Lithium cadmate-mediated deprotonative metalation of anisole: experimental and computational study

International audienceLithium cadmates bearing different ligands were compared with efficient (TMP)(3)CdLi (TMP = 2,2,6,6-tetramethylpiperidino) for their ability to deprotometalate anisole. The generated arylcadmates were evidenced using I(2). The results show that it is possible to replace only one of the TMP (with a piperidino, a diisopropylamino, a butyl, or a sec-butyl) without important yield drop. In the light of DFT calculations, reaction pathways were proposed for the deprotocadmations of anisole using a triamino, an alkyldiamino, and an aminodialkyl cadmat

Direct metallation of thienopyrimidines using a mixed lithium-cadmium base and antitumor activity of functionalized derivatives

International audienceA series of thieno[2,3-d]- and thieno[3,2-d]pyrimidines have been easily synthesized using as key step a deproto-cadmiation-trapping sequence. Some of the compounds thus synthesized were screened for anti-cancer (cytotoxic) activities, and (S)-2-(6-iodo-2-phenylthieno[2,3-d]pyrimidin- 4-ylamino)-3-phenylpropanoic acid proved to have a significant activity towards liver, human breast and cervix carcinoma cell lines

A convenient synthesis of 3- and 5-amino-1H-pyrazoles via 3(5)-amino-4-(ethylsulfinyl)-1H-pyrazole desulfinylation

International audienceSyntheses of 5-amino-3-aryl- and 3-amino-5-aryl-1H-pyrazoles from β-bromo-α-(ethylsulfanyl)cinnamonitrile are described. The β-bromo-α-(ethylsulfanyl)cinnamonitriles were oxidized with H2O2 to the corresponding β-bromo-α-(ethylsulfinyl)cinnamonitriles. Subsequent treatment of the resulting sulfoxides with hydrazine hydrate or methylhydrazine followed by hydrochloric acid hydrolysis afforded 5-amino-3-aryl- and 3-amino-5-aryl-1H-pyrazoles, respectively, in good yields

Deprotonative metalation of substituted benzenes and heteroaromatics using amino/alkyl mixed lithium-zinc combinations.

International audienceDifferent homoleptic and heteroleptic lithium-zinc combinations were prepared, and structural elements obtained on the basis of NMR spectroscopic experiments and DFT calculations. In light of their ability to metalate anisole, pathways were proposed to justify the synergy observed for some mixtures. The best basic mixtures were obtained either by combining ZnCl(2).TMEDA (TMEDA=N,N,N',N'-tetramethylethylenediamine) with [Li(tmp)] (tmp=2,2,6,6-tetramethylpiperidino; 3 equiv) or by replacing one of the tmp in the precedent mixture with an alkyl group. The reactivity of the aromatic lithium zincates supposedly formed was next studied, and proved to be substrate-, base-, and electrophile-dependent. The aromatic lithium zincates were finally involved in palladium-catalyzed cross-coupling reactions with aromatic chlorides and bromides