Ligand Exchange as the First Irreversible Step in the Nickel-Catalyzed Cross-Coupling Reaction of Grignard Reagents
Ligand Exchange as the First Irreversible Step in the Nickel-Catalyzed Cross-Coupling Reaction of Grignard Reagents
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DOI：
10.1021/ja807000a
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发表时间：
2008-11-19
影响因子：
15
通讯作者：
Nakamura, Eiichi
中科院分区：
文献类型：
--
作者：
Yoshikai, Naohiko;Matsuda, Hirokazu;Nakamura, Eiichi
通过动力学同位素效应分析和理论计算对镍催化的格氏试剂交叉偶联反应的机理进行了研究，结果表明，产物-底物配体交换过程是反应的第一个不可逆步骤，影响反应的转化效率和选择性.另一方面，氧化加成步骤是Pd催化中的第一个不可逆步骤。这一发现具有有用的影响，有效的镍催化剂的发展，也说明了催化剂周转步骤的重要性，迄今为止收到较少的关注比随后的催化步骤。
Mechanistic studies of the Ni-catalyzed cross-coupling reaction of Grignard reagents through analysis of kinetic isotope effects and theoretical calculations indicated that the product-to-substrate ligand exchange process is the first irreversible step and affects the turnover efficiency and selectivity of the reaction. On the other hand, the oxidative addition step is the first irreversible step in Pd catalysis. This finding has useful implications for the development of efficient Ni catalysis and also illustrates the importance of the catalyst turnover step that has so far received less attention than subsequent catalytic steps.