Dehydrogenative Coupling Reaction for the Synthesis of 5‐ and 6‐Heterocyclic Derivatives Catalyzed by Earth‐Abundant Metal‐Based Complexes

Abstract Heterocycle synthesis is an intense research area due to their significant importance in pharmaceutical, material chemistry and fine synthesis. Key innovations include transition metal‐based‐catalyzed heterocyclic derivatives synthesis, which facilitates diverse structural modifications, enhances selectivities and efficiency. The necessity to develop more greener technologies for the construction of new C−C and C−N bonds has strived chemists to re‐design their synthetic strategy plan and to introduce abundant starting materials. Among these new transformations, acceptorless dehydrogenative coupling (ADC) reactions have received increased attention thanks to their atom‐economy, the use of alcohols as pro‐electrophiles and the formation of water and hydrogen gas as only by‐products. These methods exemplify the interplay between traditional and cutting‐edge techniques, providing a robust synthetic toolkit to address the growing demand for biologically relevant compounds with tailored functionalities. This review will focus on the acceptorless dehydrogenative coupling methodologies for the synthesis of nitrogen‐containing 5‐ and 6‐membered heterocyclic derivatives (such as pyrroles, pyrimidines, quinazolines, and quinoxalines) in the presence of 3d‐metal complexes. The state of the art of the ADC process underscores the continuous evolution of synthetic strategies and emphases its importance in creating valuable and structurally diverse compounds, ensuring their centrality in both academic and pharmaceutical research.