We report herein a series of tailored Cp^XRh(LX)Cl catalyst systems for the outer-sphere C–H amidations discovered by high-throughput experimentation. Using a diverse repertoire of Cp-tunable group 9 [Cp^XMCl₂]₂ precatalysts in combination with bidentate LX-type co-ligands, we have established a premixing protocol for the fast and convenient in situ generation of an array of half-sandwich metal complexes. Benefitting from the designed multidimensional approach to simultaneously screen the metal center, Cp^X, LX-type co-ligands, and nitrene precursors, optimal Cp^XRh(III)(LX) catalysts were quickly identified for intra- and intermolecular C–H amidations and also for an enantioselective transformation using N-tosyloxycarbamates as the nitrenoid precursor.

中文翻译：

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多维筛选加速发现用于选择性分子内和分子间 C-H 酰胺化的铑催化剂体系

我们在此报告了一系列定制的 Cp ^X Rh(LX)Cl 催化剂体系，用于通过高通量实验发现的外球 C-H 酰胺化。使用多种 Cp 可调组 9 [Cp ^X MCl ₂ ] ₂预催化剂与双齿 LX 型共配体组合，我们建立了一种预混方案，用于快速方便地原位生成半夹心阵列金属络合物。受益于设计的多维方法同时筛选金属中心、Cp ^X、LX 型共配体和氮烯前体，最佳 Cp ^XRh(III)(LX) 催化剂被快速鉴定用于分子内和分子间 C-H 酰胺化，以及使用N-甲苯磺酰氧基氨基甲酸酯作为 Nirenoid 前体的对映选择性转化。