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Substrate-Specific Evolution of Amine Dehydrogenases for Accessing Structurally Diverse Enantiopure (R)-β-Amino Alcohols

Yin, Xinjian (author), Gong, Wenzhong (author), Zeng, Yujing (author), Qiu, Hulin (author), Liu, Lan (author), Hollmann, F. (author), Chen, Bishuang (author)

The biocatalytic oxidative deamination of β-amino alcohols holds significant practical potential in kinetic resolution and/or deracemization process to access (R)-β-amino alcohols. This study exemplifies a notable instance of acquisition and utilization of this valuable oxidative deamination activity. Initially, the mutation N261M (M0) was...

journal article 2024

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Selective Peroxygenase-Catalysed Oxidation of Toluene Derivates to Benzaldehydes

Wang, Y. (author), Teetz, Niklas (author), Holtmann, Dirk (author), Alcalde, Miguel (author), van Hengst, J.M.A. (author), Liu, Xiaoxiao (author), Wang, Mengfan (author), Qi, Wei (author), Zhang, Wuyuan (author), Hollmann, F. (author)

Biocatalytic oxidation reactions of toluene derivates to the corresponding aldehydes are typically challenged by regio- and chemoselectivity issues. In this contribution we address both challenges by a combined reactant- and reaction engineering approach. We demonstrate that the peroxygenase-catalysed transformation of ring-substituted...

journal article 2023

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Mirror, mirror on the wall which is the greenest of them all? A critical comparison of chemo- and biocatalytic oxyfunctionalisation reactions

Wu, Y. (author), Paul, C.E. (author), Hollmann, F. (author)

This review article critically compares two widely used types of catalysis, chemo- and biocatalysis, and provides insights on their greenness according to specified parameters. A comparative analysis of the environmental impact of chemo- and biocatalytic oxyfunctionalisation reactions based on published experimental data reveals that both...

journal article 2023

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Engineering a Highly Regioselective Fungal Peroxygenase for the Synthesis of Hydroxy Fatty Acids

Gomez de Santos, Patricia (author), González-Benjumea, Alejandro (author), Fernandez-Garcia, Angela (author), Aranda, Carmen (author), Wu, Y. (author), But, A. (author), Molina-Espeja, Patricia (author), Zhang, W. (author), Hollmann, F. (author)

The hydroxylation of fatty acids is an appealing reaction in synthetic chemistry, although the lack of selective catalysts hampers its industrial implementation. In this study, we have engineered a highly regioselective fungal peroxygenase for the ω-1 hydroxylation of fatty acids with quenched stepwise over-oxidation. One single mutation near...

journal article 2023

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Alcohol Dehydrogenases as Catalysts in Organic Synthesis

Silva de Miranda, Amanda (author), Milagre, C.D.D.F. (author), Hollmann, F. (author)

Alcohol dehydrogenases (ADHs) have become important catalysts for stereoselective oxidation and reduction reactions of alcohols, aldehydes and ketones. The aim of this contribution is to provide the reader with a timely update on the state-of-the-art of ADH-catalysis. Mechanistic basics are presented together with practical information about the...

journal article 2022

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Towards Biocatalytic Oxidation of Secondary Alcohols to Carbonyl Products of Relevance for Flavors and Fragrances

Puchľová, Eva (author), Hilberath, T. (author), Vranková, Kvetoslava (author), Hollmann, F. (author)

Non-enantioselective alcohol dehydrogenases (ADHs) are rarely found in the biocatalysis portfolio. Generally, highly enantioselective ADHs are sought for. Using such ADHs for the oxidation of racemic alcohols generally results in a kinetic resolution of the starting material, which is unfavourable if the ketone represents the product of interest...

journal article 2022

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Biocatalytic Aromaticity-Breaking Epoxidation of Naphthalene and Nucleophilic Ring-Opening Reactions

Zhang, W. (author), Li, Huanhuan (author), Younes, S.H.H. (author), Gómez De Santos, Patricia (author), Tieves, F. (author), Grogan, Gideon (author), Pabst, Martin (author), Alcalde, Miguel (author), Whitwood, Adrian C. (author), Hollmann, F. (author)

