JOURNAL ARTICLE
RESEARCH SUPPORT, N.I.H., EXTRAMURAL
RESEARCH SUPPORT, NON-U.S. GOV'T
RESEARCH SUPPORT, U.S. GOV'T, NON-P.H.S.
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Lithium diisopropylamide-mediated ortholithiation and anionic fries rearrangement of aryl carbamates: role of aggregates and mixed aggregates.

Structural and mechanistic studies of the lithium diisopropylamide (LDA)-mediated anionic Fries rearrangements of aryl carbamates are described. Substituents at the meta position of the arene (H, OMe, F) and the dialkylamino moiety of the carbamate (Me(2)N, Et(2)N, and i-Pr(2)N) markedly influence the relative rates of ortholithiation and subsequent Fries rearrangement. Structural studies using (6)Li and (15)N NMR spectroscopies on samples derived from [(6)Li,(15)N]LDA reveal an LDA dimer, LDA dimer-arene complexes, an aryllithium monomer, LDA-aryllithium mixed dimers, an LDA-lithium phenolate mixed dimer, and homoaggregated lithium phenolates. The highly insoluble phenolate was characterized as a dimer by X-ray crystallography. Rate studies show monomer- and dimer-based ortholithiations as well as monomer- and mixed dimer-based Fries rearrangements. Density functional theory computational studies probe experimentally elusive structural and mechanistic details.

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