Synthesis of IAN-type N,N-Ligands via Dynamic Kinetic Asymmetric Buchwald–Hartwig Amination

The Pd0-catalyzed coupling of racemic heterobiaryl bromides, triflates, or nonaflates with aryl/alkyl primary amines using QUINAP as the ligand provides the corresponding axially chiral heterobiaryl amines with excellent yields and enantioselectivities. Reactivity and structural studies of neutral a...

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Veröffentlicht in:Journal of the American Chemical Society 2016-09, Vol.138 (37), p.12053-12056
Hauptverfasser: Ramírez-López, Pedro, Ros, Abel, Romero-Arenas, Antonio, Iglesias-Sigüenza, Javier, Fernández, Rosario, Lassaletta, José M
Format: Artikel
Sprache:eng
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Zusammenfassung:The Pd0-catalyzed coupling of racemic heterobiaryl bromides, triflates, or nonaflates with aryl/alkyl primary amines using QUINAP as the ligand provides the corresponding axially chiral heterobiaryl amines with excellent yields and enantioselectivities. Reactivity and structural studies of neutral and cationic oxidative addition intermediates support a dynamic kinetic asymmetric amination mechanism based on the labilization of the stereogenic axis in the latter and suggest that coordination of the amine to the Pd center is the stereodetermining step.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b07972