Au-Mn Bond Formal Metathesis with Ar-F via Synergistic Bimetallic Activation.

IF 15.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of the American Chemical Society Pub Date : 2025-10-03 DOI:10.1021/jacs.5c13893

Siyu Xia,Weina Zhong,Tingrui Li,Zhongren Xu,Jie Han,Wukun Liu,Weipeng Li,Chengjian Zhu,Jin Xie

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引用次数: 0

Abstract

Selective C-F activation with gold-complex has been esteemed as a long-standing issue owing to a kinetically unfavorable oxidative addition elementary reaction. Herein, we report a synergistic bimetallic Au-Mn bond formal metathesis with aromatic C(sp2)-F bond, establishing a versatile platform for the synthesis of polyfluorophenyl-substituted Au(I) complexes. A wide range of structurally diverse L-Au(I)-ArFn complexes (37 examples, up to 98% yield) have been readily constructed. Mechanistic studies together with DFT calculations support that the key C-F bond cleavage proceeds via thermodynamically and kinetically feasible Au-Mn bimetallic cooperative activation, rather than direct oxidative addition toward either Au or Mn metal center. Notably, these aryl gold(I) complexes exhibit broad biological functions, including anticancer and/or anti-inflammatory efficacy, facilitating promising candidate drug discovery for pharmaceutical development. This bimetallic strategy should open new avenues to achieve unique reactivity profiles and novel mechanistic pathways.

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协同双金属活化Au-Mn键与Ar-F的形式复合。

选择性C-F活化金络合物一直被认为是一个长期存在的问题，由于动力学不利的氧化加成的基本反应。本文中，我们报道了一种协同双金属Au- mn键与芳香C(sp2)-F键的形式复合反应，为合成多氟苯基取代的Au(I)配合物建立了一个通用平台。广泛的结构多样的L-Au(I)-ArFn配合物（37个例子，高达98%的产率）已经很容易构建。机制研究和DFT计算支持关键的C-F键裂解是通过热力学和动力学上可行的Au-Mn双金属协同活化进行的，而不是直接向Au或Mn金属中心氧化加成。值得注意的是，这些芳基金(I)配合物具有广泛的生物学功能，包括抗癌和/或抗炎功效，促进了有希望的药物开发候选药物的发现。这种双金属策略应该开辟新的途径，以实现独特的反应性概况和新的机制途径。

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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来源期刊

Journal of the American Chemical Society 化学-化学综合

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.