Petermeier, PhilippPhilippPetermeierBittner, Jan PhilippJan PhilippBittnerMüller, SimonSimonMüllerByström, EmilEmilByströmKara, SelinSelinKara2022-10-102022-10-102022-08-08Green Chemistry 24: 6889-6899 (2022)http://hdl.handle.net/11420/13727As renewable lignin building blocks, hydroxystyrenes are particularly appealing as either a replacement or addition to styrene-based polymer chemistry. These monomers are obtained by decarboxylation of phenolic acids and often subjected to chemical modifications of their phenolic hydroxy groups to improve polymerization behaviour. Despite efforts, a simple, scalable, and purely (chemo)catalytic synthesis of acetylated hydroxystyrenes remains elusive. We thus propose a custom-made chemoenzymatic route that utilizes a phenolic acid decarboxylase (PAD). Our process development strategy encompasses a computational solvent assessment informing about solubilities and viable reactor operation modes, experimental solvent screening, cascade engineering, heterogenization of biocatalyst, tailoring of acetylation conditions, and reaction upscale in a rotating bed reactor. By this means, we established a clean one-pot two-step process that uses the renewable solvent CPME, bio-based phenolic acid educts and reusable immobilised PAD. The overall chemoenzymatic reaction cascade was demonstrated on a 1 L scale to yield 18.3 g 4-acetoxy-3-methoxystyrene in 96% isolated yield.en1463-9270202268896899RSChttps://creativecommons.org/licenses/by-nc/3.0/TechnikJournal Article10.15480/882.462210.1039/d2gc01629j10.15480/882.4622Other