TMP-cadmiate: A base for Efficient and Chemoselective Deprotonative Metallation Reactions of Aromatic Compounds

Florence Mongin (1) , Masanobu Uchiyama (2)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 RIKEN - RIKEN - Institute of Physical and Chemical Research [Japon]

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. The lithium arylcadmiates such generated have been evidenced using iodine. Alternative trappings of the species are palladium-catalyzed cross-coupling reactions or simple quench with acid chlorides.

Mots clés: cadmium; lithium; deprotonative metallation; DFT calculations; aromatic; heterocycle; cross-coupling; electrophile

Domaines: Chimie organique; Chimie théorique et/ou physique

Florence Mongin, Masanobu Uchiyama. TMP-cadmiate: A base for Efficient and Chemoselective Deprotonative Metallation Reactions of Aromatic Compounds. Current Organic Chemistry, 2011, 15, pp.2340-2361. ⟨10.2174/138527211796150651⟩. ⟨hal-01053743⟩