title: Anionic Snieckus-Fries rearrangement: solvent effects and role of mixed aggregates.
abstract: Lithiated aryl carbamates (ArLi) bearing methoxy or fluoro substituents in the meta position are generated from lithium diisopropylamide (LDA) in THF, n-BuOMe, Me2NEt, dimethoxyethane (DME), N,N,N',N'-tetramethylethylenediamine (TMEDA), N,N,N',N'-tetramethylcyclohexanediamine (TMCDA), and hexamethylphosphoramide (HMPA). The aryllithiums are shown with (6)Li, (13)C, and (15)N NMR spectroscopies to be monomers, ArLi-LDA mixed dimers, and ArLi-LDA mixed trimers, depending on the choice of solvent. Subsequent Snieckus-Fries rearrangements afford ArOLi-LDA mixed dimers and trimers of the resulting phenolates. Rate studies of the rearrangement implicate mechanisms based on monomers, mixed dimers, and mixed trimers.
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, USA.
authors.forename: Jason C
authors.initials: JC
authors.lastname: Riggs
authors.forename: Kanwal J
authors.initials: KJ
authors.lastname: Singh
authors.forename: Ma
authors.initials: M
authors.lastname: Yun
authors.forename: David B
authors.initials: DB
authors.lastname: Collum
mesh_terms: D000838:Anions / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D012997:Solvents / Q000737:chemistry*
chemical_list: D000838:Anions; D012997:Solvents
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