Aromatic hydroxylation reactions catalyzed by heme-thiolate enzymes proceed via an epoxide intermediate. These aromatic epoxides could be valuable building blocks for organic synthesis giving access to a range of chiral trans-disubstituted cyclohexadiene synthons. Here, we show that naphthalene epoxides generated by fungal peroxygenases can...

journal article 2021

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Valorization of Small Alkanes by Biocatalytic Oxyfunctionalization

Mahor, Durga (author), Cong, Zhiqi (author), Weissenborn, Martin J. (author), Hollmann, F. (author), Zhang, Wuyuan (author)

The oxidation of alkanes into valuable chemical products is a vital reaction in organic synthesis. This reaction, however, is challenging, owing to the inertness of C−H bonds. Transition metal catalysts for C−H functionalization are frequently explored. Despite chemical alternatives, nature has also evolved powerful oxidative enzymes (e. g.,...

review 2021

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Recent developments in the use of peroxygenases – Exploring their high potential in selective oxyfunctionalisations

Hobisch, Markus (author), Holtmann, Dirk (author), Gomez de Santos, Patricia (author), Alcalde, Miguel (author), Hollmann, F. (author), Kara, Selin (author)

Peroxygenases are an emerging new class of enzymes allowing selective oxyfunctionalisation reactions in a cofactor-independent way different from well-known P450 monooxygenases. Herein, we focused on recent developments from organic synthesis, molecular biotechnology and reaction engineering viewpoints that are devoted to bring these enzymes...

review 2021

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Flavoenzyme-mediated Regioselective Aromatic Hydroxylation with Coenzyme Biomimetics

Guarneri, A. (author), Westphal, Adrie H. (author), Leertouwer, C.J. (author), Lunsonga, Joy (author), Franssen, Maurice C.R. (author), Opperman, Diederik J. (author), Hollmann, F. (author), van Berkel, Willem J.H. (author), Paul, C.E. (author)

Regioselective aromatic hydroxylation is desirable for the production of valuable compounds. External flavin-containing monooxygenases activate and selectively incorporate an oxygen atom in phenolic compounds through flavin reduction by the nicotinamide adenine dinucleotide coenzyme, and subsequent reaction with molecular oxygen. This study...

journal article 2020

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Towards Preparative Chemoenzymatic Oxidative Decarboxylation of Glutamic Acid

Xu, X. (author), But, A. (author), Wever, Ron (author), Hollmann, F. (author)

The chemoenzymatic oxidative decarboxylation of glutamic acid to the corresponding nitrile using the vanadium chloroperoxidase from Curvularia inaequalis (CiVCPO) as HOBr generation catalysts has been investigated. Product inhibition was identified as major limitation. Nevertheless, 1630000 turnovers and k_cat of 75 s⁻¹...

journal article 2020

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Piezobiocatalysis: Ultrasound-Driven Enzymatic Oxyfunctionalization of C-H Bonds

Yoon, Jaeho (author), Kim, Jinhyun (author), Tieves, F. (author), Zhang, W. (author), Alcalde, Miguel (author), Hollmann, F. (author), Park, Chan Beum (author)

Peroxygenases have long inspired the selective oxyfunctionalization of various aliphatic and aromatic compounds, because of their broad substrate spectrum and simplicity of catalytic mechanism. This study provides a proof-of-concept of piezobiocatalysis by demonstrating peroxygenase-catalyzed oxyfunctionalization reactions fueled by...

journal article 2020

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Biocatalytic axidation of alcohols

Puetz, Hendrik (author), Puchľová, Eva (author), Vranková, Kvetoslava (author), Hollmann, F. (author)

Enzymatic methods for the oxidation of alcohols are critically reviewed. Dehydrogenases and oxidases are the most prominent biocatalysts, enabling the selective oxidation of primary alcohols into aldehydes or acids. In the case of secondary alcohols, region and/or enantioselective oxidation is possible. In this contribution, we outline the...

review 2020

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Efficient Aerobic Oxidation of trans-2-Hexen-1-ol using the Aryl Alcohol Oxidase from Pleurotus eryngii

Pedroso de Almeida, T. (author), van Schie, M.M.C.H. (author), Ma, A. (author), Tieves, F. (author), Younes, S.H.H. (author), Fernandez Fueyo, E. (author), Arends, I.W.C.E. (author), Riul, A. (author), Hollmann, F. (author)

