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Solution structures of lithium amino alkoxides used in highly enantioselective 1,2-additions.

ABSTRACT: 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 (6)Li NMR spectroscopy reveals that the lithium amino alkoxides are tetrameric. In each case, low-temperature (6)Li NMR spectra show stereoisomerically pure homoaggregates displaying resonances consistent with an S4-symmetric cubic core rather than the alternative D2d 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.

SUBMITTER: Bruneau AM

PROVIDER: S-EPMC3985715 | biostudies-literature | 2014 Feb

REPOSITORIES: biostudies-literature

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Solution structures of lithium amino alkoxides used in highly enantioselective 1,2-additions.

Bruneau Angela M AM Liou Lara L Collum David B DB

Journal of the American Chemical Society 20140205 7

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 (6)Li NMR spectroscopy reveals that the lithium amino alkoxides are tetrameric. In each case, low-temperature (6)Li NMR spectra show stereoisomerically pure homoaggregates displaying resonances consistent with an S4-symmetric cubic core rather than the a ...[more]

PMID: 24471766

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