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

Katia Snégaroff (1) , Shinsuke Komagawa (2) , Floris Chevallier (1) , Philippe C. Gros (3) , Stéphane Golhen (4) , Thierry Roisnel (4) , Masanobu Uchiyama (2) , Florence Mongin (1)

1 CPM - Chimie et Photonique Moléculaires
2 RIKEN - RIKEN - Institute of Physical and Chemical Research [Japon]
3 SRSMC - Structure et Réactivité des Systèmes Moléculaires Complexes
4 ISCR - Institut des Sciences Chimiques de Rennes

Different 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.

Mots clés: cross-coupling; density functional calculations; lithium; metalation; zinc

Domaines: Chimie organique

Katia Snégaroff, Shinsuke Komagawa, Floris Chevallier, Philippe C. Gros, Stéphane Golhen, et al.. Deprotonative metalation of substituted benzenes and heteroaromatics using amino/alkyl mixed lithium-zinc combinations.. Chemistry - A European Journal, 2010, 16 (27), pp.8191-8201. ⟨10.1002/chem.201000543⟩. ⟨hal-00737564⟩