Gold Redox Catalysis through Base-Initiated Diazonium Decomposition toward Alkene, Alkyne, and Allene Activation.
Gold Redox Catalysis through Base-Initiated Diazonium Decomposition toward Alkene, Alkyne, and Allene Activation.
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DOI：
10.1002/chem.201701970
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发表时间：
2017-08-16
期刊：
影响因子：
--
通讯作者：
Shi X
中科院分区：
文献类型：
--
作者：
Dong B;Peng H;Motika SE;Shi X
光助重氮激活金(I)氧化的发现，避免了强氧化剂的使用，极大地扩展了金氧化还原催化的范围。限制这种新型化学应用的一些实际问题是相对较低的效率(反应时间长，转化率低)和必要的严格的反应条件控制(脱气和惰性反应环境)。在这里，通过Lewis碱诱导的重氮离子活化，开发了一种替代的无光条件。在该方法中，未反应的Au(I)催化剂与Na2CO3和重氮盐结合生成Au(III)中间体。实现了多种底物的有效活化，包括炔烃、烯烃和烯丙烯，然后快速还原消除Au(III)，从而以很好的产率得到C-C偶联产物。与以前报道的光激活方法相比，我们的方法通过更快的反应速度和更广泛的反应范围提供了更高的效率和通用性。具有挑战性的底物，如富电子/中性联烯，在光引发条件下不能被激活(<；5%的产率)，可以被活化，随后以良好到极好的产率产生所需的偶联产物。
The discovery of photo-assisted diazonium activation toward gold(I) oxidation greatly extended the scope of gold redox catalysis by avoiding the use of a strong oxidant. Some practical issues that limit the application of this new type of chemistry are the relative low efficiency (long reaction time and low conversion) and the strict reaction condition control that is necessary (degassing and inert reaction environment). Herein, an alternative photo-free condition has been developed through Lewis base induced diazonium activation. With this method, an unreactive Au(I) catalyst was used in combination with Na2CO3 and diazonium salts to produce a Au(III) intermediate. The efficient activation of various substrates, including alkyne, alkene and allene was achieved, followed by rapid Au(III) reductive elimination, which yielded the C-C coupling products with good to excellent yields. Relative to the previously reported photo-activation method, our approach offered greater efficiency and versatility through faster reaction rates and broader reaction scope. Challenging substrates such as electron rich/neutral allenes, which could not be activated under the photo-initiation conditions (<5% yield), could be activated to subsequently yield the desired coupling products in good to excellent yield.
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