The selective oxidation of trans-2-hexen-1-ol to the corresponding aldehyde using a recombinant aryl alcohol oxidase from Pleurotus eryngii (PeAAOx) is reported. Especially using the two liquid phase system to overcome solubility and product inhibition issues enabled to achieve more than 2.200.000 catalytic turnovers for the production enzyme...

journal article 2019

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Formate Oxidase (FOx) from Aspergillus oryzae: One Catalyst Enables Diverse H ₂ O ₂ -Dependent Biocatalytic Oxidation Reactions

Tieves, F. (author), Willot, S.J. (author), van Schie, M.M.C.H. (author), Rauch, M.C.R. (author), Younes, S.H.H. (author), Zhang, W. (author), Dong, J. (author), Gomez de Santos, P. (author), Hollmann, F. (author)

An increasing number of biocatalytic oxidation reactions rely on H ₂ O ₂ as a clean oxidant. The poor robustness of most enzymes towards H ₂ O ₂ , however, necessitates more efficient systems for in situ H ₂ O ₂ generation. In analogy to the well-known formate dehydrogenase to...

journal article 2019

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Cascading g-C₃N₄ and Peroxygenases for Selective Oxyfunctionalization Reactions

van Schie, M.M.C.H. (author), Zhang, W. (author), Tieves, F. (author), Choi, Da Som (author), Park, Chan Beum (author), Burek, Bastien O. (author), Bloh, Jonathan Z. (author), Arends, I.W.C.E. (author), Paul, C.E. (author), Alcalde, Miguel (author), Hollmann, F. (author)

Peroxygenases are very interesting catalysts for specific oxyfunctionalization chemistry. Instead of relying on complicated electron transport chains, they rely on simple hydrogen peroxide as the stoichiometric oxidant. Their poor robustness against H₂O₂ can be addressed via in situ generation of H₂O<sub>2<...

journal article 2019

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Biocatalytic synthesis of the Green Note trans-2-hexenal in a continuous-flow microreactor

van Schie, M.M.C.H. (author), Pedroso de Almeida, T. (author), Laudadio, Gabriele (author), Tieves, F. (author), Fernandez Fueyo, E. (author), Noël, Timothy (author), Arends, I.W.C.E. (author), Hollmann, F. (author)

The biocatalytic preparation of trans-hex-2-enal from trans-hex-2-enol using a novel aryl alcohol oxidase from Pleurotus eryngii (PeAAOx) is reported. As O₂-dependent enzyme PeAAOx-dependent reactions are generally plagued by the poor solubility of O₂ in aqueous media and mass transfer limitations resulting in poor...

journal article 2018

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Biocatalytic Oxidation Reactions: A Chemist's Perspective

Dong, J. (author), Fernandez Fueyo, E. (author), Hollmann, F. (author), Paul, C.E. (author), Pesic, M. (author), Schmidt, S. (author), Wang, Yonghua (author), Younes, S.H.H. (author), Zhang, W. (author)

Oxidation chemistry using enzymes is approaching maturity and practical applicability in organic synthesis. Oxidoreductases (enzymes catalysing redox reactions) enable chemists to perform highly selective and efficient transformations ranging from simple alcohol oxidations to stereoselective halogenations of non‐activated C−H bonds. For many of...

journal article 2018

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Biocatalytic synthesis of lactones and lactams

Hollmann, F. (author), Kara, Selin (author), Opperman, Diederik J. (author), Wang, Yonghua (author)

Cyclic esters and amides (lactones and lactams) are important active ingredients and polymer building blocks. In recent years, numerous biocatalytic methods for their preparation have been developed including enzymatic and chemoenzymatic Baeyer–Villiger oxidations, oxidative lactonisation of diols, and reductive lactonisation and...

journal article 2018

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Selective Photooxidation Reactions using Water-Soluble Anthraquinone Photocatalysts

Zhang, W. (author), Gacs, Jenő (author), Arends, I.W.C.E. (author), Hollmann, F. (author)

The aerobic organocatalytic oxidation of alcohols was achieved by using water-soluble sodium anthraquinone sulfonate. Under visible-light activation, this catalyst mediated the aerobic oxidation of alcohols to aldehydes and ketones. The photo-oxyfunctionalization of alkanes was also possible under these conditions.

journal article 2017