Solution Structures and Reactivities of the Mixed Aggregates Derived from n-Butyllithium and Vicinal Amino Alkoxides
Journal of the American Chemical Society2001Vol. 123(33), pp. 8039–8046
Citations Over TimeTop 10% of 2001 papers
Abstract
Low-temperature (6)Li, (13)C, and (15)N NMR spectroscopies reveal that mixtures of n-BuLi and (1R,2S)-R'(2)NCH(R)CH(Ph)OLi (ROLi; R = Ph or Me; R'(2)N = pyrrolidino or Me(2)N) in THF/pentane afford a (n-BuLi)(3)(ROLi) (3:1) mixed tetramer and a C(2)-symmetric (n-BuLi)(2)(ROLi)(2) (2:2) mixed tetramer depending on the proportions of the reactants. The corresponding (n-BuLi)(ROLi)(3) (1:3) mixed tetramer is not observed. ROLi-mediated additions of n-BuLi to benzaldehyde proceed with up to 21:1 enantiomeric ratios that depend on the n-BuLi/ROLi stoichiometries. The enantioselectivities are considered in light of a previously posited mechanism involving reaction via the C(2)-symmetric 2:2 mixed tetramer.
Related Papers
- → Chemistry of organoditins. I. Stereochemistry of dehalogenation of vicinal dihalides.(1973)3 cited
- Catalytic vapor oxidation of toluene to benzaldehyde(2000)
- Determination of Toluene and Benzaldehyde From Oxidation of Toluene to Benzaldehyde by Gas Chromatography(2005)
- → ChemInform Abstract: DDQ‐Mediated Oxidation of sp3 C—H Bond for the Direct Synthesis of Vicinal Tricarbonyl Compounds.(2014)
- → ChemInform Abstract: Convergent, Asymmetric Synthesis of Vicinal Amino Alcohols via Rh‐Catalyzed Addition of α‐Amido Trifluoroborates to Carbonyls.(2014)