Hydrogenation Using Chemogenetically Optimized Chemzymes

Significance

This paper describes the chemogenetical optimization of artificial hydrogenases in the reduction of α-acetamidocinnamic acid and α-acetamidoacrylic acid. The metalloenzymes were prepared according to the biotin-avidin technology, 20 streptavidin isoforms obtained by saturation mutagenesis at position 112 were combined with 18 biotinylated ligands. Both α-acetamidodehydroamino acids were reduced simultaneously to investigate the substrate specificity. In general the protein-ligand combinations yield the reduced α-acetamidocinnamic acid in higher enantioselectivities and lower yields. The reaction provides the reduced olefins in up to 94% ee (360 artificial metalloenzymes have been investigated).