钴催化的C - H环缩法一步合成邻C -C和C - N二轴的退聚体

IF 16.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Angewandte Chemie International Edition Pub Date : 2022-08-02 DOI:10.1002/anie.202208912

Bing-Jie Wang, Guo-Xiong Xu, Zong-Wei Huang, Xu Wu, Prof.?Dr. Xin Hong, Dr. Qi-Jun Yao, Prof.?Dr. Bing-Feng Shi

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引用次数: 22

摘要

由于两轴之间的空间影响及其独特的拓扑结构，具有相邻二轴的atrotopselective synthesis仍然是罕见和具有挑战性的。在此，我们公开了通过无环戊二烯(Cp)的钴催化分子内C - H环化，一步构建具有邻近C - C和C - N手性二轴的二向旋退体，提供了具有独特结构的二向旋退体，具有良好的两轴立体控制(高达> 99% ee和70:1 dr)。含荧光团的光纯产品具有圆偏振发光(CPL)特性，是潜在CPL应用的候选材料。通过反异构化实验和密度泛函理论(DFT)计算，研究了二轴的旋转势垒和旋转路径。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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Single-Step Synthesis of Atropisomers with Vicinal C−C and C−N Diaxes by Cobalt-Catalyzed Atroposelective C−H Annulation

The atroposelective synthesis of atropisomers with vicinal diaxes remains rare and challenging, due to the steric influence between the two axes and their unique topology. Herein, we disclose a single-step construction of atropisomers with vicinal C−C and C−N chiral diaxes by cyclopentadiene (Cp)-free cobalt-catalyzed intramolecular atroposelective C−H annulation, providing the desired diaxial atropisomers of unique structures with decent stereocontrols of both axes (up to >99 % ee and 70 : 1 dr). The optically pure products bearing fluorophores show circular polarized luminescence (CPL) properties, being candidate materials for potential CPL applications. Atropisomerization experiments and density function theory (DFT) calculations are conducted to study the rotational barriers and rotation pathways of the diaxes.

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来源期刊

Angewandte Chemie International Edition 化学-化学综合

CiteScore

26.60

自引率

6.60%

发文量

3549

审稿时长

1.5 months

期刊介绍： Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.