Complete Enzymatic Oxidation of Methanol to Carbon Dioxide: Towards More Eco‐Efficient Regeneration Systems for Reduced Nicotinamide Cofactors

Abstract

An ovel systemf or in situ regeneration of reduced nicotinamide cofactors (NADH) is proposed:t hrough ac ascade of alcohol dehydrogenase (ADH), formaldehyde dismutase (FDM) and formate dehydrogenase (FDH) complete oxidation of methanol to carbon dioxide (CO 2 )i sc oupled to the regeneration of NADH. As ac onsequence,f rom one equivalento fm ethanol three equivalents of NADH can be obtained. Thef easibility of this cascade is demonstrated at the examples of an NADH-dependent reductiono fc onjugated C=Cdouble bonds (catalysed by an enoate reductase) and the NADH-dependent hydroxylation of phenols (catalysedb yamonooxygenase). Them ajor limitationo ft he current regeneration system is the comparablyp oor catalytic efficiency of the methanol oxidation step (low k cat and high K M value of the ADH used) necessitating higher than theoretical methanol concentrations.

Chemoenzymatic Total Synthesis of (+)- & (−)-cis-Osmundalactone

“…Here, the combination of glucose oxidase (GOx, A. niger) as oxygen-activating catalyst and chloroperoxidase (CPO, C. fumago) as oxygenation mediator exhibited high activity in the desired ring expansion, and a tenfold upscaling compared to our original protocol was tolerated without any problem, giving rise to the pyranones in around 80% isolated yield. Different other combinations of commercial peroxidases (including horseradish, soybean and lactoperoxidase) and hydrogen peroxide-releasing systems (L-alanin + amino acid oxidase and methanol + alcohol oxidase/formaldehyde dismutase 10 ) have been tested, but none of them performed as good as the original GOx/CPO setup. 11 Scheme 2.…”

FOx News: Towards Methanol‐driven Biocatalytic Oxyfunctionalisation Reactions

“…MeOH . Similarly, complete oxidation of methanol to regenerate reduced nicotinamide cofactors has been reported …”

Enzymatic halocyclization of allenic alcohols and carboxylates: a biocatalytic entry to functionalized O-heterocycles

“…Here, short-chain primary alcohols can be considered an elegant, low molecular weight alternative. 34 Unfortunately, due to the low pH requirement of the CPO-catalyzed halogenation, all attempts to implement a methanol oxidase/formaldehyde dismutase system 35 failed so far ( Table 1, entry 11).…”