Zi-Jing Zhang, Matthias M. Simon, Shuang Yu, Shu-Wen Li, Xinran Chen, Silvia Cattani, Xin Hong* and Lutz Ackermann*,
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引用次数: 0
Abstract
The catalytic asymmetric construction of axially chiral C–N atropisomers remains a formidable challenge due to their low rotational barriers and is largely reliant on toxic, cost-intensive, and precious metal catalysts. In sharp contrast, we herein describe the first nickel-catalyzed atroposelective C–H alkylation for the construction of C–N axially chiral compounds with the aid of a chiral heteroatom-substituted secondary phosphine oxide (HASPO)-ligated Ni–Al bimetallic catalyst. A wide range of alkenes, including terminal and internal alkenes, were well compatible with the reaction, providing a variety of benzimidazole derivatives in high yields and enantioselectivities (up to 97:3 e.r.). The key to success was the identification of novel HASPOs as highly effective chiral preligands. Mechanistic studies revealed the catalyst mode of action, and in-depth data science analysis elucidated the key features of the responsible chiral preligands in controlling the enantioselectivity.
期刊介绍:
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