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The mechanistic rationale involving activation of nitroalkanes towards interaction with nucleophilic reagents in the presence of polyphosphoric acid (PPA) was re-evaluated. Could nitrile oxide moieties be formed during this process? This experiment demonstrates that at least in some cases this could happen, as generated nitrile oxides were successfully intercepted as adducts of [3 + 2] cycloadditions.
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http://dx.doi.org/10.1039/d1ra06503c | DOI Listing |
J Org Chem
December 2024
Laboratory of organic and metal-organic nitrogen-oxygen systems, N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prospect, 47, Moscow 119991, Russian Federation.
The generation, interconversion, and reactivity of electrophilic species generated upon activation of nitroalkanes with protic acids (the Nef and Meyer reactions) were investigated by quantum-chemical calculations. ,-Bis(hydroxy)iminium (RC═N(OH)) and -oxoiminium (RC═N═O) cations were shown to be produced independently from -nitroalkanes, while -hydroxynitrilium cations (RC≡N-OH) were formed via nearly barrierless C-H bond cleavage in -oxoiminium cations. The -oxoiminium and -hydroxynitrilium cations whose formation is favored under highly acidic anhydrous conditions are strong electrophiles capable of reacting even with nonactivated arenes under ambient conditions.
View Article and Find Full Text PDFOrg Lett
December 2024
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan.
Reductive radical generation has become a cornerstone of modern photoredox chemistry. However, the synthesis of functionalized radical precursors remains a tedious multistep process. In this study, we focus on the potential of the nitro group as a redox-active functional group and present denitrative alkenylation of nitroalkanes, facilitated by photoreductive generation of alkyl radicals from nitroalkanes.
View Article and Find Full Text PDFMicroorganisms
October 2024
School of Marine Science and Technology, Harbin Institute of Technology, Weihai 264209, China.
Aliphatic nitro compounds cause environmental pollution by being discharged into water with industrial waste. Biodegradation needs to be further explored as a green and pollution-free method of environmental remediation. In this study, we successfully cloned a novel nitronate monooxygenase gene () from the genomic DNA library of sp.
View Article and Find Full Text PDFChemistry
December 2024
Department of Chemistry, Biochemistry, and Pharmaceutical Sciences, University of Bern (UniBe), Freiestrasse 3, 3012, Bern, Switzerland.
The evolution of catalysis and functional group transfer reagents play a significant role in the development of anti-Markovnikov alkene hydrofunctionalization reactions, facilitating the access to value-added molecules. We herein report the first rational design of a modular intermolecular anti-Markovnikov hydronitration of alkenes, enabling the direct synthesis of terminal nitroalkanes under visible light-mediated photoredox catalysis. By employing the redox-active organic nitrating reagent N-nitrosuccinimide, the produced nitryl radicals, in the presence of an olefin and a hydrogen atom transfer (HAT) mediator, lead to an anti-Markovnikov addition with complete regioselectivity.
View Article and Find Full Text PDFChem Commun (Camb)
August 2024
Organic and Medicinal Chemistry Division, CSIR-Indian Institute of Chemical Biology, 4 Raja S. C. Mullick Road, Kolkata 700032, India.
The nitro moiety is an indispensable functional group in organic synthesis due to its facile introduction and reduction to the corresponding amines for a plethora of organic transformations. Owing to its distinct electronegative and conventional properties, it has been used for activated aromatic nucleophilic substitution (SAr) reactions, Smiles reactions, Henry reactions, acyl anion equivalents, Recently, the excellent photochemical properties of nitroarenes have been rediscovered by several groups, and their untapped potential in organic synthesis under UV or visible light irradiation has been exploited. Photoexcited nitroarenes can undergo facile reduction to amines, azo-coupling, metal-free reductive C-N coupling with boronic acids a 1,2-boronate shift, hydrogen atom transfer (HAT), oxygen atom transfer for anaerobic oxidation of organic molecules, molecular editing nitrene intermediates, denitrative coupling of β-nitrostyrene, radical α-alkylation of nitroalkanes, They have also been used as a photolabile protecting group in medicinal chemistry and chemical biology applications.
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