Kinetic Analysis of Domino Catalysis: A Case Study on Gold-Catalyzed Arylation
Kinetic Analysis of Domino Catalysis: A Case Study on Gold-Catalyzed Arylation
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DOI：
10.1021/acscatal.0c03178
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发表时间：
2020-09-18
期刊：
影响因子：
12.9
通讯作者：
Lloyd-Jones, Guy C.
中科院分区：
文献类型：
--
作者：
Ball, Liam T.;Corrie, Tom J. A.;Lloyd-Jones, Guy C.
多米诺催化是提高多步反应效率的有效途径。然而，在“单一催化机制影响多重转化”的过程中，有效周转所需的动力学特征尚未得到详细探讨。本文通过金催化两个缺电子芳基硅烷偶联生成芳基化芴，分析了表面上简单的两级多米诺催化反应的动力学。原位交错H-1和F-19核磁共振光谱动力学测量、动力学模拟和取代变化的结合揭示了催化剂在两个不同循环之间的分配如何影响该过程的速率和选择性。这一见解使识别出顺序的催化剂形态和多米诺中间体的积累是有效的多米诺催化的一般动力学标准。
Domino catalysis is a well-explored route to increasing the efficiency of multistep reactions. However, the kinetic features required for efficient turnover of a process where "multiple transformations are effected by a single catalytic mechanism" have not been explored in any detail. The kinetics of a nominally simple two-stage domino catalytic reaction have been analyzed by way of a gold-catalyzed coupling of two electron-deficient arylsilanes to generate an arylated fluorene. A combination of in situ interleaved H-1 and F-19 NMR spectroscopic kinetic measurements, kinetic simulations, and variations in substitution reveal how the catalyst partitioning between the two different cycles impacts both the rate and the selectivity of the process. The insight enables identification that sequential catalyst speciation and accumulation of the domino intermediate are general kinetic criteria for efficient domino catalysis.