Generation and utility of tertiary alpha-aminoorganolithium reagents.
A general approach to tertiary alpha-aminoorganolithium reagents by reductive lithiation of alpha-aminonitriles has been developed. This class of organolithium nucleophiles reacts efficiently with carbonyl electrophiles or in intramolecular cyclizations with tethered phosphate leaving groups. Transmetalation can be used to produce alpha-aminoorganocuprate reagents that react with alkyl halide electrophiles and in 1,4-additions with enones. These methods establish a new approach for the synthesis of quaternary centers adjacent to nitrogen. [reaction: see text]
Wolckenhauer
Scott A
SA
Department of Chemistry, 516 Rowland Hall, University of California-Irvine, Irvine, CA 92697-2025, USA.
Rychnovsky
Scott D
SD
D007202:Indicators and Reagents; D018020:Lithium Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction
D007202:Indicators and Reagents; D018020:Lithium Compounds; D009570:Nitriles; D009942:Organometallic Compounds