title: Probing the Electronic Demands of Transmetalation in the Palladium-Catalyzed Cross-Coupling of Arylsilanolates.
abstract: The electronic characteristics of coupling partners in the transmetalation step for the cross-coupling reaction of arylsilanolates have been investigated. The ability to interrogate the transmetalation event by in situ preparation of the arylpalladium(II) silanolate intermediate has enabled a Hammett analysis for both the aryl electrophile and arylsilanolate to be conducted. These studies reveal that electron-donating groups on the silicon nucleophile and electron-withdrawing groups on the electrophile accelerate the transmetalation process.
authors: Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, IL 61801.
authors: Scott E
authors: SE
authors: Denmark
authors: Russell C
authors: RC
authors: Smith
authors: Wen-Tau T
authors: WT
authors: Chang