Where Chemocatalysis Meets Biocatalysis: In Water

Chemical Reviews, Journal Year: 2022, Volume and Issue: 123(9), P. 5262 - 5296

Published: Dec. 6, 2022

Chemoenzymatic catalysis, by definition, involves the merging of sequential reactions using both chemocatalysis and biocatalysis, typically in a single reaction vessel. A major challenge, solution to which, however, is associated with numerous advantages, run such one-pot processes water: majority enzyme-catalyzed take place water as Nature's medium, thus enabling broad synthetic diversity when due option use virtually all types enzymes. Furthermore, cheap, abundantly available, environmentally friendly, making it, principle, an ideal medium. On other hand, most routinely performed today organic solvents (which might deactivate enzymes), appearing make it difficult combine biocatalysis toward cascades water. Several creative approaches solutions that enable combinations chemo- be realized applied problems are presented herein, reflecting state-of-the-art this blossoming field. Coverage has been sectioned into three parts, after introductory remarks: (1) Chapter 2 focuses on historical developments initiated area research; (2) 3 describes key post-initial discoveries have advanced field; (3) 4 highlights latest achievements provide attractive main question compatibility between (used predominantly aqueous media) (that remains solvents), Chapters covering mainly literature from ca. 2018 present. 5 6 brief overview where field stands, challenges lie ahead, ultimately, prognosis looking future chemoenzymatic catalysis synthesis.

Language: Английский

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Expanding the Synthetic Toolbox through Metal–Enzyme Cascade Reactions

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(9), P. 5297 - 5346

Published: Jan. 10, 2023

The combination of metal-, photo-, enzyme-, and/or organocatalysis provides multiple synthetic solutions, especially when the creation chiral centers is involved. Historically, enzymes and transition metal species have been exploited simultaneously through dynamic kinetic resolutions racemates. However, more recently, linear cascades appeared as elegant solutions for preparation valuable organic molecules combining bioprocesses metal-catalyzed transformations. Many advantages are derived from this symbiosis, although there still bottlenecks to be addressed including successful coexistence both catalyst types, need compatible reaction media mild conditions, or minimization cross-reactivities. Therefore, here also provided by means coimmobilization, compartmentalization strategies, flow chemistry, etc. A comprehensive review presented focusing on period 2015 early 2022, which has divided into two main sections that comprise first use metals independent catalysts but working in an orchestral sequential manner, later their application bionanohybrid materials coimmobilization adequate supports. Each part classified different subheadings, based catalyzed catalyst, while development nonasymmetric stereoselective processes was considered section.

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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Chemoenzymatic synthesis of C14-functionalized steroids

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(8), P. 729 - 739

Published: April 17, 2023

Language: Английский

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Asymmetric α-benzylation of cyclic ketones enabled by concurrent chemical aldol condensation and biocatalytic reduction

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 2, 2024

Abstract Chemoenzymatic cascade catalysis has emerged as a revolutionary tool for streamlining traditional retrosynthetic disconnections, creating new possibilities the asymmetric synthesis of valuable chiral compounds. Here we construct one-pot concurrent chemoenzymatic by integrating organobismuth-catalyzed aldol condensation with ene-reductase (ER)-catalyzed enantioselective reduction, enabling formal α-benzylation cyclic ketones. To achieve this, develop pair enantiocomplementary ERs capable reducing α-arylidene ketones, lactams, and lactones. Our engineered mutants exhibit significantly higher activity, up to 37-fold, broader substrate specificity compared parent enzyme. The key success is due well-tuned hydride attack distance/angle and, more importantly, synergistic proton-delivery triade Tyr28-Tyr69-Tyr169. Molecular docking density functional theory (DFT) studies provide important insights into bioreduction mechanisms. Furthermore, demonstrate synthetic utility best in several synthons.

