One way to build chemical diversity into indoles is to oxidize them to indolyl radical cations (Ind). These intermediates can accept new functional groups across C2-C3 bonds or independently at C2. Less encountered is selective diversification at C3, a position plagued by competing dearomative side reactions. We disclose an aqueous photoredox-catalyzed method for transforming Ind into C3-substituted tryptophan mimetics that uses water as a transient protecting group to guide site-selective C3 alkylation.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11055211 | PMC |
| http://dx.doi.org/10.1021/acs.orglett.3c01398 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Photoredox-Catalyzed -Indolyl/Quinolyl Glycosylation from 2-Styrylisocyanides and Glycosyl Bromides.
Org Lett
September 2024
State Key Laboratory of Analytical Chemistry for Life Science, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023 (China).
Indole and quinoline structures are present in numerous biologically active molecules, making the synthesis of their glycosylation products a subject of extensive research and interest in drug development. Here, we report a photoredox strategy for the synthesis of -indolyl and -quinolyl glycosides using 2-styrylisocyanides and glycosyl bromides as building blocks. This approach offers mild reaction conditions, high α-selectivity, and scalability for large-scale reactions.
View Article and Find Full Text PDFAsymmetric Counteranion-Directed Electrocatalysis for Enantioselective Control of Radical Cation.
Angew Chem Int Ed Engl
January 2025
College of Pharmaceutical Sciences, Zhejiang University of Technology, 310014, Hangzhou, P. R. China.
The control of enantioselectivity in radical cation reactions presents long-standing challenges, despite a few successful examples. We introduce a novel strategy of asymmetric counteranion-directed electrocatalysis to address enantioselectivity in radical cation chemistry. This concept has been successfully demonstrated in two reactions: an asymmetric dehydrogenative indole-phenol [3+2] coupling and an atroposelective C-H/N-H dehydrogenative coupling.
View Article and Find Full Text PDFA Cytochrome P450 TxtE Model System with Mechanistic and Theoretical Evidence for a Heme Peroxynitrite Active Species.
Angew Chem Int Ed Engl
December 2024
Department of Chemistry and Biochemistry, The University of Alabama, Tuscaloosa, AL 35487, United States.
The cytochrome P450 homolog, TxtE, efficiently catalyzes the direct and regioselective aromatic nitration of the indolyl moiety of L-tryptophan to 4-nitro-L-tryptophan, using nitric oxide (NO) and dioxygen (O) as co-substrates. Pathways for such direct and selective nitration of heteroaromatic motifs present platforms for engineering new nitration biocatalysts for pharmacologically beneficial targets, among a medley of other pivotal industrial applications. Precise mechanistic details concerning this pathway are only weakly understood, albeit a heme iron(III)-peroxynitrite active species has been postulated.
View Article and Find Full Text PDFElectron-Withdrawing Substituents Enhance the Type I PDT and NIR-II Fluorescence of BODIPY J Aggregates for Bioimaging and Cancer Therapy.
Nano Lett
July 2024
Research Center for Analytical Sciences, Tianjin Key Laboratory of Biosensing and Molecular Recognition, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, China.
Organic dyes with simultaneously boosted near-infrared-II (NIR-II) fluorescence, type I photodynamic therapy (PDT), and photothermal therapy (PTT) in the aggregate state are still elusive due to the unclear structure-function relationship. Herein, electron-withdrawing substituents are introduced at the 5-indolyl positions of BODIPY dyes to form tight J-aggregates for enhanced NIR-II fluorescence and type I PDT/PTT. The introduction of an electron-rich julolidine group at the position and an electron-withdrawing substituent (-F) at the indolyl moiety can enhance intermolecular charge transfer and the hydrogen bonding effect, contributing to the efficient generation of superoxide radicals in the aggregate state.
View Article and Find Full Text PDFPreparation, characterization, antioxidant, and antifungal activity of phenyl/indolyl-acyl chitooligosaccharides.
Carbohydr Res
April 2024
College of Sciences, Inner Mongolia Agricultural University, Hohhot, 010018, China; Inner Mongolia Key Laboratory of Soil Quality and Nutrient Resource, Hohhot, 010018, China; Key Laboratory of Agricultural Ecological Security and Green Development at Universities of Inner Mongolia Autonomous Region, Hohhot, 010018, China. Electronic address:
In this study, carboxylic acids compounds were grafted onto chitooligosaccharides to prepare seven phenyl/indolyl-acyl chitooligosaccharides derivatives. The structures of the derivatives were characterized by IR spectroscopy, C NMR and elemental analysis. Meanwhile, antioxidant activities in vitro of the novel derivatives were analyzed.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!