Artificial Enzymes as Promiscuous Catalysts in Organic and Pharmaceutical Chemistry

Promiscuous enzyme activity can refer either to reactions of unnatural substrates or to reaction types not normally possible with enzymes. Directed evolution of stereo- and/or regio-selective enzymes allows both types of catalytic profiles. A major area concerns artificial metalloenzymes, accessible either by placing ligated transition metals into protein scaffolds and applying saturation mutagenesis at sites surrounding the putative binding pocket or by applying saturation mutagenesis directly to metal-containing enzymes such as P450 monooxygenases. This chapter describes and analyzes the different approaches and points out the respective current limitations and advantages.