Ligand‐Promoted Rhodium(III)‐Catalyzed ortho‐C−H Amination with Free Amines

• Published in: Angewandte Chemie International Edition Vol. 56; no. 26; pp. 7449 - 7453
• Main Authors: Wang, Huai‐Wei, Lu, Yi, Zhang, Bing, He, Jian, Xu, Hua‐Jin, Kang, Yan‐Shang, Sun, Wei‐Yin, Yu, Jin‐Quan
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 19.06.2017; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Amination; Amines; Chemical reactions; Chemistry; Chemistry, Multidisciplinary; Hydrogen bonds; ligand design; Ligands; Palladium; Physical Sciences; quinolines; Rhodium; Scaffolds; Science & Technology; ROOM-TEMPERATURE; INTERMOLECULAR AMINATION; amines; N-CHLOROAMINES; DIRECTING-GROUP; ANTHRANILIC ACIDS; C(SP)H BONDS; PALLADIUM-CATALYZED ALKYLATION; AMIDATING REAGENTS; MILD CONDITIONS; SULFONYL AZIDES; ligand design; amination; quinolines; rhodium
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201703300

Ligand development for rhodium(III)‐catalyzed C−H activation reactions has largely been limited to cyclopentadienyl (Cp) based scaffolds. 2‐Methylquinoline has now been identified as a feasible ligand that can coordinate to the metal center of Cp*RhCl to accelerate the cleavage of the C−H bond of N‐pentafluorophenylbenzamides, providing a new structural lead for ligand design. The compatibility of this reaction with secondary free amines and anilines also overcomes the limitations of palladium(II)‐catalyzed C−H amination reactions. 2‐Methylquinoline has been identified as an efficient ligand for promoting the rhodium(III)‐catalyzed directed C−H amination of N‐pentafluorophenylbenzamides, providing a new structural lead for ligand design for rhodium(III)‐catalyzed C−H activation. Secondary amines and primary anilines are compatible, which significantly expands the scope of C−H amination reactions with free amines.