Photobiocatalytic Strategies for Organic Synthesis

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(9), P. 5459 - 5520

Published: April 28, 2023

Biocatalysis has revolutionized chemical synthesis, providing sustainable methods for preparing various organic molecules. In enzyme-mediated most reactions involve molecules operating from their ground states. Over the past 25 years, there been an increased interest in enzymatic processes that utilize electronically excited states accessed through photoexcitation. These photobiocatalytic a diverse array of reaction mechanisms are complementary to one another. This comprehensive review will describe state-of-the-art strategies photobiocatalysis synthesis until December 2022. Apart reviewing relevant literature, central goal this is delineate mechanistic differences between general employed field. We organize based on relationship photochemical step and transformations. The include studies, substrate scopes, protein optimization strategies. By clearly defining mechanistically-distinct chemistry, we hope illuminate future synthetic opportunities area.

Language: Английский

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Metallaphotoredox catalysis for sp³C–H functionalizations through hydrogen atom transfer (HAT)

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(12), P. 4099 - 4120

Published: Jan. 1, 2023

sp 3 C–H functionalizations under the combination of photocatalytic HAT and transition metal catalysis.

Language: Английский

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Visible-Light Photoredox Catalysis in Water

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 88(10), P. 6284 - 6293

Published: June 14, 2022

The use of water in organic synthesis draws attention to its green chemistry features and unique ability unveil unconventional reactivities. Herein, literature about the as a reaction medium under visible-light photocatalytic conditions is summarized order highlight challenges opportunities. Accordingly, this Synopsis has been divided into four different sections focused on (1) role reactions, (2) in-/on-water (3) water-soluble photocatalysts, (4) photomicellar catalytic systems.

Language: Английский

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Chemoenzymatic Cascades Combining Biocatalysis and Transition Metal Catalysis for Asymmetric Synthesis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(18)

Published: Feb. 6, 2023

Abstract The combination of catalytic methods provides multiple advantages in organic synthesis, allowing access to diverse molecules a straightforward manner. Merging metal and enzyme catalysis is currently receiving great attention due the possibility assemble C−C coupling, olefin metathesis, hydration other reactions with exquisite stereospecificity displayed by enzymes. Thus, this minireview organized based on action species (Pd, Ru, Au, Ir, Fe…) different Special will be paid design sequential processes concurrent cascades, presenting solutions such as use surfactants or compartmentalization strategies for those cases where incompatibilities could hamper overall process.

Language: Английский

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Novel applications of photobiocatalysts in chemical transformations

RSC Advances, Journal Year: 2024, Volume and Issue: 14(4), P. 2590 - 2601

Published: Jan. 1, 2024

Photocatalysis has proven to be an effective approach for the production of reactive intermediates under moderate reaction conditions.

Language: Английский

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Enhanced Photocatalytic Efficiency in Visible-Light-Induced NADH Regeneration by Intramolecular Electron Transfer

ACS Applied Materials & Interfaces, Journal Year: 2022, Volume and Issue: 14(34), P. 38895 - 38904

Published: Aug. 20, 2022

Inspired by natural photosynthesis, photocatalytic NADH regeneration has drawn increasing interest in the recent decade as it provides a perfect approach for NAD+ reduction into NADH, which can be further consumed oxidordeuctase enzymatic redox reactions. However, two issues still remain unsolved this procedure. First, efficiency hydrogenation requires improvement. Second, rhodium electron mediator [Cp*Rh(bpy)H2O]2+ (M), is always required selective 1,4-NADH regeneration, difficult to recover because of its good solubility aqueous solution. Given high price M, highly wasteful and inefficient if only spends once. Here, we report Cp*Rh(bpy)Cl implanted conjugated microporous polymer DTS/Rh@CMPs employed effective visible light photocatalysts situ without using additional M. In addition, insertion Rh complex skeleton, demonstrated UV-vis, fluorescence, photocurrent electrochemical impedance, dramatically improves absorption capacity separation transfer efficiency. Compared with that DTS@CMP-1 an enhanced reaction yield 33% was determined DTS/Rh@CMP-1 suggesting intramolecular better activity than intermolecular reduction. Moreover, rooted firmly framework, negligible loss conversion decrease are observed. When coupled yeast alcohol dehydrogenase (YADH, from Saccharomyces cerevisiae), 1.36 mM methanol accumulated, implying excellent biocompatibility feasibility photobiocatalysis formaldehyde hydrogenation.

