We report the use of halogen bonding (XB) for the generation of aryl radicals from aryl halides under blue light irradiation and applied it in radical generation/1,5-hydrogen-atom transfer/radical cyclization cascade reactions for the synthesis of oxindoles and isoindolinones. On the basis of experimental studies, we propose that DBU can serve as a suitable XB acceptor with aryl halides for the formation of a photoactive electron donor and acceptor complex.
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http://dx.doi.org/10.1039/d2ob01818g | DOI Listing |
J Org Chem
January 2025
Department of Organic Synthesis & Process Chemistry, CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad 500007, India.
The insertion of carbene into secondary amide N-H bonds remains underexplored in organic synthesis. In this work, we discovered the visible-light-induced insertion of siloxycarbene into amide N-H bonds. This metal-free, facile reaction proceeds with atom economy under mild conditions with a broad range of secondary N-H amides, including benzanilide, acetanilide, oxindole, isatin, quinolinone, and maleimide, affording stable - and -acetals in excellent isolated yields.
View Article and Find Full Text PDFEur J Med Chem
December 2024
SynBioC Research Group, Department of Green Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Ghent, Belgium; Cancer Research Institute Ghent (CRIG), Ghent, Belgium. Electronic address:
Histone deacetylase 6 (HDAC6) is a promising target for treating neurodegenerative disorders, several cancer types and viral infections. Unique among HDACs, the HDAC6 isoform possesses a zinc finger ubiquitin-binding domain (UBD) crucial for managing misfolded protein aggregates and facilitating viral infection. HDAC6 binds aggregated polyubiquitinated proteins through its UBD, mediating their transport to the aggresome and subsequent removal via autophagy.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
State Key Laboratory of Microbial Resources, Institute of Microbiology, Chinese Academy of Sciences, Beijing 100101, China.
The structural groups of 2-oxindole and tricyclic 3a-hydroxy-hexahydropyrrolo-[2,3-]indole (HO-HPI) are important pharmacophores. Chemical synthesis of complex alkaloids containing a 2-oxindole or HO-HPI moiety, especially the latter one, has been a long-standing challenge. Herein, we characterized the P450 enzyme AfnD, and its homologue proteins, HmtT, ClpD, KtzM, and LtzR, as cyclopeptide 2-oxindole and HO-HPI monooxygenases (cpOPMOs) that could introduce a 2-oxindole or HO-HPI moiety into the tryptophan-containing cyclopeptides in a pH-dependent manner.
View Article and Find Full Text PDFChemSusChem
January 2025
Polish Academy of Sciences, Institute of Organic Chemistry, Kasprzaka 44/52, 01-224, Warsaw, POLAND.
We demonstrate the application of mechanochemistry in the synthesis of indolone-based photoswitches (hemiindigos, hemithioindigos, and oxindoles) via Knoevenagel condensation reactions. Utilizing ball-milling and an organic base (piperidine) acting as catalyst and solvent for liquid assisted grinding (LAG) conditions, we achieve rapid, solvent-free transformations, obtaining a set of known and previously unreported photoswitches, including highly functional amino acid-based photoswitches, multichromophoric derivatives and photoswitchable cavitands based on resorcin[4]arenes. The reaction under mechanochemical conditions gives moderate-to-high yields and is highly stereoselective leading to Z-isomers of hemiindigos and hemithioindigos and E-isomers of oxindoles.
View Article and Find Full Text PDFMolecules
December 2024
College of Environmental and Chemical Engineering, Dalian University, Dalian 116622, China.
-Butyl hypochlorite was employed as a versatile reagent for chlorooxidation of indoles, chlorination of 2-oxindoles, and decarboxylative chlorination of the indole-2-carboxylic acids. Four types of products including 2-chloro-3-oxindoles, 2,2-dichloro-3-oxindoles, 3,3-dichloro-2-oxindoles, and 2,3-dichloroindoles could be selectively obtained in moderate to excellent yields by switching the substrates. Various synthetically useful functional groups, such as halogen atoms, cyano, nitro, and methoxycarbonyl groups, remain intact during the reactions.
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