Song Geyang, Song Jiameng, Li Qi, Kang Tengfei, Dong Jianyang, Li Gang, Fan Juan, Wang Chao, Xue Dong
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, China.
J Am Chem Soc. 2024 Oct 2;146(39):26936-26946. doi: 10.1021/jacs.4c08130. Epub 2024 Sep 18.
Transition-metal-catalyzed amination of aryl halides is one of the most employed methods for constructing -arylation adducts. However, the broad success of these reactions largely relies on the screening of precatalysts, elaborated ligands, and case-by-case optimization of reaction conditions (solvent, base, additive, temperature, ) for electronically or structurally diverse nucleophiles. Herein, we report an adaptive photochemical C-N coupling of aryl halides with various nitrogen nucleophiles (aliphatic and aromatic amines, amides, sulfonamides, pyrazoles, and ammonium salts) by Co(II) catalysis under the same reaction conditions (same precatalyst, same ligand, same base, same solvent, same temperature) without the addition of any exogenous photocatalyst. This photochemical amination features a wide substrate scope (>130 examples, up to 95% yield) with excellent functional group tolerance. Mechanistic studies indicate that these C-N coupling reactions may proceed via a Co(I)/Co(III) catalytic cycle.
过渡金属催化的芳基卤化物胺化反应是构建芳基化加合物最常用的方法之一。然而，这些反应的广泛成功很大程度上依赖于对预催化剂、精心设计的配体的筛选，以及针对电子或结构多样的亲核试剂对反应条件（溶剂、碱、添加剂、温度等）进行逐例优化。在此，我们报道了一种在相同反应条件下（相同的预催化剂、相同的配体、相同的碱、相同的溶剂、相同的温度），通过钴（II）催化实现芳基卤化物与各种氮亲核试剂（脂肪族和芳香族胺、酰胺、磺酰胺、吡唑和铵盐）的自适应光化学C-N偶联反应，且无需添加任何外源光催化剂。这种光化学胺化反应具有广泛的底物范围（>130个实例，产率高达95%），对官能团具有优异的耐受性。机理研究表明，这些C-N偶联反应可能通过Co（I）/Co（III）催化循环进行。
