Herein, we report the development of a tailored cobalt catalyst system of Cp*Co(III)(LX) toward intramolecular C-H nitrene insertion of azidoformates to afford cyclic carbamates. The cobalt complexes were easy to prepare and bench-stable, thus offering a convenient reaction protocol. The catalytic reactivity was significantly improved by the electronic tuning of the bidentate LX ligands, and the observed regioselectivity was rationalized by the conformational analysis and DFT calculations of the transition states. The superior performance of the newly developed cobalt catalyst system could be broadly applied to both C(sp2)-H and C(sp3)-H carbamation reactions under mild conditions.

中文翻译：

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用于选择性分子内 C-H 酰胺化反应的多功能 Cp*Co(III)(LX) 催化剂系统

在此，我们报告了针对叠氮甲酸酯的分子内 CH 氮烯插入以提供环状氨基甲酸酯的 Cp*Co(III)(LX) 定制钴催化剂系统的开发。钴配合物易于制备且在实验室中稳定，因此提供了方便的反应方案。双齿LX配体的电子调谐显着提高了催化反应性，并且通过构象分析和过渡态的DFT计算使观察到的区域选择性合理化。新开发的钴催化剂体系的优异性能可广泛应用于温和条件下的 C(sp2)-H 和 C(sp3)-H 氨基甲酸化反应。