Enzymatic Conversion of CO₂: From Natural to Artificial Utilization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(9), P. 5702 - 5754

Published: Jan. 24, 2023

Enzymatic carbon dioxide fixation is one of the most important metabolic reactions as it allows capture inorganic from atmosphere and its conversion into organic biomass. However, due to often unfavorable thermodynamics difficulties associated with utilization CO

Language: Английский

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Biocatalysis: landmark discoveries and applications in chemical synthesis

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(6), P. 2828 - 2850

Published: Jan. 1, 2024

Biocatalysis has become an important tool in chemical synthesis, allowing access to complex molecules with high levels of activity and selectivity low environmental impact. Key discoveries protein engineering, bioinformatics, recombinant technology DNA sequencing have contributed towards the rapid acceleration field. This tutorial review explores enzyme engineering strategies high-throughput screening approaches that been applied for discovery development enzymes synthetic application. Landmark developments field are discussed carefully selected highlight diverse applications within pharmaceutical, agricultural, food industries. The design artificial biocatalytic cascades is also examined. will give readers insight into landmark milestones helped shape grow this branch catalysis since first enzyme.

Language: Английский

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Biocatalytic Enantioselective Synthesis of Atropisomers

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(23), P. 3362 - 3375

Published: Nov. 7, 2022

ConspectusAtropisomeric compounds are found extensively as natural products, ligands for asymmetric transition-metal catalysis, and increasingly bioactive pharmaceutically relevant targets. Their enantioselective synthesis is therefore an important ongoing research target. While a vast majority of known atropisomeric structures (hetero)biaryls, which display hindered rotation around C–C single bond, our group's long-standing interest in the control molecular conformation has led to identification stereoselective preparation variety other classes "nonbiaryl" displaying restricted C–C, C–N, C–O, C–S bonds.Biocatalytic transformations finding increasing application both academic industrial contexts result significant broadening range biocatalytic reactions sources enzymes available synthetic chemist. In this Account, we summarize main strategies currently biaryl, heterobiaryl, nonbiaryl atropisomers. As case with more traditional approaches these compounds, most methodologies construction enantioenriched atropisomers follow one two distinct strategies. The first direct bonds. Synthetically applicable type transformation limited, despite extensive into biosynthesis (hetero)biaryls by oxidative homocoupling or cross-coupling electron-rich arenes. second molecule bond that will form axis already exists, approach represents organic This strategy encompasses techniques including kinetic resolution (KR), desymmetrization, dynamic (DKR), (DYKAT).Nondynamic (KR) conformationally stable biaryl derivatives provided earliest numerous examples synthetically useful compounds. Lipases (i.e., mediate formation hydrolysis esters) particularly effective have attracted broad attention. success researchers broaden scope lipase-mediated desymmetrization reactions, addition limited number DKR DYKAT examples. By contrast, group used redox enzymes, engineered galactose oxidase (GOase) commercially ketoreductases (KREDs), desymmetrize prochiral diaryl ether derivatives. Building on experience conformational processes, later harnessed intramolecular noncovalent interactions facilitate at ambient temperatures, allowed development efficient heterobiaryl aldehydes using KREDs. With Account provide overview current prospective chemist molecules.

Language: Английский

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Synthesis of Enantiopure Sulfoxides by Concurrent Photocatalytic Oxidation and Biocatalytic Reduction

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(17)

Published: Feb. 21, 2022

Abstract The concurrent operation of chemical and biocatalytic reactions in one pot is still a challenging task, and, particular for photocatalysts, examples besides simple cofactor recycling systems are rare. However, especially due to the complementary chemistry that two fields catalysis promote, their combination has potential unlock intriguing, unprecedented overall reactivities. Herein we demonstrate reduction photocatalytic oxidation process. Specifically, enantioselective sulfoxide using ( S )‐selective methionine reductases was coupled an unselective light‐dependent sulfoxidation. Protochlorophyllide established as new green photocatalyst Overall, cyclic deracemization process produce nonracemic sulfoxides achieved target compounds were obtained with excellent conversions (up 91 %) superb optical purity (>99 % ee ).

Language: Английский

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An Up-to-Date Review on the Remediation of Dyes and Phenolic Compounds from Wastewaters Using Enzymes Immobilized on Emerging and Nanostructured Materials: Promises and Challenges

Nanomaterials, Journal Year: 2023, Volume and Issue: 13(15), P. 2152 - 2152

Published: July 25, 2023

Addressing the critical issue of water pollution, this review article emphasizes need to remove hazardous dyes and phenolic compounds from wastewater. These pollutants pose severe risks due their toxic, mutagenic, carcinogenic properties. The study explores various techniques for remediation organic contaminants wastewater, including an enzymatic approach. A significant challenge in wastewater treatment is loss enzyme activity difficulty recovery post-treatment. To mitigate these issues, examines strategy immobilizing enzymes on newly developed nanostructured materials like graphene, carbon nanotubes (CNTs), metal–organic frameworks (MOFs). offer high surface areas, excellent porosity, ample anchoring sites effective immobilization. evaluates recent research immobilization supports applications biocatalytic nanoparticles. It also analyzes impact operational factors (e.g., time, pH, temperature) dye compound removal using enzymes. Despite promising outcomes, acknowledges challenges large-scale implementation offers recommendations future tackle obstacles. This concludes by suggesting that emerging could present a sustainable, environmentally friendly solution escalating pollution crisis.

