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 ω-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, we developed a series of in vitro reaction cascades where an alkenol produced by the decarboxylation of ω 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. In addition, the combination of enzymatic decarboxylation with a ruthenium catalyst in a chemo-enzymatic cascade provides a novel way to synthesize long-chain diols.