An Isolated Lithium <i>ortho</i>-Carboranyl Cuprate Complex for the Synthesis of Multiple-Carborane-Substituted Arenes from (Hetero)Aryl Bromides and Chlorides
Carborane-substituted arenes have emerged as versatile building blocks in medicinal chemistry, materials science, and coordination chemistry owing to the unique three-dimensional aromaticity, exceptional stability, and bioisosteric properties of carboranes. However, the existing synthetic routes to...
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2025
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| Summary: | Carborane-substituted arenes have emerged as versatile building blocks in medicinal chemistry, materials science, and coordination chemistry owing to the unique three-dimensional aromaticity, exceptional stability, and bioisosteric properties of carboranes. However, the existing synthetic routes to carborane-substituted arenes via C–C bond formation often rely on complex and laborious <i>in situ</i> procedures using aryl iodides, thus severely limiting the scope of their practical applications. Here, we report the isolation and characterization of a lithium bis(<i>o</i>-carboran-1-yl)cuprate complex (<b>Li/Cu-1</b>) that enables the efficient “dump-and-stir” synthesis of carborane-substituted arenes from readily available aryl bromides and chlorides. Remarkably, isophthalonitrile functions as a ligand for the Li center in <b>Li/Cu-1</b>, leaving the Cu center available for the oxidative addition to aryl halides. This represents a paradigm shift from traditional approaches using pyridines as ligands for Cu centers. Our method provides access to a diverse array of unprecedented molecules, including multiple-carborane-substituted or carborane-fused arenes, thereby converting a hitherto difficult transformation in synthetic chemistry into a practical and scalable process. |
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