Non-classical anionic naked N-heterocyclic carbenes: fundamental properties and emerging applications in synthesis and catalysis

Ongoing research exploring the chemistry of N-heterocyclic carbenes (NHCs) has led to the development and discovery of new NHC subclasses that deviate beyond Arduengo’s prototypical N,N′-disubstituted imidazol-2-ylidene-based structures. These systems continue to enable and extend the fundamental role of NHC ligands in synthesis and catalysis. In this regard, the advent of protic NHCs has garnered particular interest. This derives in part from their applications to the selective preparation of unique molecular scaffolds and their unprecedented bifunctional reactivity, which can be exploited in transition metal-catalyzed processes. In comparison, the synthetic applications of closely related anionic naked NHCs remain rather underexplored. With this in mind, this review highlights the interesting fundamental properties of non-classical anionic naked NHCs, and focuses on their emerging applications in synthesis and catalysis.