Enzymatic site-selectivity enabled by structure-guided directed evolution

Biocatalytic site-selective (regioselective) organic transformations have been practiced for decades, but the traditional limitations of enzymes regarding narrow substrate acceptance and the often observed insufficient degree of selectivity have persisted until recently. With the advent of directed evolution, it is possible to engineer site-selectivity to suit the needs of organic chemists. This review features recent progress in this exciting research area, selected examples involving P450 monooxygenases, halogenases and Baeyer-Villiger monooxygenases being featured for illustrative purposes. The complementary nature of enzymes and man-made catalysts is emphasized.