Language: Английский

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Efficient Production of L‐Homophenylalanine by Enzymatic‐Chemical Cascade Catalysis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: June 28, 2022

L-Homophenylalanine (L-HPA) is a vital building block for the synthesis of numerous chiral drugs. However, high cost starting materials limits industrial production L-HPA. In this study, an enzymatic-spontaneous chemical cascade route L-HPA was designed based on retrosynthetic analysis. This route, using simple benzaldehyde and pyruvate as materials, extremely cost-effective. The enzymes were screened further assembled in E. coli, TipheDH identified rate-limiting enzyme. Therefore, engineered to improve its specific activity (by 82 %) expression level 254 %), thus generating best strain (W14). W14 exhibited optimum enzyme ratio (1.7 : 1.1 1 1.8) demonstrated 100.9 g L-1 (with 94 % conversion, >99 ee) 5-L reactor. effectively exploits power cascades offers insight into avenues synthesizing other valuable chemicals from inexpensive blocks.

Language: Английский

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Combining Electro-, Photo-, and Biocatalysis for One-Pot Selective Conversion of Furfural into Value-Added C4 Chemicals

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(2), P. 1371 - 1380

Published: Jan. 9, 2023

Chemobiocatalysis has emerged as a powerful tool in synthetic chemistry, but one-pot multistep syntheses incorporating multiple types of catalysts remain challenging because the greatly increased incompatible issues between different catalysts. In this work, we reported combination electro-, photo-, and biocatalysis for selective valorization biomass-derived furfural into various C4 chemicals including maleic acid (MA), fumaric (FA), d- l-malic (MalA), l-aspartic (l-Asp). MA was concurrently synthesized from via cascade electrochemical oxidations with 4-acetamido-2,2,6,6-tetramethylpiperidine-N-oxyl (ACT) photo-oxygenation eosin Y (EY) up to 97% yield. ACT is versatile catalyst capable oxidizing both intermediate 5-hydroxy-2-(5H)-furanone. Then, harnessed produce enantiopure after photoelectrocatalysis. Furfural selectively converted d-MalA sequential photoelectrooxidation biocatalytic hydration 91% yield maleate hydratase readily inactivated under light irradiation. Also, cis–trans isomerase (MaiA) found be highly sensitive chemical oxidation; thus, two-step synthesis FA its derivatives l-MalA l-Asp performed by sequentially using ACT/EY one/dual-enzyme 79–97% yields. Both reaction engineering strategies were applied address incompatibility MaiA photoelectrooxidation. Consequently, produced concurrent manner 67% The present work demonstrates great power chemobiocatalysis platform chemicals.

Language: Английский

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Spatiotemporal control for integrated catalysis

Nature Reviews Methods Primers, Journal Year: 2023, Volume and Issue: 3(1)

Published: April 6, 2023

Language: Английский

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Status check: biocatalysis; its use with and without chemocatalysis. How does the fine chemicals industry view this area?

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(16), P. 6092 - 6107

Published: Jan. 1, 2023

Stages of the penetration catalytic technology and necessity for fruitful collaboration.

Language: Английский

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A straightforward chemobiocatalytic route for one-pot valorization of glucose into 2,5-bis(hydroxymethyl)furan

Bioresources and Bioprocessing, Journal Year: 2024, Volume and Issue: 11(1)

Published: April 18, 2024

Abstract Direct conversion of inexpensive biomass into value-added chemicals via furanic platform molecules is highly attractive. In this work, we present a straightforward chemobiocatalytic route for glucose valorization 2,5-bis(hydroxymethyl)furan (BHMF) in one pot, with no purification the intermediate 5-hydroxymethylfurfural (HMF). Six candidate alcohol dehydrogenase (ADH) genes were located from Meyerozyma guilliermondii SC1103, based on comparative transcriptome analysis and real-time quantitative polymerase chain reaction. An ADH ( Mg ADH1) was identified upon evaluation catalytic performances recombinant Saccharomyces cerevisiae harboring ADHs HMF reduction. Soluble expression enzyme S. greatly enhanced by its codon optimization, leading to improved tolerance (up 400 mM). fed-batch process, desired product approximately 473 mM (60.5 g/L) produced within 30 h _ ADH1. A toward BHMF constructed merging CaCl 2 -mediated isomerization dehydration biocatalytic reduction an overall yield 42%, starting glucose. This work may pave way green manufacture valuable biobased chemicals.

Language: Английский

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