Chemoselective Aerobic Oxidation of Unproteced Diols Catalyzed by Pd-(NHC) (NHC = N-heterocyclic carbene) Complexes

Abstract

[[abstract]]Neutral Pd(X)(η3-allyl) (X = Cl, OAc (acetate)) complexes bearing mono-coordinating NHC ligands have been synthesized, characterized and employed to catalyze the aerobic oxidation of unprotected 1,2- and 1,3-diols selectively to hydroxy ketones. A comparison of the catalytic performance of these precursors with a reference system has shown that the precursor with the ligands N,N′-bis(adamantyl)imidazol-2-ylidene and chloride is the most efficient for the chemoselective oxidation of 1,2-diols is concerned. High-pressure 1H NMR (HPNMR) experiments in combination with catalytic batch reactions have provided valuable information on the activation of the precursor as well as on the stability of the catalysts