Computational characterization of the role of the base in the Suzuki-Miyaura cross-coupling reaction
Computational characterization of the role of the base in the Suzuki-Miyaura cross-coupling reaction
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DOI：
10.1021/ja050583i
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发表时间：
2005-06-29
影响因子：
15
通讯作者：
Maseras, F
中科院分区：
文献类型：
--
作者：
Braga, AAC;Morgon, NH;Maseras, F
碱在Suzuki-Miyaura交叉偶联反应的金属转移步骤中的作用通过DFT计算与Becke 3LYP泛函分析。研究的模型体系由Pd（CH= CH_2）（PH_3）（2）Br作为起始催化剂络合物、CH_2 =CHB（OH）（2）作为有机硼酸和OH-作为碱组成。两个主要的机制建议，包括攻击的第一个钯络合物或有机硼酸的碱，通过相应的中间体和过渡态的几何优化进行评估。对未催化的反应和起始络合物为Pd（CH= CH 2）（PH 3）（2）（OH）的过程进行了补充计算。这些计算，与现有的实验数据一起考虑，强烈表明，在催化循环中的transmetalation的主要机制开始与碱和有机硼酸的反应。
The role of the base in the transmetalation step of the Suzuki-Miyaura cross-coupling reaction is analyzed computationally by means of DFT calculations with the Becke3LYP functional. The model system studied consists of Pd(CH=CH2)(PH3)(2)Br as the starting catalyst complex, CH2=CHB(OH)(2) as the organoboronic acid, and OH- as the base. The two main mechanistic proposals, consisting of the base attacking first either the palladium complex or the organoboronic acid, are evaluated through geometry optimization of the corresponding intermediates and transition states. Supplementary calculations are carried out on the uncatalyzed reaction and on a process where the starting complex is Pd(CH=CH2)(PH3)(2)(OH). These calculations, considered together with available experimental data, strongly suggest that the main mechanism of transmetalation in the catalytic cycle starts with the reaction of the base and the organoboronic acid.