Homogeneous Oxygenase Catalysis

Abstract

Oxygenases-catalyzed reductive activation of molecular oxygen and incorporation of O atoms into an organic molecule is undoubtedly one of the most attractive research areas. Typically, these oxygenation reactions proceed with high selectivity and reactivity, which is seldom found in its "biomimetic" chemocatalytic counterparts. Furthermore, enzymatic oxygenation can avoid undesired overoxidation, which is frequently observed in (industrial) chemical transformation. Therefore, it is not surprising that tremendous attention has been paid to enzymatic oxygenation. Their application in organic synthesis has been steadily growing over the years. The goal of the present Review is to provide a handy reference for chemists interested in using homogeneous oxygenase catalysis and those interested in discovering new types of biomimetic oxidations and oxygenations with dioxygen. In this Review, we will review the recent advances in in homogeneous oxygenase catalysis to reveal the great achievements and potentials in this field.

Biotechnological Methods of Sulfoxidation: Yesterday, Today, Tomorrow

“…It deserves special attention due to its good thermostability and tolerance to solvents. For this reason, it is attractive for practical use [12,83]. However, PAMO has a somewhat narrow range of substrates favoring relatively simple aromatic compounds, such as benzyl alkyl sulfides.…”

“…PAMO was not suitable for the synthesis of alkyl heteroaryl sulfoxides because of its generally low activity and/or selectivity. In addition to aromatic substrates, PAMO can also moderately convert non-aromatic substrates [12].…”

“…In this work, we will focus on discussing the biotechnological methods of oxidation of sulfides because biocatalysis is undoubtedly a method of gentle and environmentally friendly synthesis of sulfoxides [12].…”

Formate Oxidase (FOx) from Aspergillus oryzae: One Catalyst Enables Diverse H2O2‐Dependent Biocatalytic Oxidation Reactions

“…Enzymatic oxidation and oxyfunctionalisation reactions are currently receiving tremendous interest in the context of preparative organic chemistry. [1] Especially if selectivity is desired, enzymatic reactions often excel over the chemical counterparts.A mongst available biocatalysts,m onooxygenases are of particular interest. [2] Monooxygenases,however, rely on molecular oxygen, which is reductively activated at the enzyme active site.T he reducing equivalents required are mostly derived more or less directly from reduced nicotinamide cofactors (NAD(P)H).…”

Formiat‐Oxidase (FOx) aus Aspergillus oryzae: ein Katalysator für verschiedene H2O2‐abhängige biokatalytische Oxidationen

“…Enzyme finden immer grçßeres Interesse als Oxidationsund Oxyfunktionalisierungskatalysatoren in der organischen Synthese. [1] Enzyme zeichnen sich insbesondere in ihrer Se-lektivitätg egenüber ihren chemischen Gegenstücken aus. Derzeit stehen Monooxygenasen im Vordergrund.…”