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.
J Am Chem Soc. 2016 Sep 21;138(37):12053-6. doi: 10.1021/jacs.6b07972. Epub 2016 Sep 9.
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.
手性杂芳基溴化物、三氟甲磺酸酯或全氟代磺酸酯与芳基/烷基伯胺的 Pd(0)催化偶联反应，使用 QUINAP 作为配体，可提供相应的具有优异产率和对映选择性的轴手性杂芳基伯胺。中性和阳离子氧化加成中间体的反应性和结构研究支持基于后者立体生成轴的不稳定的动态动力学不对称氨基化反应机理，并表明胺与 Pd 中心的配位是决定立体化学的步骤。
