不对称钴催化氟原子构建第四纪立体中心

IF 15.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Jingyi Wang, Jin Yang, Jian He* and Zhan Lu*, 
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引用次数: 0

摘要

氟化季碳手性中心合成方法的进步在有机化学和药物化学领域受到高度追捧。本研究通过钴催化α-溴-α-氟酮与芳基/烯基锌试剂的不对称根岸偶联反应,成功制备了此类化合物。手性不对称N,N,N-三齿(CUT)配体的调整对提高钴催化反应活性和选择性、防止氢脱溴副产物的形成、容纳位阻底物和杂环具有关键作用。控制和动力学实验表明,金属转化是限速步骤,这一机制特征将新开发的不对称钴催化交叉偶联与以前的方法区分开来。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Asymmetric Cobalt Catalysis for the Construction of Quaternary Stereogenic Centers with Fluorine Atoms

Asymmetric Cobalt Catalysis for the Construction of Quaternary Stereogenic Centers with Fluorine Atoms

The advancement of robust synthetic methodologies for generating fluorinated quaternary carbon chiral centers is highly sought after in the fields of organic and medicinal chemistry. This study successfully provides such compounds through cobalt-catalyzed asymmetric Negishi coupling reactions of α-bromo-α-fluoro ketones with aryl/alkenyl zinc reagents. The adjustment of chiral unsymmetric N,N,N-tridentate (CUT) ligands played a key role in improving reactivity and selectivity in the cobalt catalysis, preventing the formation of hydrodebromination byproducts, and accommodating sterically hindered substrates and heterocycles. Control and kinetic experiments reveal that transmetalation serves as the rate-limiting step, a mechanistic characteristic that sets the newly developed asymmetric cobalt-catalyzed cross-couplings apart from previous methodologies.

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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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