Institute of Chemistry and BioMedical Sciences, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering , Nanjing University , Nanjing , 210093 , China.
Department of Chemistry and Biochemistry , Texas Tech University , Lubbock , Texas 79409-1061 , United States.
Org Lett. 2018 Oct 5;20(19):6260-6264. doi: 10.1021/acs.orglett.8b02738. Epub 2018 Sep 20.
An additive-assisted iridium-catalyzed directed C(sp)-H amination with 2,2,2-trichloroethoxycarbonyl azide as an amino source is reported. Both carboxylate anions and the corresponding cations in the additives are crucial to achieve satisfactory efficiency. Sodium acetate or n-pentanoic acid can promote the amination of various primary C(sp)-H bonds adjacent to secondary, tertiary, and quaternary carbons in ketoximes or N-aromatic heterocycles, respectively, providing a practical route to versatile β-amino ketoxime and N-heteroaryl ethanamine derivatives. The amination products can be treated as isocyanate analogues and can be converted to other useful amino functionalities. An iridacyclic compound was isolated and identified as a plausible intermediate.
本文报道了一种添加剂辅助的铱催化导向 C(sp^2)-H 胺化反应，以 2,2,2-三氯乙氧基羰基叠氮化物作为氨基源。添加剂中的羧酸根阴离子和相应的阳离子对于实现令人满意的效率至关重要。醋酸钠或正戊酸可以分别促进酮肟或 N-芳杂环中各种仲、叔和季碳原子相邻的 C(sp^2)-H 键的胺化反应，为合成各种β-氨基酮肟和 N-芳杂环乙胺衍生物提供了一条实用的路线。胺化产物可以作为异氰酸酯类似物处理，并转化为其他有用的氨基官能团。分离并鉴定得到了一种铱环化合物作为可能的中间体。
