title: On the remarkably different role of salt in the cross-coupling of arylzincs from that seen with alkylzincs.
abstract: The role of halide salt additives has been investigated in the Negishi reaction involving aryl zinc reagents. Diarylzincs readily transmetallate to Pd in relatively non-polar media (e.g., THF) with zero salt present and coupling proceeds. Arylzinc halides (ArZnX) fail to couple in THF without salt, but do couple with it. However, unlike alkylzincs that form higher-order zincates in order to facilitate transmetallation, all that is required with arylzincs in an increase in solvent dielectric as even ZnX2 works as an additive, which completely terminates alkylzinc coupling.
authors.affiliation: Department of Chemistry, York University, 4700 Keele Street, Toronto, ON, M3J 1P3 (Canada) http://www.yorku.ca/organ/
authors.forename: Lucas C
authors.initials: LC
authors.lastname: McCann
authors.forename: Michael G
authors.initials: MG
authors.lastname: Organ
keywords: Negishi reaction; PEPPSI; cross-couple; palladium; transition-metal catalysis