Abstract
Oxidation is one of the most important processes used by the chemical industry. However, many of the methods that are used pose significant sustainability and environmental issues. Biocatalytic oxidation offers an alternative to these methods, with a now significant enzymatic oxidation toolbox on offer to chemists. Oxidases are one of these options, and as they only depend on molecular oxygen as a terminal oxidant offer perfect atom economy alongside the selectivity benefits afforded by enzymes. This review will focus on examples of oxidase biocatalysts that have been used for the sustainable production of important molecules and highlight some important processes that have been significantly improved through the use of oxidases. It will also consider emerging classes of oxidases, and how they might fit in a future biorefinery approach for the sustainable production of important chemicals.
Highlights
Biocatalytic oxidation offers an alternative to these methods, with a significant enzymatic oxidation toolbox on offer to chemists
This review will focus on examples of oxidase biocatalysts that have been used for the sustainable production of important molecules and highlight some important processes that have been significantly improved through the use of oxidases
Enzymatic oxidation of alcohols has emerged as an attractive alternative, with a toolbox of different enzymes available that are capable of oxidizing a large range of substrates [4]
Summary
Selective oxidation reactions are one of the most important transformations in the chemical sector. There are a host of biocatalytic options for enzymatic oxidation, including dehydrogenases, oxidases, monooxygenases and peroxygenases (scheme 1) [4] Of these different enzyme classes, oxidases are attractive from a green perspective. Being dependent exclusively on molecular oxygen as a co-substrate effectively reduces reagent input for oxidases to zero due to oxygen’s natural abundance It does present processing issues, primarily due to the low availability of oxygen in aqueous systems being limited to around 270 μM (8 mg L−1) [5]. It will discuss how different classes of oxidases have been used for bulk and speciality chemical syntheses, and how these different processes are enabling more efficient chemical transformations than previous chemical counterparts It will cover how different enzyme engineering approaches have been used to deliver toolboxes of starting points for further evolution and, in some cases, process-ready enzymes that can operate on an industrial scale as sustainable oxidation catalysts. There will be a discussion of the future of oxidase biocatalysis, and how recently discovered enzymes (e.g. lytic polysaccharide monooxygenases (LPMOs)) could play a role in a full biorefinery approach to chemical production
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