多功能 Cp*Co(III)(LX) 催化剂体系用于选择性的分子内 C-H 酰胺化反应。
Versatile Cp*Co(III)(LX) Catalyst System for Selective Intramolecular C-H Amidation Reactions.
机构信息
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, South Korea.
Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 34141, South Korea.
出版信息
J Am Chem Soc. 2020 Jul 15;142(28):12324-12332. doi: 10.1021/jacs.0c04448. Epub 2020 Jul 1.
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(sp)-H and C(sp)-H carbamation reactions under mild conditions.
在此，我们报告了一种定制的钴催化剂体系 Cp*Co(III)(LX) 的开发，该体系可用于叠氮甲酸酯的分子内 C-H 氮烯插入，以得到环状氨基甲酸酯。钴配合物易于制备且在实验台上稳定，因此提供了一种方便的反应方案。通过双齿 LX 配体的电子调谐，显著提高了催化反应活性，通过过渡态的构象分析和 DFT 计算，对观察到的区域选择性进行了合理化。在温和条件下，新开发的钴催化剂体系的优异性能可广泛应用于 C(sp)-H 和 C(sp)-H 碳化反应。
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