Solution Structures of Lithium Amino Alkoxides Used in Highly Enantioselective 1,2-Additions.

Lithium ephedrates and norcarane-derived lithium amino alkoxides used to effect highly enantioselective 1,2-additions on large scales have been characterized in toluene and tetrahydrofuran. The method of continuous variations in conjunction with Li NMR spectroscopy reveals that the lithium amino alk...

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Published in:Journal of the American Chemical Society Vol. 136; no. 7; pp. 2885 - 2892
Main Authors: Bruneau, Angela M., Liou, Lara, Collum, David B.
Format: Article
Published: American Chemical Society 2/19/2014
Subjects:
Online Access:View this record in EBSCOhost
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      dt: 2/19/2014
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        atl: Solution Structures of Lithium Amino Alkoxides Used in Highly Enantioselective 1,2-Additions.
      aug:
        au:
          Bruneau, Angela M.
          Liou, Lara
          Collum, David B.
        affil: Department of Chemistry and Chemical Biology Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, United States
      su:
        Tetrahydrofuran
        Organometallic compounds
        Density functionals
        Nuclear magnetic resonance spectroscopy
        Aromatic compounds
        Toluene
      sug:
        subj:
          Tetrahydrofuran
          Organometallic compounds
          Density functionals
          Nuclear magnetic resonance spectroscopy
          Aromatic compounds
          Toluene
      ab: Lithium ephedrates and norcarane-derived lithium amino alkoxides used to effect highly enantioselective 1,2-additions on large scales have been characterized in toluene and tetrahydrofuran. The method of continuous variations in conjunction with Li NMR spectroscopy reveals that the lithium amino alkoxides are tetrameric. In each case, low-temperature Li NMR spectra show stereoisomerically pure homoaggregates displaying resonances consistent with an S-symmetric cubic core rather than the alternative D core. These assignments are supported by density functional theory computations and conform to X-ray crystal structures. Slow aggregate exchanges are discussed in the context of amino alkoxides as chiral auxiliaries.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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          year: 2014
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