A Retro‐biosynthesis‐Based Route to Generate Pinene‐Derived Polyesters

Significantly increased production of biobased polymers is a prerequisite to replace petroleum‐based materials towards reaching a circular bioeconomy. However, many renewable building blocks from wood and other plant material are not directly amenable for polymerization, due to their inert backbones and/or lack of functional group compatibility with the desired polymerization type. Based on a retro‐biosynthetic analysis of polyesters, a chemoenzymatic route from (−)‐α‐pinene towards a verbanone‐based lactone, which is further used in ring‐opening polymerization, is presented. Generated pinene‐derived polyesters showed elevated degradation and glass transition temperatures, compared with poly(ϵ‐decalactone), which lacks a ring structure in its backbone. Semirational enzyme engineering of the cyclohexanone monooxygenase from Acinetobacter calcoaceticus enabled the biosynthesis of the key lactone intermediate for the targeted polyester. As a proof of principle, one enzyme variant identified from screening in a microtiter plate was used in biocatalytic upscaling, which afforded the bicyclic lactone in 39 % conversion in shake flask scale reactions.