American Chemical Society
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Are n-BuLi/TMEDA-Mediated Arene Ortholithiations Directed? Substituent-Dependent Rates, Substituent-Independent Mechanisms

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journal contribution
posted on 2000-08-26, 00:00 authored by Scott T. Chadwick, Roger A. Rennels, Jennifer L. Rutherford, David B. Collum
Rate studies of the lithiation of benzene and related alkoxy-substituted aromatics by n-BuLi/TMEDA mixtures implicate similar mechanisms in which the proton transfers are rate limiting with transition structures of stoichiometry [(n-BuLi)2(TMEDA)2(Ar−H)] (Ar−H = benzene, C6H5OCH3, m-C6H4(OCH3)2, C6H5OCH2OCH3, and C6H5OCH2CH2N(CH3)2). Cooperative substituent effects and an apparent importance of inductive effects suggest a mechanism in which alkoxy−lithium interactions are minor or nonexistent in the rate-limiting transition structures. Supported by ab initio calculations, transition structures based upon triple ions of general structure [(n-Bu)2Li]-//+Li(TMEDA)2 are discussed.