Mechanistic Investigation into the Gold-Catalyzed Decarboxylative Cross-Coupling of Iodoarenes
Mechanistic Investigation into the Gold-Catalyzed Decarboxylative Cross-Coupling of Iodoarenes
复制标题
DOI：
10.1021/acscatal.1c01631
复制
发表时间：
2021-07-16
期刊：
影响因子：
12.9
通讯作者：
Topczewski, Joseph J.
中科院分区：
文献类型：
--
作者：
Daley, Ryan A.;Morrenzin, Aaron S.;Topczewski, Joseph J.
虽然许多金催化的反应已经被彻底开发，但大多数都不被认为涉及金的氧化还原事件。相比之下，最近的进展已经证明了氧化还原金催化的可行性。这份报告描述了一个详细的机械调查的金催化脱羧的交叉耦合，这可能是通过高价Au（I/III）途径收益。这项调查包括动力学分析，化学计量实验与Au（III）配合物，和密度泛函理论计算。这些数据支持一个营业额限制氧化除了形成一个Au（III）芳基配合物，与关闭周期的休息状态。主要的途径似乎是通过银介导的脱羧与随后的Ag（I）到Au（III）transmetalation。这些数据为SbF 6-和NTf 2-之间的显著协同效应提供了一些理论依据。
While many gold-catalyzed reactions have been thoroughly developed, most are not thought to involve redox events at gold. In contrast, recent advances have demonstrated the feasibility of redox gold catalysis. This report describes a detailed mechanistic investigation of the gold-catalyzed decarboxylative cross-coupling, which likely proceeds via a high-valent Au(I/III) pathway. This investigation includes a kinetic analysis, stoichiometric experiments with Au(III) complexes, and density functional theory calculations. These data support a turnover-limiting oxidative addition to form a Au(III) aryl complex, with an off-cycle resting state. The dominant pathway appears to proceed through a silver-mediated decarboxylation with a subsequent Ag(I) to Au(III) transmetalation. These data provide some rationale for the significant counterion effects between SbF6- and NTf2-.