Nickel versus Palladium in Cross-Coupling Catalysis: On the Role of Substrate Coordination to Zerovalent Metal Complexes
Nickel versus Palladium in Cross-Coupling Catalysis: On the Role of Substrate Coordination to Zerovalent Metal Complexes
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DOI：
10.1055/s-0039-1690045
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发表时间：
2020-02-01
影响因子：
2.6
通讯作者：
Nelson, David J.
中科院分区：
文献类型：
--
作者：
Cooper, Alasdair K.;Burton, Paul M.;Nelson, David J.
通过竞争实验、稳健性筛选和密度泛函理论计算，详细比较了配位官能团对镍和钯催化的Suzuki-Miyaura反应性能的影响。镍可以与多种官能团相互作用，这在竞争性交叉偶联反应中表现为选择性。外源添加剂上这些官能团的存在对交叉偶联反应有影响，范围从产率的轻微提高到反应的完全停止。相比之下，钯与这些官能团的相互作用不够强，不足以在交叉偶联反应中诱导选择性；钯催化的交叉偶联反应的选择性主要由芳基卤化物的电子性质决定。
A detailed comparison of the effect of coordinating functional groups on the performance of Suzuki-Miyaura reactions catalysed by nickel and palladium is reported, using competition experiments, robustness screening, and density functional theory calculations. Nickel can interact with a variety of functional groups, which manifests as selectivity in competitive cross-coupling reactions. The presence of these functional groups on exogenous additives has effects on cross-coupling reactions that range from a slight improvement in yield to the complete cessation of the reaction. In contrast, palladium does not interact sufficiently strongly with these functional groups to induce selectivity in cross-coupling reactions; the selectivity of palladium-catalysed cross-coupling reactions is predominantly governed by aryl halide electronic properties.