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Article Dans Une Revue Journal of Organic Chemistry Année : 2007

Deprotonative metalation of five-membered aromatic heterocycles using mixed lithium-zinc species

Résumé

Deprotonation of benzoxazole, benzothiazole, benzo[b]thiophene, benzo[b]furan, N-Boc protected indole and pyrrole, and N-phenylpyrazole using an in situ mixture of ZnCl2*TMEDA (0.5 equiv) and lithium 2,2,6,6-tetramethylpiperidide (1.5 equiv) in THF at room temperature was described. The reaction was evidenced by trapping with iodine, regioselectively giving the expected functionalized derivatives in 52 to 73% yields. A mixture of mono- and disubstituted derivatives was obtained starting from thiazole. Cross-coupling reactions of 2-metalated benzo[b]thiophene and benzo[b]furan with heteroaromatic chlorides proved possible under palladium catalysis. A reaction pathway where the lithium amide and zinc diamide present in solution behave synergically was proposed for the deprotonation reaction, taking account of NMR and DFT studies carried out on the basic mixture.

Domaines

Chimie organique
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Dates et versions

hal-00784514 , version 1 (05-02-2014)

Identifiants

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J.M. L'Helgoual'Ch, Anne Seggio, Floris Chevallier, M. Yonehara, Erwann Jeanneau, et al.. Deprotonative metalation of five-membered aromatic heterocycles using mixed lithium-zinc species. Journal of Organic Chemistry, 2007, 73 (1), pp.177-183. ⟨10.1021/jo7020345⟩. ⟨hal-00784514⟩
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