Language: Английский

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Site and Enantioselective Aliphatic C−H Oxidation with Bioinspired Chiral Complexes

The Chemical Record, Journal Year: 2021, Volume and Issue: 21(12), P. 4000 - 4014

Published: Oct. 5, 2021

Abstract Selective oxidation of aliphatic C−H bonds stands as an unsolved problem in organic synthesis, with the potential to offer novel paths for preparing molecules biological interest. The quest reagents that can perform this class reactions finds oxygenases and their mechanisms action inspiration motifs. Among numerous families synthetic catalysts have been explored, complexes linear tetraazadentate ligands combining two amines aromatic amine heterocycles display a structural versatility proven instrumental design showing site enantioselectivities, not accessible by conventional oxidants. This manuscript makes review recent advances field.

Language: Английский

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Enantioselective UHPLC Screening Combined with In Silico Modeling for Streamlined Development of Ultrafast Enantiopurity Assays

Analytical Chemistry, Journal Year: 2021, Volume and Issue: 94(3), P. 1804 - 1812

Published: Dec. 21, 2021

Enantioselective chromatography has been the preferred technique for determination of enantiomeric excess across academia and industry. Although sequential multicolumn enantioselective supercritical fluid screenings are widespread, access to automated ultra-high-performance liquid (UHPLC) platforms using state-of-the-art small particle size chiral stationary phases (CSPs) is an underdeveloped area. Herein, we introduce a UHPLC screening workflow capable combining 14 columns (packed with sub-2 μm fully porous sub-3 superficially particles) nine mobile phase eluent choices. This setup operates under vast selection reversed-phase chromatography, hydrophilic interaction polar-organic mode, polar-ionic mode conditions minimal manual intervention high success rate. Examples highly efficient enantioseparations illustrated from integration computer-assisted modeling. Furthermore, describe nuances in silico method development separations via second-degree polynomial regression fit LC simulator (ACD/Labs) software. The retention models were found be very accurate resolution single multicomponent mixtures species different types CSPs, differences between experimental simulated times less than 0.5%. Finally, illustrate how this approach lays foundation streamlined ultrafast applied high-throughput enantiopurity analysis its use second dimension two-dimensional experiments.

Language: Английский

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Engineered P450 Atom-Transfer Radical Cyclases are Bifunctional Biocatalysts: Reaction Mechanism and Origin of Enantioselectivity

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(29), P. 13344 - 13355

Published: July 13, 2022

New-to-nature radical biocatalysis has recently emerged as a powerful strategy to tame fleeting open-shell intermediates for stereoselective transformations. In 2021, we introduced novel metalloredox that leverages the innate redox properties of heme cofactor P450 enzymes, furnishing new-to-nature atom-transfer cyclases (ATRCases) with excellent activity and stereoselectivity. Herein, report combined computational experimental study shed light on mechanism origins enantioselectivity this system. Molecular dynamics quantum mechanics/molecular mechanics (QM/MM) calculations revealed an unexpected role key beneficial mutation I263Q. The glutamine residue serves essential hydrogen bond donor engages carbonyl moiety substrate promote bromine atom abstraction enhance cyclization. Therefore, evolved ATRCase is bifunctional biocatalyst, wherein enables biocatalysis, while further enhances enantioselectivity. Unlike many enzymatic stereocontrol rationales based rigid binding model, our computations demonstrate high degree rotational flexibility allyl in enzyme-substrate complex succeeding intermediates. controlled by cyclization transition states rather than orientation ground-state complexes preceding steps. During cyclization, anchoring effects Q263 steric interactions concurrently control π-facial selectivity, allowing highly enantioselective C-C formation. Our findings are corroborated experiments mutants generated from site-directed mutagenesis.

Language: Английский

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Regiodivergent and Enantioselective Hydroxylation of C−H bonds by Synergistic Use of Protein Engineering and Exogenous Dual‐Functional Small Molecules

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(4)

Published: Nov. 24, 2022

It is a great challenge to optionally access diverse hydroxylation products from given substrate bearing multiple reaction sites of sp3 and sp2 C-H bonds. Herein, we report the highly selective divergent alkylbenzenes by an engineered P450 peroxygenase driven dual-functional small molecule (DFSM). Using combinations various P450BM3 variants with DFSMs enabled more than half all possible hydroxylated each excellent regioselectivity (up >99 %), enantioselectivity % ee), high total turnover numbers 80963). Crystal structure analysis, molecular dynamic simulations, theoretical calculations revealed that synergistic effects between exogenous protein environment controlled regio- enantioselectivity. This work has implications for exogenous-molecule-modulated enzymatic regiodivergent enantioselective potential applications in synthetic chemistry.

Language: Английский

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Radical Termination via β-Scission Enables Photoenzymatic Allylic Alkylation Using “Ene”-Reductases

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(15), P. 9801 - 9805

Published: July 27, 2022

Allylations are practical transformations that forge C–C bonds while introducing an alkene for further chemical manipulations. Here, we report a photoenzymatic allylation of α-chloroamides with allyl silanes using flavin-dependent "ene"-reductases (EREDs). An engineered ERED can catalyze annulative allylic alkylation to prepare 5, 6, and 7-membered lactams high levels enantioselectivity. Ultrafast transient absorption spectroscopy indicates radical termination occurs via β-scission the silyl group afford radical, distinct mechanism by comparison traditional allylations involving silanes. Moreover, this represents alternative strategy EREDs. This was applied intermolecular couplings sulfones enol ethers. Overall, method highlights opportunity EREDs strategies beyond hydrogen atom transfer.

Language: Английский

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