Deprotonative metalation of substituted benzenes and heteroaromatics using amino/alkyl mixed lithium-zinc combinations.
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.
Chimie et Photonique Moléculaires, UMR 6510 CNRS, Université de Rennes 1, Bâtiment 10A, Case 1003, Campus Scientifique de Beaulieu, 35042 Rennes Cedex, France.
Katia
K
Snégaroff
Shinsuke
S
Komagawa
Floris
F
Chevallier
Philippe C
PC
Gros
Stéphane
S
Golhen
Thierry
T
Roisnel
Masanobu
M
Uchiyama
Florence
F
Mongin