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Our previous studies into visible-light-mediated aza-Henry reactions demonstrated that molecular oxygen played a vital role in catalyst turnover as well as the production of base to facilitate the nucleophilic addition of nitroalkanes. Herein, improved conditions for the generation of iminium ions from tetrahydroisoquinolines that allow for versatile nucleophilic trapping are reported. The new conditions provide access to a diverse range of functionality under mild, anaerobic reaction conditions as well as mechanistic insights into the photoredox cycle.
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http://dx.doi.org/10.1021/ol202883v | DOI Listing |
Angew Chem Int Ed Engl
September 2025
State Key Laboratory of Chemo and Biosensing, School of Biomedical Sciences, Hunan University, Changsha, 410082, China.
Activity-based ubiquitin probes (Ub-ABPs) are powerful tools for studying the functional landscape of deubiquitinases (DUBs). While most existing Ub probes have focused on examining the native state of DUBs, oxidative stress, especially in cancer and inflammatory contexts, can oxidize the catalytic cysteine of DUBs, significantly altering their activity. Here, we developed three novel ubiquitin-based activity probes (Ub-ABPs) to selectively trap the sulfenylated form of deubiquitinases (DUB-SOH).
View Article and Find Full Text PDFOrg Biomol Chem
August 2025
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., Moscow, 119991, Russian Federation.
A selective method has been developed for the synthesis of unsymmetrical geminal bisperoxides the ozonolysis of semicarbazones in a hydroperoxide containing medium. The replacement of the CN moiety by two different peroxide fragments bonded to the same carbon atom in a one-pot process is a step towards solving the complex problem of organic synthesis: geminal difunctionalization with two closely related, but not identical, functional groups. Our approach is based on the relatively unexplored ozonolysis of the CN fragment.
View Article and Find Full Text PDFWater Res
August 2025
State Key Laboratory of Water Pollution Control and Green Resource Recycling, College of Environmental Science and Engineering, Shanghai Institute of Pollution Control and Ecological Security, Tongji University, Shanghai 200092, China. Electronic address:
Photo-Fenton process produces reactive oxygen species (ROS) capable of degrading organic compounds across diverse chemical environments. However, the challenge of coupling multifunctional modules limited the attentions, which are supposed to be paid on intertwined physicochemical processes in porous heterogeneous aerogel. This study elucidated the hitherto neglected synergistic mechanisms of photo-excitated HO activation through photon-harvesting and localized surface plasmon resonance (LSPR) effect enhanced by defective sites (coordinatively unsaturated sites (CUS) and oxygen vacancy (V)).
View Article and Find Full Text PDFJ Org Chem
August 2025
School of Chemistry, University of Hyderabad, Hyderabad 500046, India.
A palladium(II)-catalyzed synthesis of pyrrolizine- and indolizine-fused heterocycles was established involving a cascade functionalization of internal alkynes in good yields (up to 84%). A catalyst- and solvent-dependent intramolecular carboxypalladation of the multifunctional alkynes followed by trapping the in situ generated σ-vinylpalladium species delivered isobenzofuran-fused pyrrolizines and isochromeno[3,4-]indolizin-5-ones. Further, benzo[][1,3]oxazin-2-one-fused pyrrolizines were obtained by replacing the carboxylic ester with a -Boc-protected amine as the nucleophilic partner.
View Article and Find Full Text PDFChem Sci
August 2025
Leibniz-Institut für Katalyse e.V. Albert-Einstein-Str. 29a 18059 Rostock Germany
Regioselective transformation is among the long-standing challenges in organic synthesis, particularly involving gas trapping. We present here a novel photocatalytic strategy for the regioselective carbonylation reaction toward α-aminoketones. Experimental studies reveal that protonic acids dissociated from protonated amines facilitate the reactions of low-reactive aldehydes and enhance the electrophilicity of imines, thereby promoting the efficient coupling of less nucleophilic acyl radicals.
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