The application of atomically precise nanocluster-based catalysts in organic synthesis has been practiced for decades. Such nanoclusters have been used as ideal catalysts as their structures are designable at the atomic level, their confined structures are conducive to mechanistic study, and most of them can be recycled during the synthesis process. The catalysis of coupling reactions using nanoclusters is an advanced methodology to build complicated carbohydrate scaffolds in one step. The history of atomically precise nanocluster-catalyzed coupling reactions is short; however, the past decade has witnessed the prosperity of this field-atomically precise nanocluster-catalyzed carbon–carbon coupling reactions including many named reactions, carbon–heteroatom coupling reactions, and multi-component coupling reactions have been reported and extensively applied in medicinal chemistry and materials science. The components and geometries of metal nanoclusters, such as ligands, motifs, metal cores, and supports, affect their catalytic abilities synergistically. This review summarizes carbon–carbon and carbon–heteroatom coupling reactions over atomically precise nanoclusters and highlights the correlations between nanoclusters’ catalytic properties and their specific components. Guidance for choosing suitable nanoclusters for specific coupling reactions and possible research directions in this field have been proposed. We hope that this review will provide researchers attempting to study the coupling reactions catalyzed by metal nanoclusters with a comprehensively catalytic toolbox and insightful research fundamentals, so as to provide tailor-made approaches to achieve more efficient cluster-based catalysts towards coupling reactions.

中文翻译：

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原子级精确的纳米团簇催化偶联反应


原子级精确的纳米团簇催化剂在有机合成中的应用已经实践了几十年。这种纳米团簇已被用作理想的催化剂，因为它们的结构可以在原子水平上设计，其受限结构有利于机理研究，并且大多数可以在合成过程中回收。使用纳米团簇催化偶联反应是一种一步构建复杂碳水化合物支架的先进方法。原子级精确的纳米团簇催化偶联反应的历史很短；然而，过去十年见证了这种场原子精确纳米团簇催化的碳-碳偶联反应的繁荣，包括许多命名反应、碳-杂原子偶联反应和多组分偶联反应已被报道并广泛应用于药物化学和化学领域。材料科学。金属纳米团簇的成分和几何形状，如配体、基序、金属核和载体，协同影响其催化能力。这篇综述总结了原子级精确纳米团簇上的碳-碳和碳-杂原子偶联反应，并强调了纳米团簇的催化性能与其特定组分之间的相关性。提出了为特定偶联反应选择合适纳米团簇的指南以及该领域可能的研究方向。我们希望这篇综述能为尝试研究金属纳米团簇催化的偶联反应的研究人员提供全面的催化工具箱和富有洞察力的研究基础，从而为实现更高效的基于团簇的偶联反应催化剂提供量身定制的方法。