On the ligand-free palladium cluster catalysed Suzuki-Miyaura reaction.
On the ligand-free palladium cluster catalysed Suzuki-Miyaura reaction.
复制标题
关于无配体钯簇催化的铃木-宫浦反应。
DOI：
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发表时间：
2020
期刊：
影响因子：
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通讯作者：
Parag A. Deshpande
中科院分区：
文献类型：
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作者：
Prasad Reddy Sesha Surya Vara Karri;Parag A. Deshpande
在过去的几十年里，C-C交叉偶联反应已广泛用于开发药物和农产品的合成方案。在所有报道的C-C交叉偶联反应中，铃木-宫浦反应是优选的，因为它的反应条件温和，相关试剂的商业可用性以及含硼副产物的易于去除。最近，Corma 和同事 [Leyva-Perez 等人，Angew。 Chem., 2013, 125, 11768]报道了水稳定的三原子和四原子钯簇作为 C-C 偶联反应的高活性催化物种。目前的工作重点是利用密度泛函理论计算对 Pd3 和 Pd4 团簇的 Suzuki-Miyaura 反应进行详细的机理研究。本研究分析了碱在反应中的作用，发现碱可以降低 Pd3 和 Pd4 的金属转移活化势垒。开发了溴苯和苯基硼酸在 Pd3 和 Pd4 簇上的 Suzuki-Miyaura 耦合的自由能图谱。 Pd3 和 Pd4 上的氧化加成的最高自由能垒分别为 34.7 和 30.4 kcal mol-1，表明氧化加成是限速步骤。详细的能量学最终证明了小原子钯团簇催化铃木-宫浦反应的活性。
C-C cross coupling reactions have been widely used for developing synthesis protocols for pharmaceuticals and agricultural products in the past few decades. Of all the reported C-C cross coupling reactions, the Suzuki-Miyaura reaction is preferred because of its mild reaction conditions, the commercial availability of associated reagents and the ease of removal of boron containing by-products. Recently, Corma and co-workers [Leyva-Perez et al., Angew. Chem., 2013, 125, 11768] reported water-stabilized three- and four-atom Pd clusters as highly active catalytic species for C-C coupling reactions. The present work focuses on developing detailed mechanistic insights into the Suzuki-Miyaura reaction with Pd3 and Pd4 clusters utilizing density functional theory calculations. The role of the base in the reaction was analysed in this study, which was found to lower the activation barriers of transmetalation over both Pd3 and Pd4. Free energy landscapes for Suzuki-Miyaura coupling of bromobenzene and phenylboronic acid over Pd3 and Pd4 clusters were developed. The highest free energy barriers of 34.7 and 30.4 kcal mol-1 were observed for the oxidative addition over Pd3 and Pd4, respectively, indicating the oxidative addition as the rate limiting step. Detailed energetics conclusively proved the active nature of small-atom Pd clusters for catalyzing the Suzuki-Miyaura reaction.
影响因子：
2.9
作者：
Humphrey, W;Dalke, A;Schulten, K
通讯作者：
Schulten, K