Electrochemical Synthesis of Phosphorylated Indoles and Trp-Containing Oligopeptides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(22), P. 4700 - 4704

Published: May 28, 2024

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Language: Английский

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Unlocking HFIP for Fluoroalkylation with Molecular Photoelectrocatalysis

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

Despite the increasing interest in radical-based fluoroalkylation techniques, organofluorine compounds bearing partially fluorinated hexafluoroisopropyl group remain extremely scarce due to lack of appropriate reagents. Herein we report an unprecedented photoelectrocatalytic method for C-H hexafluoroisopropylation indoles and tryptophan peptides, utilizing readily available hexafluoro-2-propanol (HFIP) as reagent. In this process, HFIP is converted into radicals, enabling reactions. This study broadens potential applications molecular photoelectrocatalysis, highlighting its capacity enable transformations that are difficult accomplish through traditional electrochemical or photochemical approaches.

Language: Английский

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Electrochemical synthesis of vicinal azidoacetamides

Chemical Communications, Journal Year: 2022, Volume and Issue: 59(4), P. 422 - 425

Published: Dec. 6, 2022

Vicinal diamines are an important structural motif in bioactive natural products and pharmaceutical intermediates. Herein, environmentally friendly efficient electrochemical approach to azidoacetamides, as one variant of vicinal diamines, has been developed. This reaction features mild conditions broad substrate scope, without the use any chemical oxidant or transition-metal catalysts. The obtained azidoacetamides could be conveniently converted into various other diamine derivatives.

Language: Английский

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Electro-induced C-H/S-H Cross-Coupling for the Functionalization/Macrocyclization of Cysteine-Containing Peptides

Published: April 7, 2025

The electrochemical platform that underpins the promising future of selective modifications peptides and proteins, however, is still rather underdeveloped. Here in, an electro-induced umpolung approach enables efficient functionalization/macrocyclization cysteine-containing reported. Notably, this method utilizes simple halogen source takes metal-mediated atom transfer as main pathway to enable in-situ polarity reversal, highlighting unique possibilities associated with activation methods. Under mild conditions, cysteine residue can be well-labelled high chemo-selectivity excellent conversion. This transformation tolerate a wide range valuable enamines, azoles, partners, also utilized macrocyclization tactic for cyclic peptide synthesis other areas.

Language: Английский

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Interfacial Micro‐Environment of Electrocatalysis and Its Applications for Organic Electro‐Oxidation Reaction

Small, Journal Year: 2023, Volume and Issue: 20(4)

Published: Sept. 15, 2023

Abstract Conventional designing principal of electrocatalyst is focused on the electronic structure tuning, which effectively promotes electrocatalysis. However, as a typical kind electrode–electrolyte interface reaction, electrocatalysis performance also closely dependent interfacial micro‐environment (IME), including pH, reactant concentration, electric field, surface geometry structure, hydrophilicity/hydrophobicity, etc. Recently, organic electro‐oxidation reaction (OEOR), simultaneously reduces anodic polarization potential and produces value‐added chemicals, has emerged competitive alternative to oxygen evolution role IME played in OEOR receiving great interest. Thus, this article provides timely review its applications toward OEOR. In review, for conventional gas‐involving reactions, contrast, first presented, then recent progresses diverse are summarized; especially, some representative works thoroughly discussed. Additionally, cutting‐edge analytical methods characterization techniques introduced comprehensively understand last section, perspectives challenges regulation shared.

Language: Английский

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When transition-metal catalysis meets electrosynthesis: a recent update

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(22), P. 4390 - 4419

Published: Jan. 1, 2024

The merger of organic electrosynthesis with 3d transition-metal catalysis has offered huge opportunities for modern synthesis. This review summarizes the key advancements in this direction published recent two years.

Language: Английский

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Synthesis of 3-sulfonylisoindolin-1-ones from olefinic amides and sodium sulfinates via electrooxidative tandem cyclization

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(29), P. 5897 - 5901

Published: Jan. 1, 2024

Sulfonyl groups are motifs that widely found in biologically active compounds and drug molecules, many isolated natural products as well pharmaceuticals contain sulfonyl groups. Herein, we present the synthesis of sulfonyl-substituted isoindolones by a electrochemical oxidative radical cascade cycloaddition reaction olefinic amides with sodium sulfite under oxidant- catalyst-free conditions. Various sulfinates were compatible gave desired yields up to 99%.

Language: Английский

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Paired Electro‐Synthesis of Remote Amino Alcohols with/in H2O

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 13, 2024

Abstract Amino alcohols, particularly remote amino alcohols and peptide are valuable due to their functional diversity in biologically active compounds. However, traditional synthesis methods face significant challenges, making electrochemistry an attractive alternative. We have developed a mild biocompatible sequential paired electrolysis strategy, leveraging copper‐electrocatalysis synthesize diverse including unnatural alcohols. Both experimental results density theory (DFT) calculations demonstrated that water serves as both the hydroxyl source solvent, facilitating generation of CuH with Cu(I) at cathode, which turn reduces aldehyde intermediates formed during reaction.

Language: Английский

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Electrochemical Modification of Polypeptides at Selenocysteine

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(50)

Published: Oct. 11, 2023

Abstract Mild strategies for the selective modification of peptides and proteins are in demand applications therapeutic peptide protein discovery, study fundamental biomolecular processes. Herein, we describe development an electrochemical selenoetherification (e‐SE) platform efficient site‐selective functionalization polypeptides. This methodology utilizes unique reactivity 21st amino acid, selenocysteine, to effect formation valuable bioconjugates through stable selenoether linkages under mild conditions. The power e‐SE is highlighted late‐stage C‐terminal FDA‐approved cancer drug leuprolide assembly a library anti‐HER2 affibody conjugates bearing complex cargoes. Following by e‐SE, utility functionalized affibodies vitro imaging targeting HER2 positive breast lung cell lines also demonstrated.

Language: Английский

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Electrochemistry-enabled residue-specific modification of peptides and proteins

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 22(6), P. 1085 - 1101

Published: Dec. 29, 2023

This review focuses on up-to-date developments of electrochemistry-promoted residue-specific modification peptides and proteins. Specific protocols for five redox-active amino acid residues, namely cysteine, tyrosine, tryptophan, histidine methionine, were explained in detail.

Language: Английский

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