Pd/Mg(OH)2/MgO–ZrO2 Nanocomposite Systems for Highly Efficient Suzuki–Miyaura Coupling Reaction at Room Temperature: Implications for Low-Carbon Green Organic Synthesis
Pd/Mg(OH)2/MgO–ZrO2 Nanocomposite Systems for Highly Efficient Suzuki–Miyaura Coupling Reaction at Room Temperature: Implications for Low-Carbon Green Organic Synthesis
复制标题
Pd/Mg(OH)2/MgO·ZrO2 纳米复合体系用于室温下高效 Suzuki·Miyaura 偶联反应：对低碳绿色有机合成的启示
DOI：
10.1021/acsanm.2c01179
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发表时间：
2022
影响因子：
5.9
通讯作者：
Tao Shengyang
中科院分区：
文献类型：
--
作者：
Zhang Lijing;Han Jiaqi;Wang Yuchao;Yang Wenbo;Tao Shengyang
实现高效的室温铃木-宫仓偶联(SMC)对发展低碳有机合成具有重要意义。然而，构建一种具有高活性的纳米催化剂用于室温SMC反应仍然是一个巨大的挑战。本文以MgO-ZrO2杂化纳米纤维为基础，合理地研制了一种强碱支载的Pd/Mg(OH)2/MgO-ZrO2纳米催化剂。物理化学表征表明，纳米纤维表面的氧化镁原位转化为氢氧化镁，使载体表面的碱度大大增加。强碱性能极大地促进SMC过程的氧化加成和转金属反应，导致反应活化能明显降低(Ph-BR的Ea=9.0kJmol-1)。在室温下反应8min，偶联转化率可达100%，最大TOF>为6516h~(-1)。在底物适应性和氯苯活化方面也表现出良好的性能。合理设计高碱度常温SMC催化剂，将是发展低碳绿色有机合成的有益尝试。
Achieving a room-temperature Suzuki–Miyaura coupling (SMC) with high efficiency is of great significance to the development of low-carbon organic synthesis. Nevertheless, it is still a great challenge to construct a promising nanocatalyst with high activity for room-temperature SMC reaction. In this paper, a strong alkaline-supported nanocatalyst Pd/Mg(OH)2/MgO–ZrO2was rationally developed based on MgO–ZrO2hybrid nanofibers. Physicochemical characterizations present that the in situ conversion of MgO to Mg(OH)2on the surface of the nanofibers results in a great increase in surface alkalinity of the carrier. The strong alkalinity can greatly accelerate the oxidation addition and transmetalation of the SMC process, resulting in the obvious reduction of activation energy of the reaction (Ea= 9.0 kJmol–1for Ph–Br). The coupling conversion can reach up to 100% at room temperature within 8 min with a maximum TOF > 6516 h–1. It also shows an excellent performance in substrate applicability and chlorobenzene activation. The rational design of a high-basicity catalyst for room-temperature SMC will be a rewarding attempt for the development of low-carbon green organic synthesis.