Bio‐based α,ω‐Functionalized Hydrocarbons from Multi‐step Reaction Sequences with Bio‐ and Metallo‐catalysts Based on the Fatty Acid Decarboxylase OleTJE

OleT from Jeotgalicoccus sp. ATCC 8456 catalyzes the decarboxylation of -functionalized fatty acids to the corresponding alkenols, which can themselves serve as starting material for the synthesis of polymers and fine chemicals. To show the versatility of possible reactions, a series of in vitro reaction cascades was developed where an alkenol produced by the decarboxylation of -hydroxy fatty acids can be further converted into alkenylamines and diols. By coupling OleT with an alcohol dehydrogenase or alcohol oxidase as well as an amino-transaminase, an oxidative decarboxylation followed by the oxidation of the terminal alcohol and a subsequent reductive transamination could be carried out. By using different cofactors or electron sources, the reactions could be performed sequentially or simultaneously. The combination of enzymatic decarboxylation with a ruthenium catalyst in a chemo-enzymatic cascade provides a novel way to synthesize long-chain diols.