title: Metalated nitriles: organolithium, -magnesium, and -copper exchange of alpha-halonitriles.
abstract: [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.
authors.affiliation: Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282-1530, USA. flemingf@duq.edu
authors.forename: Fraser F
authors.initials: FF
authors.lastname: Fleming
authors.forename: Zhiyu
authors.initials: Z
authors.lastname: Zhang
authors.forename: Wang
authors.initials: W
authors.lastname: Liu
authors.forename: Paul
authors.initials: P
authors.lastname: Knochel
mesh_terms: 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
chemical_list: D006846:Hydrocarbons, Halogenated; D009570:Nitriles; D009942:Organometallic Compounds; D003300:Copper; D008094:Lithium; D008274:Magnesium