Metalated nitriles: organolithium, -magnesium, and -copper exchange of alpha-halonitriles.
[reaction: see text] alpha-Halonitriles react with alkyllithium, organomagnesium, and lithium dimethylcuprate reagents generating reactive, metalated nitriles. The rapid halogen-metal exchange with alkyllithium and Grignard reagents allows selective exchange in the presence of reactive carbonyl electrophiles, including aldehydes, providing a high-yielding alkylation protocol. Lithiated and magnesiated nitriles react with propargyl bromide by S(N)2 displacement whereas organocopper nitriles react by S(N)2' displacement, correlating with the formation of a C-metalated nitrile.
Fleming
Fraser F
FF
Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282-1530, USA. flemingf@duq.edu
Zhang
Zhiyu
Z
Liu
Wang
W
Knochel
Paul
P
D003300:Copper / Q000737:chemistry*; D006846:Hydrocarbons, Halogenated / Q000138:chemical synthesis / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D008274:Magnesium / Q000737:chemistry*; D008968:Molecular Conformation; D009570:Nitriles / Q000138:chemical synthesis*; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism
D006846:Hydrocarbons, Halogenated; D009570:Nitriles; D009942:Organometallic Compounds; D003300:Copper; D008094:Lithium; D008274:Magnesium