A Hybrid Cellular-Heterogeneous Catalyst Strategy for the Production of Olefins from Glucose

Abstract

Living systems provide a promising approach to chemical synthesis, having been optimized by evolution to convert renewable carbon sources such as glucose to an enormous range of small molecules. However, a large number of synthetic structures can still be difficult to obtain solely from cells, such as unsubstituted hydrocarbons. In this work, we demonstrate the use of a hybrid cellular-heterogeneous catalytic strategy to produce olefins from glucose, using a selective hydrolase to generate an activated intermediate that is readily deoxygenated. Using a new family of iterative thiolase enzymes, we have genetically engineered a microbial strain that produces 4.3 ± 0.4 g L−1 of fatty acid from glucose with 86% captured as 3-hydroxyoctanoic and 3-hydroxydecanoic acids. This 3-hydroxy substituent serves as a leaving group enabling heterogeneous tandem decarboxylation-dehydration routes to olefinic products on Lewis acidic catalysts without the additional redox input required for enzymatic or chemical deoxygenation of simple fatty acids.