【文章名】Structure and Dynamics of alpha-Aryl Amide and Ketone Enolates: THF, PMDTA, TMTAN, HMPA, and Crypt-Solvated Lithium Enolates, and Comparison with Phosphazenium Analogues
Structure and Dynamics of alpha-Aryl Amide and Ketone Enolates: THF, PMDTA, TMTAN, HMPA, and Crypt-Solvated Lithium Enolates, and Comparison with Phosphazenium Analogues
[摘要]：A variety of multinuclear NMR techniques, in combination with X-ray diffraction methods, were used to probe the solution structure of alpha-aryl lithium enolates of bis(4-fluorobenzyl) ketone (1-H), phenyl 4-fluorobenzyl ketone (2-H), and N,N-dimethyl 4-fluorophenylacetamide (3-H) in ethereal solvents and in the presence of cosolvent additives PMDTA, TMTAN, HMPA, and cryptand [2.1.1]. All three enolates were dimers in THF solution, and were converted to monomers by the triamine additives, PMDTA and TMTAN. The exchange of the triamine-solvated monomers with their ethereal-solvated dimer counterparts was probed by using dynamic NMR (DNMR). The cosolvent HMPA formed monomers along with minor amounts of lithiate species, (RO)(2)Li- and (RO)(3)Li2-, which were also observed when cryptand [211] was used as a cosolvent, or when mixed lithium phosphazenium enolate solutions were prepared. Dynamic exchange of lithiate species was investigated by DNMR spectroscopy. The barrier to rotation of the conjugated 4-fluorophenyl ring of these diverse enolate structures was measured and found to be consistent with a resonance picture where lower aggregation states lead to increased delocalization of negative charge. The lithium enolate aggregates identified were compared to the "naked" alpha-4-fluorophenyl enolates generated with the phosphazene base P4. The barrier to aryl ring rotation was 2.7 kcal/mol higher for the phosphazenium enolate 3-Li center dot P4H compared to the dimer (3-Li)(2). Structural characterization of a phosphazenium enolate through X-ray crystallography was obtained for the first time. Additional aspects of the Schwesinger base P4 were investigated which included characterization of the solution exchange behavior of the protonated and unprotonated forms as well as determination of the solid state structure by X-ray diffraction.
