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

Abstract 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.