The direct C–H functionalization methodology has first been applied to perform transition metal-free C–H/C–Li cross-couplings of 2H-imidazole 1-oxides with carboranyllithium. This atom- and step-economical approach, based on one-pot reactions of nucleophilic substitution of hydrogen (SN H) in non-aromatic azaheterocycles, affords novel imidazolyl-modified carboranes of two types (N-oxides and their deoxygenative analogues), which are particularly of interest in the design of advanced materials.

Azaheterocyclic derivatives of 1,2-dicarba-closo-dodeca­borane (ortho-carborane) are known to be of particular interest due to numerous plausible applications, particularly, in medicine, materials science, and advanced technologies. Three principal synthetic strategies resulting in azaheterocyclic carboranes, in which boron-enriched and azaheterocyclic fragments are linked to each other, either directly by means of the C–C bonds or through a short spacer (CH2, CH2S, CH2O, etc.), have been outlined. These synthetic approaches are of general character and can be used both individually and in combination to afford promising organoboron clusters of diverse architectures.1 Introduction2 C–C Cross-Coupling Strategies in the Synthesis of Azahetero­cyclic Carboranes3 Carboryne-Based Transformation Strategies4 Condensation Strategies: Reactions of Decaborane B10H14 with Substituted Acetylenes5 Conclusion and Outlook

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