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The photolytic radical-induced vicinal azidooxygenation of synthetically important and diverse functionalized substrates including unactivated alkenes is reported. The photoredox-catalyst/additive-free protocol enables intermolecular oxyazidation by simultaneously incorporating two new functionalities; and across the double bond in a selective manner. Mechanistic investigations reveal the intermediacy of the azidyl radical facilitated the photolysis of λ-azidoiodane species and cascade proceeding to generate an active carbon-centered radical. The late-stage transformations of azido- and oxy-moieties were amply highlighted by assembling high-value drug analogs and bioactive skeletons.
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http://dx.doi.org/10.1021/acsomega.1c03991 | DOI Listing |
ChemSusChem
April 2025
Organic and Medicinal Chemistry Division, CSIR-Indian Institute of Chemical Biology, Jadavpur, Kolkata, 700032, India.
A TEMPO-N charge-transfer complex enables the electrochemical C-H azidation of various N-heterocycles. The TEMPO ion, generated from TEMPO, assists in producing N by forming a TEMPO-N complex with N . The formation of this complex is supported by UV-vis absorption spectra, cyclic voltammetry studies, and ESI-HRMS studies.
View Article and Find Full Text PDFACS Omega
October 2021
Carbohydrate Chemistry Research Laboratory (CCRL), Department of Chemistry, Malaviya National Institute of Technology (MNIT), Jaipur302 017, India.
The photolytic radical-induced vicinal azidooxygenation of synthetically important and diverse functionalized substrates including unactivated alkenes is reported. The photoredox-catalyst/additive-free protocol enables intermolecular oxyazidation by simultaneously incorporating two new functionalities; and across the double bond in a selective manner. Mechanistic investigations reveal the intermediacy of the azidyl radical facilitated the photolysis of λ-azidoiodane species and cascade proceeding to generate an active carbon-centered radical.
View Article and Find Full Text PDFOrg Lett
December 2019
Carbohydrate Chemistry Research Laboratory (CCRL), Department of Chemistry , Malaviya National Institute of Technology (MNIT), Jaipur 302017 , India.
Photoswitchable strategy for selective azidation of structurally diverse olefins under transition-metal-free conditions is reported. The unprecedented reactivity of trimethylsulfonium [bis(azido)iodate(I)] species under visible light allows radical azidooxygenation of the C═C π bond with distinctive selectivity. In the absence of visible light, the reaction proceeds through an ionic intermediate which led to complementary regioselectivity to provide α-alkyl azides.
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