title: Chemoselective Alkylations with N- and C-Metalated Nitriles.
abstract: Metalated nitriles exhibit complementary chemoselectivities in electrophilic alkylations. N-Lithiated or C-magnesiated nitriles can be prepared from the same nitrile precursor and selectively reacted with a 1:1 mixture of methyl cyanoformate and benzyl bromide or bifunctional electrophiles through chemoselective attack onto either an alkyl halide or a carbonyl electrophile. A mechanistic explanation for the chemoselectivity preferences is provided that rests on the structural and complexation differences between N- and C-metalated nitriles.
authors.affiliation: Department of Chemistry and Biochemistry, Duquesne University , Pittsburgh, Pennsylvania 15282-1530, United States.
authors.forename: Xun
authors.initials: X
authors.lastname: Yang
authors.affiliation: Department of Chemistry and Biochemistry, Duquesne University , Pittsburgh, Pennsylvania 15282-1530, United States.
authors.forename: Dinesh
authors.initials: D
authors.lastname: Nath
authors.affiliation: Department of Chemistry and Biochemistry, Duquesne University , Pittsburgh, Pennsylvania 15282-1530, United States.
authors.forename: Fraser F
authors.initials: FF
authors.lastname: Fleming