Chiral discrimination of small substituents in biaryl atropisomer construction: enantioselective synthesis of axially chiral 1-azafluorene via Ni-catalyzed [2+2+2] cycloaddition

IF 10.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Science China Chemistry Pub Date : 2023-10-08 DOI:10.1007/s11426-023-1749-x

Jin-Huang Peng, Yu-Qing Zheng, Li-Gang Bai, Wen-Bo Liu

引用次数: 0

Abstract

Construction of axially chiral 1-azafluorenes via nickel-catalyzed [2+2+2] cycloaddition of alkynes and (o-alkynyl)benzyl nitriles is described. This strategy enables enantioselective discrimination of two sterically similar ortho substituents, such as H and F, during the construction of tri-ortho-substituted biaryl atropisomers. Mechanistic studies including the stereochemistry model and the stability of the atropenantiomers toward racemization are provided. The unique steric hindrance provided by 1-azafluorene skeleton and the fine chiral cavity of the nickel catalyst are key to achieving high enantioselectivity.

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双芳基阻聚体结构中小取代基的手性识别：Ni催化[2+2+2]环加成对映选择性合成轴向手性1-氮杂芴

描述了通过镍催化炔烃和（邻炔基）苄基腈的[2+2+2]环加成构建轴向手性1-氮杂芴。在构建三个邻位取代的双芳基阻聚体的过程中，该策略能够对两个空间相似的邻位取代基（如H和F）进行对映选择性区分。提供了包括立体化学模型和反对映异构体外消旋稳定性在内的机理研究。1-氮杂芴骨架提供的独特空间位阻和镍催化剂精细的手性腔是实现高对映选择性的关键。

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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来源期刊

Science China Chemistry CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

7.30%

发文量

3787

审稿时长

2.2 months

期刊介绍： Science China Chemistry, co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China and published by Science China Press, publishes high-quality original research in both basic and applied chemistry. Indexed by Science Citation Index, it is a premier academic journal in the field. Categories of articles include: Highlights. Brief summaries and scholarly comments on recent research achievements in any field of chemistry. Perspectives. Concise reports on thelatest chemistry trends of interest to scientists worldwide, including discussions of research breakthroughs and interpretations of important science and funding policies. Reviews. In-depth summaries of representative results and achievements of the past 5–10 years in selected topics based on or closely related to the research expertise of the authors, providing a thorough assessment of the significance, current status, and future research directions of the field.