Biocatalytic Routes for Terminal Alkene Synthesis

Abstract

Terminal alkenes are conventionally produced through energy-intensive petrochemical processes. Enzymatic decarboxylation of bio-derived carboxylic acids has emerged as a sustainable alternative, enabling mild reaction conditions and using biomass-derived substrates. This article highlights the catalytic reactions of four enzyme families capable of generating terminal alkenes, including phenolic acid and ferulic acid decarboxylases, which convert lignin-derived phenolics into styrene derivatives, and CYP152 peroxygenases and nonheme di-iron UndB decarboxylase, which catalyze the oxidative decarboxylation of fatty acids to form linear α-olefins. Despite distinct catalytic mechanisms, these enzymes share common challenges related to decarboxylation efficiency, limited substrate scope, and enzyme stability. We summarize recent mechanistic and engineering advances, identify unifying and distinctive catalytic principles, and discuss future opportunities for improving enzymatic terminal alkene synthesis.