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Co‐Condensation Reactions of Substituted Aromatic Compounds with Lithium Atoms at 77 K
Author(s) -
Dunne John P.,
Bockmeyer Matthias,
Tacke Matthias
Publication year - 2003
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200390065
Subject(s) - chemistry , anisole , benzene , mesitylene , lithium (medication) , medicinal chemistry , thioanisole , photochemistry , isoindoline , organic chemistry , catalysis , medicine , endocrinology
Abstract Lithium atoms were co‐condensed with +I‐substituted benzene derivatives like trimethyl(phenyl)silane and tert ‐butylbenzene in the presence of THF at 77 K, which resulted in C−H bond activation, to produce the aryllithium compound as well as the coupling of the substituted phenyl radicals. Other +I‐substituted benzene derivatives like xylene and mesitylene failed to react with lithium atoms in the presence of THF. Oxygen and nitrogen donor substituted benzene derivatives (anisole, N , N ‐dimethylaniline, and N , N ‐dimethylbenzylamine) showed activation of the ortho C−H bond when co‐condensed with lithium atoms in the presence of THF. However, when thioanisole was co‐condensed with lithium atoms and THF, a C−S bond cleavage occurred instead. These results were interpreted with the aid of DFT calculations, which show π‐ and σ‐complexes between the lithium clusters and benzene derivatives as reactive intermediates. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)