Bridging between Organocatalysis and Biocatalysis: Asymmetric Addition of Acetaldehyde to β‐Nitrostyrenes Catalyzed by a Promiscuous Proline‐Based Tautomerase

Abstract

Non-natural beauty: The enzyme 4-oxalocrotonate tautomerase (4-OT) promiscuously (i.e., with non-natural activity) catalyzes the Michael-type addition of acetaldehyde to nitrostyrene. Catalysis likely proceeds via enamine formation of the amino-terminal proline residue of 4-OT with acetaldehyde (see picture), reminiscent of organocatalysis. High stereoselectivity, low catalyst loading, and water as reaction medium characterize this methodology. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.