Abstract
The effects of the solvent and the ligand chirality on the regioselectivity of oxidative esterification of propylene and cyclohexene by PdII carboxylates were studied using achiral (MeCO2−, Me2CHCH2CO2−), racemic ((±)-CF3CF2CF2OC*F(CF3)CO2−), and chiral ((S)−(+)−MeC*H(Et)CO2−, (+)−CF3CF2CF2OC*F(CF3)CO2−) carboxylate ligands. The oxidation of alkenes in aprotic media (CHCl3, CH2Cl2, CO2, THF) affords mainly allylic esters (in the case of cyclohexene also homoallylic esters) and the oxidative esterification at the vinylic position is absent. In weakly solvating media (CHCl3, CH2Cl2) the regioselectivity of cyclohexene oxidation (the allyl to homoallyl ratio) increases substantially on going from achiral or racemic acido ligands to chiral acido ligands. In a more donor medium (THF) the ligand chirality effect almost vanishes. The effects of the ligand chirality and the nature of the solvent on the mechanism of alkene oxidation by PdII complexes are discussed.
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