Enantioselective decarboxylative alkylation using synergistic photoenzymatic catalysis

Nature Catalysis, Год журнала: 2023, Номер 7(1), С. 35 - 42

Опубликована: Дек. 18, 2023

Язык: Английский

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Directed Evolution of an Iron(II)‐ and α‐Ketoglutarate‐Dependent Dioxygenase for Site‐Selective Azidation of Unactivated Aliphatic C−H Bonds**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(15)

Опубликована: Фев. 9, 2023

Abstract Fe II ‐ and α‐ketoglutarate‐dependent halogenases oxygenases can catalyze site‐selective functionalization of C−H bonds via a variety C−X bond forming reactions, but achieving high chemoselectivity for using non‐native functional groups remains rare. The current study shows that directed evolution be used to engineer variants the dioxygenase SadX address this challenge. Site‐selective azidation succinylated amino acids amine was achieved as result mutations throughout structure. installed azide group reduced primary amine, succinyl required enzymatically cleaved provide corresponding amine. These results promising starting point evolving additional with activity on structurally distinct substrates enabling enzymatic other groups.

Язык: Английский

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Enzyme-controlled stereoselective radical cyclization to arenes enabled by metalloredox biocatalysis

Nature Catalysis, Год журнала: 2023, Номер 6(7), С. 628 - 636

Опубликована: Июль 20, 2023

Язык: Английский

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Bioelectrocatalytic Synthesis: Concepts and Applications

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(46)

Опубликована: Июль 10, 2023

Abstract Bioelectrocatalytic synthesis is the conversion of electrical energy into value‐added products using biocatalysts. These methods merge specificity and selectivity biocatalysis energy‐related electrocatalysis to address challenges in sustainable pharmaceuticals, commodity chemicals, fuels, feedstocks fertilizers. However, specialized experimental setups domain knowledge for bioelectrocatalysis pose a significant barrier adoption. This review introduces key concepts bioelectrosynthetic systems. We provide tutorial on biocatalyst utilization, setup cells, analytical assessing bioelectrocatalysts. Key applications bioelectrosynthesis ammonia production small‐molecule are outlined both enzymatic microbial serves as necessary introduction resource non‐specialist interested research.

Язык: Английский

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Non-Native Site-Selective Enzyme Catalysis

Chemical Reviews, Год журнала: 2023, Номер 123(16), С. 10381 - 10431

Опубликована: Июль 31, 2023

The ability to site-selectively modify equivalent functional groups in a molecule has the potential streamline syntheses and increase product yields by lowering step counts. Enzymes catalyze site-selective transformations throughout primary secondary metabolism, but leveraging this capability for non-native substrates reactions requires detailed understanding of limitations enzyme catalysis how these bounds can be extended protein engineering. In review, we discuss representative examples involving group manipulation C-H bond functionalization. We include illustrative native catalysis, our focus is on cases often using engineered enzymes. then use enzymes chemoenzymatic target-oriented synthesis conclude with survey tools techniques that could expand scope catalysis.

Язык: Английский

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Catalyzing the future: recent advances in chemical synthesis using enzymes

Current Opinion in Chemical Biology, Год журнала: 2024, Номер 83, С. 102536 - 102536

Опубликована: Окт. 5, 2024

Язык: Английский

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Photoenzymatic Redox-Neutral Radical Hydrosulfonylation Initiated by FMN

ACS Catalysis, Год журнала: 2024, Номер 14(9), С. 6710 - 6716

Опубликована: Апрель 16, 2024

The photoinduced unnatural reactions catalyzed by flavin-dependent enzymes usually proceed through reduction pathways, which required the use of electron-sacrificial reagents. Herein, we developed a photoenzymatic redox-neutral radical hydrosulfonylation induced oxidated flavin (FMN) with sulfinates or sulfonyl hydrazines as precursors. reaction involved excited FMN acquiring an electron from substrate, and resulting sulfuryl was captured alkene. It is then stereoselectively quenched semiquinone (FMNsq) hydrogen atom transfer. This study circumvents need for NADPH recycling systems expands potential patterns in photobiocatalysis.

Язык: Английский

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Unnatural Thiamine Radical Enzymes for Photobiocatalytic Asymmetric Alkylation of Benzaldehydes and α-Ketoacids

ACS Catalysis, Год журнала: 2024, Номер 14(12), С. 9144 - 9150

Опубликована: Май 30, 2024

Despite substantial progress made toward elucidating the natural radical enzymology with thiamine pyrophosphate (TPP)-dependent pyruvate:ferredoxin oxidoreductases (PFORs) and pyruvate oxidases (POXs), repurposing naturally occurring two-electron TPP-dependent enzymes to catalyze single-electron transformations significant synthetic value remains a daunting task. Enabled by synergistic use of visible-light photocatalyst fluorescein set engineered derived from benzoylformate decarboxylase (BFD) benzaldehyde lyase (BAL), we developed an asymmetric photobiocatalytic decarboxylative alkylation benzaldehydes α-keto acids produce highly enantioenriched α-branched ketones. Mechanistically, propose that this dual catalytic involves oxidation enzyme-bound Breslow intermediate subsequent interception photoredox-generated transient alkyl radical. In conjunction visible light photoredox catalysis, biocatalysis represents emerging platform discover optimize are unknown biological systems not amenable small-molecule catalysis.

Язык: Английский

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A New Age of Biocatalysis Enabled by Generic Activation Modes

JACS Au, Год журнала: 2024, Номер 4(6), С. 2068 - 2080

Опубликована: Май 31, 2024

Biocatalysis is currently undergoing a profound transformation. The field moves from relying on nature's chemical logic to discipline that exploits generic activation modes, allowing for novel biocatalytic reactions and, in many instances, entirely new chemistry. Generic modes enable wide range of reaction types and played pivotal role advancing the fields organo- photocatalysis. This perspective aims summarize principal harnessed enzymes develop biocatalysts. Although extensively researched past, highlighted when applied within enzyme active sites, facilitate transformations have largely eluded efficient selective catalysis. advance attributed multiple tunable interactions substrate binding pocket precisely control competing pathways transition states. We will highlight cases synthetic methodologies achieved by engineered provide insights into potential future developments this rapidly evolving field.

Язык: Английский

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Mechanisms of C(sp3)–H and C=C selective oxidative heterofunctionalizations by non-heme Fe and Mn mimics of oxygenase enzymes

Coordination Chemistry Reviews, Год журнала: 2024, Номер 508, С. 215793 - 215793

Опубликована: Март 18, 2024

Язык: Английский

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