Transition-Metal-Catalyzed Dehydrocoupling: A Convenient Route to Bonds between Main-Group Elements

The development of transition‐metal‐catalyzed dehydrocoupling reactions as a synthetic method for the formation of main‐group element–element bonds provides an increasingly attractive and convenient alternative to traditional routes such as salt metathesis/elimination‐type reactions. Since the first reported examples in the early 1980s, there has been a rapid expansion of this field, with extensions to a wide variety of metal‐mediated homonuclear and heteronuclear bond‐forming processes. Applications of this new chemistry in molecular and polymer synthesis, materials science, hydrogen storage and the transfer hydrogenation of organic substrates are attracting growing attention. An overview of this emerging area is presented in this Concepts article with a focus on recent results. Catalytic dehydrocoupling (see scheme) plays an increasingly important role in the formation of new molecules, polymers, and materials based on main‐group elements, and also has potential applications with respect to the development of transfer hydrogenation reactions in organic synthesis and hydrogen‐storage materials.