Synthesis of IAN-type N,N-Ligands via Dynamic Kinetic Asymmetric Buchwald-Hartwig Amination.
The Pd(0)-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.
Instituto Investigaciones Químicas (CSIC-US) , C/Américo Vespucio, 49, 41092 Sevilla, Spain.
Pedro
P
Ramírez-López
Instituto Investigaciones Químicas (CSIC-US) , C/Américo Vespucio, 49, 41092 Sevilla, Spain.|Departamento de Química Orgánica, University of Seville , C/Prof. García González, 1, 41012 Sevilla, Spain.
Abel
A
Ros
Instituto Investigaciones Químicas (CSIC-US) , C/Américo Vespucio, 49, 41092 Sevilla, Spain.
Antonio
A
Romero-Arenas
Departamento de Química Orgánica, University of Seville , C/Prof. García González, 1, 41012 Sevilla, Spain.
Javier
J
Iglesias-Sigüenza
Departamento de Química Orgánica, University of Seville , C/Prof. García González, 1, 41012 Sevilla, Spain.
Rosario
R
Fernández
Instituto Investigaciones Químicas (CSIC-US) , C/Américo Vespucio, 49, 41092 Sevilla, Spain.
José M
JM
Lassaletta