Cover Image
QR Code

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...

Full description

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:
Tetrahydrofuran
Organometallic compounds
Density functionals
Nuclear magnetic resonance spectroscopy
Aromatic compounds
Toluene
Online Access:View this record in EBSCOhost
Summary: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.