Aggregation studies of complexes containing a chiral lithium amide and n-Butyllithium.
A system consisting of a chiral lithium amide and n-BuLi in tol-d(8) solution was investigated with (1)H and (13)C INEPT DOSY, (6)Li and (15)N NMR, and other 2D NMR techniques. A mixed 2:1 trimeric complex was identified as the major species as the stoichiometry approached 1.5 equiv of n-BuLi to 1 equiv of amine compound. (1)H and (13)C INEPT DOSY spectra confirmed this lithium aggregate in the solution. The formula weight of the aggregate, correlated with diffusion coefficients of internal references, indicated the aggregation number of this complex. Plots of log D(rel) vs log FW are linear (r > 0.9900). (6)Li and (15)N NMR titration experiments also corroborated these results. These NMR experiments indicate that this mixed aggregate is the species that is responsible for asymmetric addition of n-BuLi to aldehydes.
Li
Deyu
D
Department of Chemistry, Brown University, Providence, Rhode Island 02912, USA.
Sun
Chengzao
C
Liu
Jia
J
Hopson
Russell
R
Li
Weibin
W
Williard
Paul G
PG
D000577:Amides / Q000737:chemistry*; D000588:Amines / Q000737:chemistry; D002247:Carbon Isotopes; D003080:Cold Temperature; D007554:Isotopes; D008024:Ligands; D018020:Lithium Compounds / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D009587:Nitrogen Isotopes; D009942:Organometallic Compounds / Q000737:chemistry*; D012996:Solutions; D017186:Titrimetry
D000577:Amides; D000588:Amines; D002247:Carbon Isotopes; D007554:Isotopes; D008024:Ligands; D018020:Lithium Compounds; D009587:Nitrogen Isotopes; D009942:Organometallic Compounds; D012996:Solutions; C046771:butyllithium