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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Mechanistic Investigation of Aromatic C(sp(2))-H and Alkyl C(sp(3))-H Bond Insertion by Gold Carbenes
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Mechanistic Investigation of Aromatic C(sp(2))-H and Alkyl C(sp(3))-H Bond Insertion by Gold Carbenes

机译：金卡宾对芳族C（sp（2））-H和烷基C（sp（3））-H键插入的机理研究

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摘要

It was recently reported that the gold-carbenes have an unprecedented catalysis toward the functionalization of C(sp(2))-H bonds of aromatic compounds. However, the associated mechanisms of C(sp(2))-H bonds inserted by gold-carbenes have not been comprehensively understood. We carried Out a detailed mechanistic investigation of gold-carbene insertion into the C(sp(2))-H bond of anisole by means of theoreticd calculations and control experiments. It significantly reveals that the aromatic C(sp(2))-H bond activation starts with the electrophilic addition of aromatic carbon toward, the carbene carbon and subsequently followed the [1,3]-proton shift to form an enol intermediate. The rearrangement of enol proceeds through the mechanisms of proton transfer assisted by water molecules or enol intermediates, which are supported by Our control experiments. It was also found that the C(sp(3))-H insertions of alkanes by gold-carbenes proceed through a concerted process via a three-centered transition state. The further comparison of different mechanisms provides a clear theoretical scheme to account for the difference in aromatic C(sp(3))-H and alkyl C(sp(3))-H bond activation, which is instructive for the further experimental functionalization of C-H bonds by gold-carhenes.
机译：最近有报道说，金卡宾对芳香化合物的C（sp（2））-H键的功能化具有空前的催化作用。但是，尚未完全了解金卡宾插入的C（sp（2））-H键的相关机制。我们通过理论计算和控制实验对金卡宾插入苯甲醚的C（sp（2））-H键进行了详细的机理研究。它显着揭示了芳族C（sp（2））-H键的活化开始于向碳烯碳的亲电加成芳族碳，然后跟随[1,3]-质子转移形成烯醇中间体。烯醇的重排通过水分子或烯醇中间体辅助的质子转移机理进行，这得到了我们的对照实验的支持。还发现金卡宾的烷烃的C（sp（3））-H插入通过三中心过渡态通过协同过程进行。进一步比较不同的机制提供了一个清晰的理论方案，以说明芳香族C（sp（3））-H和烷基C（sp（3））-H键活化的差异，这对进一步实验功能化具有指导意义CH-通过金-carhenes键。

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