First examples of post‐polymerization functionalization of poly(3,4‐ethylenedioxythiophene) (PEDOT) derivatives are reported using tetrathiafulvalene (TTF) as a redox sensitive probe. EDOT derivatives bearing ω‐iodo‐alkyl or ω‐iodo‐polyether chains attached at the ethylenedioxy bridge have been electropolymerized and the resulting polymers have been derivatized using a TTF bearing a thiolate anion liberated under mild conditions. Cyclic voltammetry confirms the rapidity and efficiency of the derivatization process. This facile post‐polymerization functionalization coupled with the unique properties of PEDOT should lead to interesting developments in the field of modified electrodes, which includes selective electrochemical sensors.

In situ mixtures of CdCl(2)TMEDA (0.5 equiv; TMEDA = N,N,N',N'-tetramethylethylenediamine) or InCl(3) (0.33 equiv) with [Li(tmp)] (tmp = 2,2,6,6-tetramethylpiperidino; 1.5 or 1.3 equiv, respectively) were compared with the previously described mixture of ZnCl(2)TMEDA (0.5 equiv) and [Li(tmp)] (1.5 equiv) for their ability to deprotonate anisole, benzothiazole, and pyrimidine. [(tmp)(3)CdLi] proved to be the best base when used in tetrahydrofuran at room temperature, as demonstrated by subsequent trapping with iodine. The Cd-Li base then proved suitable for the metalation of a large range of aromatics including benzenes bearing reactive functional groups (CONEt(2), CO(2)Me, CN, COPh) or heavy halogens (Br, I), and heterocycles (from the furan, thiophene, pyrrole, oxazole, thiazole, pyridine, and diazine series). Five-membered heterocycles benefiting from doubly activated positions were similarly dideprotonated at room temperature. The aromatic lithium cadmates thus obtained were involved in palladium-catalyzed cross-coupling reactions or simply quenched with acid chlorides.

No abstract

No abstract

This communication describes the deproto-metalation of a large range of aromatics including heterocycles using a newly developed lithium-cadmium base; the reaction proceeds at room temperature with an excellent chemoselectivity and efficiency, and proved to be regioselective in most cases.