Metals and Metal Complexes in Cooperative Catalysis with Enzymes within Organic‐Synthetic One‐Pot Processes

The combination of metal catalysis and enzyme catalysis turned out to be suitable for numerous different chemocatalytic as well as biocatalytic reactions, which enabled the development of proof of concepts for a broad variety of chemoenzymatic one-pot processes. Notably, a range of metal catalysts turned out to be compatible with enzymes as a prerequisite for establishing such one-pot processes. The developed one-pot processes based on cooperative metal and enzyme catalysis can be clustered into three major types of combinations, which are (i) metal-catalyzed in situ-regeneration of cofactors required for enzyme-catalyzed redox reactions under consumption of the cofactors NAD(P)H or NAD(P)+, (ii) racemization of a substrate with a metal catalyst combined with an enantioselective transformation of the substrate catalyzed by an enzyme toward dynamic kinetic resolutions, and (iii) consecutive one-pot processes in which formed intermediates were directly converted into the corresponding products (e.g., a reversible initial metal-catalyzed transformation and a subsequent irreversible enzymatic transformation).