Enantioselective Aminohydroxylation of Styrenyl Olefins Catalyzed by an Engineered Hemoprotein

Chiral 1,2‐amino alcohols are widely represented in biologically active compounds from neurotransmitters to antivirals. While many synthetic methods have been developed for accessing amino alcohols, the direct aminohydroxylation of alkenes to unprotected, enantioenriched amino alcohols remains a challenge. Using directed evolution, we have engineered a hemoprotein biocatalyst based on a thermostable cytochrome c that directly transforms alkenes to amino alcohols with high enantioselectivity (up to 2500 TTN and 90 % ee) under anaerobic conditions with O‐pivaloylhydroxylamine as an aminating reagent. The reaction is proposed to proceed via a reactive iron‐nitrogen species generated in the enzyme active site, enabling tuning of the catalyst's activity and selectivity by protein engineering. Auf direkte Art: Ein Hämoprotein‐Katalysator wurde entwickelt, der Alkene mit hoher Enantioselektivität direkt in Aminoalkohole überführt. Der Proteinkatalysator, der durch gerichtete Evolution aus einem thermostabilen Cytochrom c erhalten wurde, nutzt O‐Pivaloylhydroxylamin, um eine reaktive Eisen‐Stickstoff‐Spezies zu erzeugen.