: Hashmi, A. Stephen K. [VerfasserIn]
• Verfasst von: Comba, Peter [VerfasserIn]
• Verfasst von: Schaub, Thomas [VerfasserIn]
• Titel: Direct asymmetric ruthenium-catalyzed reductive amination of alkyl-aryl ketones with ammonia and hydrogen
• Verf.angabe: Joan Gallardo-Donaire, Marko Hermsen, Jedrzej Wysocki, Martin Ernst, Frank Rominger, Oliver Trapp, A. Stephen K. Hashmi, Ansgar Schäfer, Peter Comba, and Thomas Schaub
• Jahr: 2018
• Jahr des Originals: 2017
• Umfang: 7 S.
• Fussnoten: Published: December 1, 2017 ; Gesehen am 13.06.2018
• Titel Quelle: Enthalten in: American Chemical SocietyJournal of the American Chemical Society
• Ort Quelle: Washington, DC : ACS Publications, 1879
• Jahr Quelle: 2018
• Band/Heft Quelle: 140(2018), 1, Seite 355-361
• ISSN Quelle: 1520-5126
• DOI: doi:10.1021/jacs.7b10496
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 157631104X

Abstract

The asymmetric ruthenium-catalyzed reductive amination employing ammonia and hydrogen to primary amines is described. Here we demonstrate the capability of our catalyst to perform a chemo- and enantioselective process while using simple ammonia gas as a reagent, one of the most attractive and industrially relevant nitrogen sources. The presence of a catalytic amount of ammonium iodide was essential for obtaining good yields and enantioselectivities. The mechanism of this reaction was investigated by DFT and we found a viable pathway that also explains the trend and magnitude of enantioselectivity through the halide series in good agreement with the experimental data. The in-depth investigation of substrate conformers during the reaction turned out to be crucial in obtaining an accurate prediction of the enantioselectivity. Furthermore, we report the crystallographic data of the chiral [Ru(I)H(CO)((S,S)-f-binaphane)(PPh3)] complex, which we identified as the most efficient catalyst in our investigation.