Oxidative Addition of Secondary C–X Bonds to Palladium(0): A Beneficial Anomeric Acceleration

Abstract

The oxidative addition of secondary electrophiles to Pd(0) is significantly accelerated by anomeric effects. In contrast to cyclohexyl bromide, acetobromo-α-d-glucose undergoes invertive oxidative addition to tris(triethylphosphine)palladium(0) to generate a stable, isolable organometallic complex, Pd(PEt3)2(Br)(AcO-β-glucose), which has been fully characterized but is prone to β-acetoxy elimination.