IOct (IOctyl) - pushing the limits of IBu: highly hindered electron-rich N-aliphatic N-heterocyclic carbenes.

IBu (IBu = 1,3-di--butylimidazol-2-ylidene) represents the most important and most versatile -alkyl N-heterocyclic carbene available in organic synthesis and catalysis. Herein, we report the synthesis, structural characterization and catalytic activity of IOct (IOctyl), -symmetric, higher homologues of IBu. The new ligand class, including saturated imidazolin-2-ylidene analogues has been commercialized in collaboration with MilliporeSigma: IOct, 929 298; SIOct, 929 492 to enable broad access of the academic and industrial researchers within the field of organic and inorganic synthesis. We demonstrate that replacement of the -Bu side chain with -Oct results in the highest steric volume of -alkyl N-heterocyclic carbenes reported to date, while retaining the electronic properties inherent to N-aliphatic ligands, such as extremely strong σ-donation crucial to the reactivity of -alkyl N-heterocyclic carbenes. An efficient large-scale synthesis of imidazolium IOct and imidazolinium SIOct carbene precursors is presented. Coordination chemistry to Au(i), Cu(i), Ag(i) and Pd(ii) as well as beneficial effects on catalysis using Au(i), Cu(i), Ag(i) and Pd(ii) complexes are described. Considering the tremendous importance of IBu in catalysis, synthesis and metal stabilization, we anticipate that the new class of IOct ligands will find wide application in pushing the boundaries of new and existing approaches in organic and inorganic synthesis.