Stoltz-Grubbs （KOtBu/Et3SiH）硅基化的机理：单电子转移是杂解和自由基途径之间缺失的一环。

IF 16.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Angewandte Chemie International Edition Pub Date : 2025-10-20 DOI:10.1002/anie.202517336

Ian D Jenkins,Ka Ho Chow,Elizabeth H Krenske

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引用次数: 0

摘要

本文报道了杂芳烃的Stoltz-Grubbs （KOtBu/Et3SiH）硅基化反应的新机制，成功地解决了该反应中未解释的重要实验特征。该机制结合了氢化物转移、氢原子转移（HAT）和单电子转移（SET）步骤（底物氢化物加合物被确定为新的SET供体），并得到了广泛的理论计算的支持。先前提出的异分化和自由基机制不涉及SET。SET的机制作用的发现解释了为什么硅基化反应同时表现出异裂解和自由基的特征，以及为什么它不需要游离的硅基自由基。以前无法解释的同位素标记反应物反应的实验结果和电子接受添加剂的抑制作用也可以基于SET机制来理解。

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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Mechanism of the Stoltz-Grubbs (KOtBu/Et3SiH) Silylation: Single-Electron Transfer is the Missing Link between the Heterolytic and Radical Pathways.

A new mechanism for the Stoltz-Grubbs (KOtBu/Et3SiH) silylation of heteroarenes is reported that successfully resolves the important unexplained experimental features of the reaction. The mechanism combines hydride transfer, hydrogen atom transfer (HAT), and single electron transfer (SET) steps (with the substrate hydride adduct being identified as a new SET donor) and is supported by extensive theoretical calculations. Previously proposed heterolytic and radical mechanisms do not involve SET. The discovery of a mechanistic role for SET explains why the silylation reaction simultaneously displays both heterolytic and radical character, and why it does not require free silyl radicals. Previously unexplained experimental results from reactions of isotopically labelled reactants and on the inhibitory effects of electron-accepting additives can also be understood based on the SET mechanism.

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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.