Molecular conformations induced by the rotation about single bonds play a crucial role in chemical transformations. Revealing the relationship between the conformations of chiral catalysts and the enantiodiscrimination is a formidable challenge due to the great difficulty in isolating the conformers. Herein, we report a chiral catalytic system composed of an achiral catalytically active unit and an axially chiral 1,1′-bi-2-naphthol (BINOL) unit which are connected via a C–O single bond. The two conformers of the catalyst induced by the rotation about the C–O bond, are determined via single-crystal X-ray diffraction and found to respectively lead to the formation of highly important axially chiral 1,1′-binaphthyl-2,2′-diamine (BINAM) and 2-amino-2′-hydroxy-1,1′-binaphthyl (NOBIN) derivatives in high yields (up to 98%), with excellent enantioselectivities (up to 98:2 e.r.) and opposite absolute configurations. The results highlight the importance of conformational dynamics of chiral catalysts in asymmetric catalysis.

由单键旋转引起的分子构象在化学转化中起着至关重要的作用。由于分离构象异构体的难度很大，揭示手性催化剂的构象与对映异构体之间的关系是一项艰巨的挑战。在此，我们报道了一种由非手性催化活性单元和轴向手性 1,1'-bi-2-naphthol (BINOL) 单元组成的手性催化体系，它们通过 C-O 单键连接。由围绕 C-O 键的旋转诱导的催化剂的两个构象异构体通过单晶 X 射线衍射测定，发现分别导致形成非常重要的轴向手性 1,1'-binaphthyl-2,2 '-二胺 (BINAM) 和 2-氨基-2'-羟基-1,1'-联萘 (NOBIN) 衍生物的高产率（高达 98%），具有出色的对映选择性（高达 98:2 er）和相反的绝对构型。结果突出了手性催化剂构象动力学在不对称催化中的重要性。