Metal complexes-catalyzed hydrolysis and alcoholysis of organic substrates such as alkenyl esters, alkenyl ethers, and azlactones (oxazol-5(4 H)-ones) are described. These reactions were applied for kinetic resolution of chiral compounds and high selectivities were achieved with vinyl ethers of 2-substituted cyclohexanols, 1,1′-bi-2-naphthols, 1,1′-bi-2-phenols, and 4,4-disubstituted azlactones. Oxidative carbon–carbon bond cleavage reactions, which were found in the course of the study of asymmetric hydrolysis were also described.