Photocatalytic Functionalization of Dehydroalanine‐Derived Peptides in Batch and Flow DOI Creative Commons
Nikolaos Kaplaneris, Merve Akdeniz, Méritxell Fillols

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: March 18, 2024

Abstract Unnatural amino acids, and their synthesis by the late‐stage functionalization (LSF) of peptides, play a crucial role in areas such as drug design discovery. Historically, LSF biomolecules has predominantly utilized traditional synthetic methodologies that exploit nucleophilic residues, cysteine, lysine or tyrosine. Herein, we present photocatalytic hydroarylation process targeting electrophilic residue dehydroalanine (Dha). This possesses an α , β ‐unsaturated moiety can be combined with various arylthianthrenium salts, both batch flow reactors. Notably, setup proved instrumental for efficient scale‐up, paving way unnatural acids peptides substantial quantities. Our approach, being inherently mild, permits diversification even when they contain sensitive functional groups. The readily available salts facilitate seamless integration Dha‐containing wide range arenes, blueprints, natural products, culminating creation unconventional phenylalanine derivatives. synergistic effect high group tolerance modular characteristic aryl electrophile enables peptide conjugation ligation conditions.

Language: Английский

Electrochemical Late-Stage Functionalization DOI Creative Commons
Yulei Wang, Suman Dana, Hao Long

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(19), P. 11269 - 11335

Published: Sept. 26, 2023

Late-stage functionalization (LSF) constitutes a powerful strategy for the assembly or diversification of novel molecular entities with improved physicochemical biological activities. LSF can thus greatly accelerate development medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical synthesis has emerged as an environmentally friendly platform transformation organic compounds. Over past decade, electrochemical late-stage (eLSF) gained major momentum, which is summarized herein up to February 2023.

Language: Английский

Citations

144
Strain-Release Photocatalysis DOI
Peter Bellotti, Frank Glorius

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(38), P. 20716 - 20732

Published: Sept. 15, 2023

The concept of strain in organic compounds is as old modern chemistry and was initially introduced to justify the synthetic setbacks along synthesis small ring systems (pars construens strain). In last decades, chemists have developed an arsenal strain-release reactions destruens strain) which can generate─with significant driving force─rigid aliphatic that act three-dimensional alternatives (hetero)arenes. Photocatalysis added additional dimension processes by leveraging energy photons create chemical complexity under mild conditions. This perspective presents latest advancements photocatalysis─with emphases on mechanisms, catalytic cycles, current limitations─the unique architectures be produced, possible future directions.

Language: Английский

Citations

132
Late-Stage C–H Functionalization of Azines DOI

Celena M. Josephitis,

Hillary M. H. Nguyen, Andrew McNally

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(12), P. 7655 - 7691

Published: May 3, 2023

Azines, such as pyridines, quinolines, pyrimidines, and pyridazines, are widespread components of pharmaceuticals. Their occurrence derives from a suite physiochemical properties that match key criteria in drug design is tunable by varying their substituents. Developments synthetic chemistry, therefore, directly impact these efforts, methods can install various groups azine C–H bonds particularly valuable. Furthermore, there growing interest late-stage functionalization (LSF) reactions focus on advanced candidate compounds often complex structures with multiple heterocycles, functional groups, reactive sites. Because factors electron-deficient nature the effects Lewis basic N atom, distinct arene counterparts, application LSF contexts difficult. However, have been many significant advances reactions, this review will describe progress, much which has occurred over past decade. It possible to categorize radical addition processes, metal-catalyzed activation transformations occurring via dearomatized intermediates. Substantial variation reaction within each category indicates both rich reactivity heterocycles creativity approaches involved.

Language: Английский

Citations

109
Recent advances in the electrochemical generation of 1,3-dicarbonyl radicals from C–H bonds DOI

Qinhui Wan,

Zhongyi Zhang,

Zhong‐Wei Hou

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(11), P. 2830 - 2848

Published: Jan. 1, 2023

Recent advances in the electrochemical generation of 1,3-dicarbonyl radicals from C–H bonds and their mechanistic insights synthetic applications have been summarized.

Language: Английский

Citations

80
Resurgence and advancement of photochemical hydrogen atom transfer processes in selective alkane functionalizations DOI Creative Commons
Liang Chang, Shun Wang, Qing An

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(25), P. 6841 - 6859

Published: Jan. 1, 2023

The selective functionalization of alkanes has long been recognized as a prominent challenge and an arduous task in organic synthesis. Hydrogen atom transfer (HAT) processes enable the direct generation reactive alkyl radicals from feedstock have successfully employed industrial applications such methane chlorination process,

Language: Английский

Citations

70
Photodriven Methane Conversion on Transition Metal Oxide Catalyst: Recent Progress and Prospects DOI Creative Commons
Pu Wang, Run Shi, Jiaqi Zhao

et al.

Advanced Science, Journal Year: 2023, Volume and Issue: 11(8)

Published: Oct. 26, 2023

Methane as the main component in natural gas is a promising chemical raw material for synthesizing value-added chemicals, but its harsh conversion process often causes severe energy and environment concerns. Photocatalysis provides an attractive path to active convert methane into various products under mild conditions with clean sustainable solar energy, although many challenges remain at present. In this review, recent advances photocatalytic are systematically summarized. As basis of conversion, activation first elucidated from structural molecules. The study committed categorizing elucidating research progress laws intricate reactions according target products, including partial oxidation, reforming, coupling, combustion, functionalization. Advanced reactor designs also designed enrich options reliability performance evaluation. prospects discussed, which turn offers guidelines methane-conversion-related photocatalyst exploration, reaction mechanism investigation, advanced photoreactor design.

