title: Reversible alkene insertion into the Pd-N bond of Pd(II)-sulfonamidates and implications for catalytic amidation reactions.
abstract: Alkene insertion into Pd-N bonds is a key step in Pd-catalyzed oxidative amidation of alkenes. A series of well-defined Pd(II)-sulfonamidate complexes have been prepared and shown to react via insertion of a tethered alkene. The Pd-amidate and resulting Pd-alkyl species have been crystallographically characterized. The alkene insertion reaction is found to be reversible, but complete conversion to oxidative amination products is observed in the presence of O(2). Electronic-effect studies reveal that alkene insertion into the Pd-N bond is favored kinetically and thermodynamically with electron-rich amidates.
authors: Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA
authors: Paul B
authors: PB
authors: White
authors: Shannon S
authors: SS
authors: Stahl
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000586:Amination; D002384:Catalysis; D018360:Crystallography, X-Ray; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D013449:Sulfonamides / Q000737:chemistry*
chemical_list: D000475:Alkenes; D013449:Sulfonamides; D010165:Palladium; D009584:Nitrogen