Abstract
Efficient deprotonative cadmiation reactions of functionalized aromatics including heterocycles have been realized using TMP-cadmiate, (TMP)3CdLi (TMP = 2,2,6,6-tetramethylpiperidino). The reagent is compatible with reactive functional groups (amide, ester, nitrile and even ketone functions), heavy halogens (Br, I), five-membered aromatic heterocycles (furan, thiophene, oxazole, thiazole, and pyrrole derivatives) and even aromatic aza-heterocycles (pyridine, diazine compounds). Some heterocycles benefiting from doubly activated positions can be dimetallated at room temperature. The deprotonative cadmiation pathways/mechanisms have been studied using computational/theoretical techniques. Such generated lithium arylcadmiates have been evidenced using iodine. Alternative trappings of the species are palladium-catalyzed cross-coupling reactions or simple quench with acid chlorides.
Keywords: Cadmium, lithium, deprotonative metallation, DFT calculations, aromatic, heterocycle, cross-coupling, electrophile, Halopyridines, deproto-metallation, Cyanopyridines, Pyridine Esters, Bare Diazines, FERROCENES, LITHIUM ARYLCADMIATES
Call for Papers in Thematic Issues
Catalytic C-H bond activation as a tool for functionalization of heterocycles
The major topic is the functionalization of heterocycles through catalyzed C-H bond activation. The strategies based on C-H activation not only provide straightforward formation of C-C or C-X bonds but, more importantly, allow for the avoidance of pre-functionalization of one or two of the cross-coupling partners. The beneficial impact of ...read more
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