Language: Английский

Citations

44
Single-Electron Oxidation-Initiated Enantioselective Hydrosulfonylation of Olefins Enabled by Photoenzymatic Catalysis DOI

Qinglong Shi,

Xiu‐Wen Kang, Zhiyong Liu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2748 - 2756

Published: Jan. 12, 2024

Controlling the enantioselectivity of hydrogen atom transfer (HAT) reactions has been a long-standing synthetic challenge. While recent advances on photoenzymatic catalysis have demonstrated great potential non-natural photoenzymes, all transformations are initiated by single-electron reduction substrate, with only one notable exception. Herein, we report an oxidation-initiated enantioselective hydrosulfonylation olefins using novel mutant gluconobacter ene-reductase (GluER-W100F-W342F). Compared to known systems, our approach does not rely formation electron donor–acceptor complex between substrates and enzyme cofactor simplifies reaction system obviating addition regeneration mixture. More importantly, GluER variant exhibits high reactivity broad substrate scope. Mechanistic studies support proposed mechanism reveal that tyrosine-mediated HAT process is involved.

Language: Английский

Citations

39
Photocatalyzed Enantioselective Functionalization of C(sp3)–H Bonds DOI
Guo‐Qiang Xu, Wei David Wang, Peng‐Fei Xu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1209 - 1223

Published: Jan. 3, 2024

Owing to its diverse activation processes including single-electron transfer (SET) and hydrogen-atom (HAT), visible-light photocatalysis has emerged as a sustainable efficient platform for organic synthesis. These provide powerful avenue the direct functionalization of C(sp3)–H bonds under mild conditions. Over past decade, there have been remarkable advances in enantioselective bond via combined with conventional asymmetric catalysis. Herein, we summarize involving discuss two main pathways this emerging field: (a) SET-driven carbocation intermediates are followed by stereospecific nucleophile attacks; (b) photodriven alkyl radical further enantioselectively captured (i) chiral π-SOMOphile reagents, (ii) stereoselective transition-metal complexes, (iii) another distinct stereoscopic species. We aim key reaction design, catalyst development, mechanistic understanding, new insights into rapidly evolving area research.

Language: Английский

Citations

36
Frontiers in Photoelectrochemical Catalysis: A Focus on Valuable Product Synthesis DOI Creative Commons
Marshet Getaye Sendeku, Tofik Ahmed Shifa, Fekadu Tsegaye Dajan

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(21)

Published: Feb. 11, 2024

Abstract Photoelectrochemical (PEC) catalysis provides the most promising avenue for producing value‐added chemicals and consumables from renewable precursors. Over last decades, PEC catalysis, including reduction of feedstock, oxidation organics, activation functionalization C─C C─H bonds, are extensively investigated, opening new opportunities employing technology in upgrading readily available resources. However, several challenges still remain unsolved, hindering commercialization process. This review offers an overview targeted at synthesis high‐value sustainable First, fundamentals evaluating reactions context product both anode cathode recalled. Then, common photoelectrode fabrication methods that have been employed to produce thin‐film photoelectrodes highlighted. Next, advancements systematically reviewed discussed conversion various feedstocks highly valued chemicals. Finally, prospects field presented. aims facilitating further development precursors products other pharmaceuticals.

Language: Английский

Citations

29
Rational Molecular Editing: A New Paradigm in Drug Discovery DOI Creative Commons
Chunhua Ma, Craig W. Lindsley, Junbiao Chang

et al.

Journal of Medicinal Chemistry, Journal Year: 2024, Volume and Issue: 67(14), P. 11459 - 11466

Published: June 21, 2024

ADVERTISEMENT RETURN TO ARTICLES ASAPPREVEditorialNEXTRational Molecular Editing: A New Paradigm in Drug DiscoveryChunhua MaChunhua MaState Key Laboratory of Antiviral Drugs, Pingyuan Laboratory, NMPA for Research and Evaluation Innovative Drug, School Chemistry Chemical Engineering, Henan Normal University, Xinxiang, 453007, ChinaMore by Chunhua Mahttps://orcid.org/0000-0001-7613-6471, Craig W. Lindsley*Craig LindsleyVanderbilt University Medical Center, Franklin, Tennessee 37027, United States*E-mail: [email protected]More Lindsleyhttps://orcid.org/0000-0003-0168-1445, Junbiao Chang*Junbiao ChangCollege Chemistry, State Zhengzhou 450001, China*E-mail: Chang, Bin Yu*Bin YuCollege Yuhttps://orcid.org/0000-0002-7207-643XCite this: J. Med. Chem. 2024, XXXX, XXX, XXX-XXXPublication Date (Web):June 21, 2024Publication History Received13 June 2024Published online21 2024https://pubs.acs.org/doi/10.1021/acs.jmedchem.4c01347https://doi.org/10.1021/acs.jmedchem.4c01347editorialACS PublicationsPublished 2024 American Society. This publication is available under these Terms Use. Request reuse permissions free to access through this site. Learn MoreArticle Views-Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since November 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated reflect usage leading up last few days.Citations number other articles citing article, calculated Crossref daily. Find more information about citation counts.The Altmetric Attention Score a quantitative measure attention that research has received online. Clicking on donut icon will load page at altmetric.com with additional details score social media presence given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InRedditEmail (2 MB) Get e-AlertscloseSUBJECTS:Drug discovery,Macrocyclization,Molecules,Pharmaceuticals,Scaffolds e-Alerts

Language: Английский

Citations

23