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Deprotonative Metalation of Substituted Benzenes and Heteroaromatics Using Amino/Alkyl Mixed Lithium–Zinc Combinations
Author(s) -
Snégaroff Katia,
Komagawa Shinsuke,
Chevallier Floris,
Gros Philippe C.,
Golhen Stéphane,
Roisnel Thierry,
Uchiyama Masanobu,
Mongin Florence
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201000543
Subject(s) - homoleptic , anisole , metalation , chemistry , lithium (medication) , tetramethylethylenediamine , alkyl , electrophile , zinc , reactivity (psychology) , electrophilic aromatic substitution , medicinal chemistry , main group element , organic chemistry , inorganic chemistry , transition metal , catalysis , metal , medicine , alternative medicine , pathology , endocrinology
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.