Biocatalytic Michael‐Type Additions of Acetaldehyde to Nitroolefins with the Proline‐Based Enzyme 4‐Oxalocrotonate Tautomerase Yielding Enantioenriched γ‐Nitroaldehydes.

Call me Michaelase: The enzyme 4-oxalocrotonate tautomerase (4-OT) promiscuously catalyzes the Michael-type addition of acetaldehyde to a collection of aromatic and aliphatic nitro-olefins with high stereoselectivity producing precursors of g-aminobutyric acid (GABA) analogues (see scheme).