Cross‐Coupling of C−H and N−H Bonds: A Hydrogen Evolution Strategy for the Construction of C−N Bonds

• Published in: European journal of organic chemistry Vol. 2022; no. 31
• Main Authors: Ravindar, Lekkala, Hasbullah, Siti Aishah, Hassan, Nurul Izzaty, Qin, Hua‐Li
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 19.08.2022
• Subjects: Chemical reactions; Couplings; Cross coupling; C−H Amidation; C−H Amination; Dehydrogenation; Electro-oxidation; Hydrogen evolution; Photo-catalyst; Transition metal catalyst
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.202200596

The progress in C−N bond construction is significant in synthetic and biological chemistry. Cross‐dehydrogenative couplings of C−H and N−H motifs serve as a unique class of the most atom‐economical and straightforward strategies for constructing C−N bonds. Herein, we enclosed the most updated methodologies developed in the assembly of C−N bonds via photo‐catalyzed, transition‐metal‐catalyzed, electrochemical, and metal‐free amination and amidation reactions of saturated and unsaturated C−H bonds. Compared with the well‐established transition‐metal‐catalyzed protocols, electricity, or visible light‐mediated amination and amidation reactions are competent and appealing. Plausible mechanistic pathways are also described in representative amidation and amination reactions to provide insights for the future development of environmentally kind processes. Dehydrogenative C−H/N−H cross‐coupling serves as one of the most straightforward and atom‐economical approaches for C−N bond formation. This review covers most of the strategies involving electrochemical, photo‐catalyzed, transition‐metal‐catalyzed, and metal‐free amination and amidation reactions of saturated and unsaturated C−H bonds.