Probing the electronic demands of transmetalation in the palladium-catalyzed cross-coupling of arylsilanolates

Article abstract of DOI:10.1016/j.tet.2011.03.066

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.