Language: Английский

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Exciting Enzymes: Current State and Future Perspective of Photobiocatalysis

ChemPhotoChem, Journal Year: 2023, Volume and Issue: 7(7)

Published: May 2, 2023

Abstract The recent increase of interest in photocatalysis spread to biocatalysis and triggered a rush for the development light‐dependent enzyme‐mediated or enzyme‐coupled processes. After several years intense research on photobiocatalysis, it is time evaluate state field structured manner. In this Perspective, we suggest group photobiocatalysis into distinct disciplines provide principal guidelines standards reporting photobiocatalytic results as well advice performing reactions. Overall, assess that contributes diversity biocatalytic reactions while offering selectivity enzymes photocatalysis. We foresee ongoing excitement enzymatic processes will lead discovery novel mechanisms complement with new bond‐forming additional innovative strategies utilize light possible benign energy source.

Language: Английский

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Recent Advances in Visible Light‐induced Asymmetric Transformations of Carbonyl Compounds into Chiral Alcohols

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(21)

Published: Aug. 16, 2023

Abstract Visible light‐induced photocatalysis has been widely investigated, which offers exciting opportunities to build new catalytic platforms that are unattainable under ground state conditions. Asymmetric a longstanding challenge due the high reactivity of photogenerated intermediates leading strong background reaction. Carbonyl group is an important fundamental scaffold in organic synthesis. The photocatalytic asymmetric transformations carbonyl compounds for synthesizing enantioenriched secondary and tertiary alcohols significant value but remain problematic. Even so, series intriguing works concerning this topic have reported recent year. This review summarizes advances area, mainly dividing into single synergetic catalyst systems, mechanism each reaction discussed.

Language: Английский

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Metallaphotoredox catalysis for sp3 C–H functionalizations through single-electron transfer

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(9), P. 963 - 976

Published: Sept. 24, 2024

Language: Английский

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Strategies for Transferring Photobiocatalysis to Continuous Flow Exemplified by Photodecarboxylation of Fatty Acids

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(22), P. 14040 - 14049

Published: Oct. 31, 2022

The challenges of light-dependent biocatalytic transformations lipophilic substrates in aqueous media are manifold. For instance, photolability the catalyst as well insufficient light penetration into reaction vessel may be further exacerbated by a heterogeneously dispersed substrate. Light addressed performing continuous flow, which allows two modes applying catalyst: (i) heterogeneously, immobilized on carrier, requires light-permeable supports, or (ii) homogeneously, dissolved mixture. Taking photodecarboxylation palmitic acid catalyzed fatty-acid photodecarboxylase from Chlorella variabilis (CvFAP) showcase, strategies for transfer photoenzyme-catalyzed flow were identified. A range different supports evaluated immobilization CvFAP, whereby Eupergit C250 L was carrier choice. As photostability limiting factor, homogeneous system preferred instead employing heterogenized enzyme. This implied that photolabile enzymes preferably applied solution if repair mechanisms cannot provided. Furthermore, when comparing wavelengths and intensities, extinction coefficients considered to ensure comparable absorption at each wavelength. Employing conditions CvFAP-catalyzed afforded space-time yield unsurpassed any reported batch process (5.7 g·L–1·h–1, 26.9 mmol·L–1·h–1) this reaction, demonstrating advantage attaining higher productivity photobiocatalytic processes.

Language: Английский

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