Cross-coupling reactions of alkenylsilanolates. Investigation of the mechanism and identification of key intermediates through kinetic analysis.
The mechanism of the fluoride-free, palladium-catalyzed cross-coupling reaction of potassium (E)-heptenyldimethylsilanolate, K(+)(E)-1(-), with 2-iodothiophene has been investigated through kinetic analysis. The order of each component was determined by plotting the initial rates of the reaction against concentration. These data provided a mechanistic picture which involves a fast and irreversible oxidative insertion of palladium into the aryl iodide and a subsequent intramolecular transmetalation step from a complex containing a silicon-oxygen-palladium linkage. First-order behavior at low concentrations of silanolate with excess palladium(0) complex supports the formation of this complex as the turnover-limiting step. The change to zeroth-order dependence on silanolate at high concentrations is consistent with the intramolecular transmetalation becoming the turnover-limiting step.
Denmark
Scott E
SE
Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA. denmark@scs.uiuc.edu
Sweis
Ramzi F
RF
D000475:Alkenes / Q000737:chemistry*; D007700:Kinetics; D010165:Palladium / Q000737:chemistry; D012821:Silanes / Q000737:chemistry*; D013876:Thiophenes / Q000737:chemistry*
D000475:Alkenes; D012821:Silanes; D013876:Thiophenes; D010165:Palladium