Atomically precise nanocluster-catalyzed coupling reactions

Abstract

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.