Copper(I)-Catalyzed Dehydrogenative Amidation of Arenes Using Air as the Oxidant

• Published in: Advanced synthesis & catalysis Vol. 357; no. 6; pp. 1311 - 1315
• Main Authors: Li, Gang, Jia, Chunqi, Chen, Qingliang, Sun, Kai, Zhao, Feng, Wu, Hankui, Wang, Zhiyong, Lv, Yunhe, Chen, Xiaolan
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 13.04.2015; WILEY‐VCH Verlag; Wiley
• Subjects: air; Amides; amination; Aromatic compounds; Bonding; Chemistry; Chemistry, Applied; Chemistry, Organic; copper; CH activation; Dehydrogenation; Derivatives; Oxidants; Oxidizing agents; Physical Sciences; Science & Technology; Solvents; Terminals; ROOM-TEMPERATURE; ELECTROPHILIC AMINATION; air; C-H BONDS; ACTIVATION REACTIONS; ARYLBORONIC ACIDS; AROMATIC-AMINES; BORONIC ACIDS; QUINOLINE N-OXIDES; CATALYZED INTERMOLECULAR AMINATION; C-H activation; copper; amination; dehydrogenation; ARYL IODIDES
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.201400883

The copper(I) bromide‐catalyzed intermolecular dehydrogenative amidation of arenes via CH bond activation assisted by a 2‐pyridyl or 1‐pyrazolyl chelating group using air as the terminal oxidant has been achieved at 140 °C. N‐Aryl amides, N‐alkyl amides, benzamide derivatives, imides, and lactams all are good coupling partners to obtain moderate to excellent yields. The amount of solvent is critical for the transformation: both increasing and decreasing the amount of solvent decreased the yield. Notably, the amidation of bimolecular 2‐phenylpyridine with the dual NH bonds of a primary amide proceeded smoothly in one‐pot to afford a good yield under the same conditions. The amidation can be performed with a good yield at the gram scale.