Vinyl-pyrazole as a biomimetic acetaldehyde surrogate

Abstract

Inspired by the enzyme acetylene hydratase, we investigated the reactivity of acetylene with tungsten(II) pyrazole complexes. Our research revealed that the complex [WBr₂(pz-NHCCH₃)(CO)₃] (pz = 3,5-dimethyl-pyrazolate) facilitates the stochiometric reaction between pzH and acetylene to give N-vinyl-pz. This vinyl compound readily hydrolyzes to acetaldehyde, mirroring the product of acetylene hydration in the enzymatic process. The formation of the vinyl compound likely involves a reactive intermediate complex where acetylene acts as a two-electron donor, in contrast to isolable acetylene complexes that are inert to nucleophilic attack by water. Results suggest an alternative mechanism for the enzyme, including vinylation of a neighboring amino acid by acetylene in the active site prior to hydration.