Recent Advances in Theoretical Studies on Cu-Mediated Bond Formation Mechanisms Involving Radicals DOI
Ji‐Ren Liu,

Guo-Xiong Xu,

Li‐Gao Liu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2429 - 2454

Published: Feb. 1, 2024

Copper-catalyzed radical transformations establish a powerful toolkit to construct versatile complex organic compounds. The copper-mediated bond formation step of radicals plays critical role in controlling chemo- and stereoselectivity copper-catalyzed transformation reactions. This involves three possible pathways: ion-type formation, substitution, reductive elimination. review highlights the recent advances theoretical studies on mechanisms models selectivity Cu-mediated radical-involved providing general mechanistic comprehension this key elementary copper catalysis.

Language: Английский

Enantioselective decarboxylative alkylation using synergistic photoenzymatic catalysis DOI
Shang‐Zheng Sun, Bryce T. Nicholls, David C. Bain

et al.

Nature Catalysis, Journal Year: 2023, Volume and Issue: 7(1), P. 35 - 42

Published: Dec. 18, 2023

Language: Английский

Citations

36
Directed Evolution of an Iron(II)‐ and α‐Ketoglutarate‐Dependent Dioxygenase for Site‐Selective Azidation of Unactivated Aliphatic C−H Bonds** DOI Creative Commons

Christian A. Gomez,

Dibyendu Mondal,

Qian Du

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(15)

Published: Feb. 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.

Language: Английский

Citations

35
Enzyme-controlled stereoselective radical cyclization to arenes enabled by metalloredox biocatalysis DOI
Wen‐Zhen Fu, Natalia M. Neris, Yue Fu

et al.

Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(7), P. 628 - 636

Published: July 20, 2023

Language: Английский

Citations

31
Bioelectrocatalytic Synthesis: Concepts and Applications DOI Creative Commons
Dylan G. Boucher, Emily Carroll, Zachary A. Nguyen

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: July 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.

Language: Английский

Citations

25
Non-Native Site-Selective Enzyme Catalysis DOI
Dibyendu Mondal, Harrison M. Snodgrass,

Christian A. Gomez

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 10381 - 10431

Published: July 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.

Language: Английский

Citations

24
Catalyzing the future: recent advances in chemical synthesis using enzymes DOI
Julia C. Reisenbauer, Kathleen M. Sicinski, Frances H. Arnold

et al.

Current Opinion in Chemical Biology, Journal Year: 2024, Volume and Issue: 83, P. 102536 - 102536

Published: Oct. 5, 2024

Language: Английский

Citations

11
Mechanisms of C(sp3)–H and C=C selective oxidative heterofunctionalizations by non-heme Fe and Mn mimics of oxygenase enzymes DOI
Konstantin P. Bryliakov

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 508, P. 215793 - 215793

Published: March 18, 2024

Language: Английский

Citations

9
Photoenzymatic Redox-Neutral Radical Hydrosulfonylation Initiated by FMN DOI

Linye Jiang,

Dannan Zheng,

Xiaoyang Chen

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6710 - 6716

Published: April 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.

Language: Английский

Citations

9
Efficient Transferase Engineering for SAM Analog Synthesis from Iodoalkanes DOI Creative Commons
Kai H. Schülke,

Jana S. Fröse,

Alina Klein

et al.

ChemBioChem, Journal Year: 2024, Volume and Issue: 25(10)

Published: March 13, 2024

Abstract S ‐Adenosyl‐ l ‐methionine (SAM) is an important cosubstrate in various biochemical processes, including selective methyl transfer reactions. Simple methods for the (re)generation of SAM analogs could expand chemistry accessible with SAM‐dependent transferases and go beyond methylation Here we present efficient enzyme engineering strategy to synthesize different from “off‐the‐shelf” iodoalkanes through enzymatic alkylation ‐adenosyl‐ ‐homocysteine (SAH). This was achieved by mutating multiple hydrophobic structurally dynamic amino acids simultaneously. Combinatorial mutagenesis guided natural acid diversity generated a highly functional mutant library. approach increased speed as well scale providing panel optimized enzymes orders magnitude higher activities substrates just one round engineering. The exhibit catalytic efficiencies up 31 M −1 s , convert iodoalkanes, bearing cyclopropyl or aromatic moieties, catalyze ‐alkylation SAH very high stereoselectivities (>99 % de ). We further report throughput chromatographic screening system reliable rapid analog analysis. believe that described herein will advance field biocatalytic enabling regeneration reagents.

Language: Английский

Citations

8
Unnatural Thiamine Radical Enzymes for Photobiocatalytic Asymmetric Alkylation of Benzaldehydes and α-Ketoacids DOI
Xin Liu,

Sheng Xu,

Heyu Chen

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(12), P. 9144 - 9150

Published: May 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.

Language: Английский

Citations

8