The Pd3(dppm)3(CO)2+ cluster: an efficient electrochemically assisted Lewis acid catalyst for the fluorination and alcoholysis of acyl chlorides.
The dicationic palladium cluster Pd3(dppm)3(CO)2+ (dppm = bis(diphenylphosphino)methane) reacts with acid chlorides RCOCl (R = n-C6H13, t-Bu, Ph) to afford quantitatively the chloride adduct Pd3(dppm)3(CO)(Cl)+ and the acyl cation RCO+ as the organic counterpart. The dicationic reactive cluster can be reformed by electrolyzing the chloride complex with a copper anode leaving CuCl as a byproduct. The combination of these two reactions provides an electrocatalytic way to form the acylium from the acid chloride. Indeed, in CH2Cl2, 0.2 M NBu4PF6, or NBu4BF4, the electrolysis of the acid chloride in the presence of a catalytic amount of the cluster (1%) gives in good yields the acid fluoride RCOF, arising from the coupling of the acylium with a F(-) issued from the fluorinated supporting electrolyte. Alternatively, in CH2Cl2 or 0.2 M NBu4ClO4, by operating with an alcohol R'OH as the nucleophile, the electrolysis gives the ester RC(O)OR' as the only final product.
Lemaître
Frédéric
F
Laboratoire de Synthèse et d'Electrosynthèse Organométalliques, CNRS UMR 5632, Faculté des Sciences Gabriel, Université de Bourgogne, 6 Boulevard Gabriel, 21000 Dijon, France.
Lucas
Dominique
D
Mugnier
Yves
Y
Harvey
Pierre D
PD