Manganese-Catalyzed Asymmetric Hydrogenation for Atroposelective Dynamic Kinetic Resolution of Heterobiaryl Ketone N -Oxides

作者：Yin-Bo Wan, Xiang‐Ping Hu · 发表于：ACS Catalysis · 年份：2024 · DOI：10.1021/acscatal.4c04979 · 被引用次数：18 · 研究领域：Axial and Atropisomeric Chirality Synthesis、Molecular spectroscopy and chirality、Asymmetric Hydrogenation and Catalysis

An atroposelective dynamic kinetic resolution of configurationally labile heterobiaryl ketone N -oxides via Mn-catalyzed asymmetric hydrogenation has been disclosed. By use of a structurally finely tuned chiral ferrocenyl P,N,N-ligand, the hydrogenation proceeds smoothly under mild conditions with simultaneous installation of central and axial chirality, giving a wide range of atropisomeric 1-arylisoquinoline and 2-arylpyridine N -oxides bearing a chiral alcohol structure with high diastereo- and enantioselectivities. The diastereomer of the hydrogenation product could be readily prepared in a stereospecific way with the complete inversion of the central chirality via Mitsunobu reaction. The value of this central- and axial-chiral heterobiaryl N -oxide scaffold is preliminarily demonstrated by its successful utility as a chiral catalyst in asymmetric allylation of benzaldehyde with allyltrichlorosilane.