α-Functionalization of conjugated nitroalkenes and nitrodienes using various electrophiles in the presence of amine catalysts such as imidazole and DMAP and the synthetic applications of the products are reviewed. The electrophiles include formaldehyde, activated non-enolizable carbonyl compounds, activated imines, azodicarboxylates as well as activated alkenes such as nitroalkenes, MVK and acrylate. Reports on synthetic applications of the products, though only appearing in the last three years, highlight the potential of these multi-functional scaffolds to take part in diverse transformations such as Michael addition, cycloaddition and many cascade reactions leading to complex molecules including natural products.
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http://dx.doi.org/10.2533/chimia.2012.913 | DOI Listing |
J Org Chem
December 2024
Department of Chemistry, Sidho-Kanho-Birsha University, Purulia 723104, W.B., India.
Distinctive, green, innovative, and well-organized photoinduced (metal- or photocatalyst-free) regioselective decarbonylative and decarboxylative C-O bond functionalization protocols to access aryl 2-aminobenzoates and 2-substituted benzoxazinone derivatives in excellent yields have been devised. These are achieved through the chemoselective scission of isatoic anhydride with ketones, diaryliodonium triflate, nitroalkene, phthalazinone, and phenol derivatives, which, in turn, served as the representative "electrophilic and nucleophilic" coupling partners. Control experiments and DFT calculations reveal that electrophilic radical-bearing coupling partners specifically follow the decarbonylation pathway, while nucleophilic radical-bearing conjugates facilitate the decarboxylation process.
View Article and Find Full Text PDFMolecules
October 2024
Department of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Krakow, Poland.
The regio- and stereoselectivity and the molecular mechanisms of the [3 + 2] cycloaddition reactions between -propanethial S-oxide and selected conjugated nitroalkenes were explored theoretically in the framework of the Molecular Electron Density Theory. It was found that cycloadditions with the participation of nitroethene as well as its methyl- and chloro-substituted analogs can be realized via a single-step mechanism. On the other hand, [3 + 2] cycloaddition reactions between -propanethial S-oxide and 1,1-dinitroethene can proceed according to a stepwise mechanism with a zwitterionic intermediate.
View Article and Find Full Text PDFJ Org Chem
November 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.
Org Lett
September 2024
Soft Molecular Activation Research Center (SMARC), Chiba Iodine Resource Innovation Center (CIRIC), Synthetic Organic Chemistry, Department of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522, Japan.
A bis(imidazolidine)-derived NCN nickel-pincer complex (Bu-PhBidine-Ni-OTf: ) was synthesized by the oxidative addition of imidazolidine-containing aryl triflate to Ni(cod) in MeCN. exhibited asymmetric induction in three reactions. In the Friedel-Crafts reaction of indoles with -Boc imines, 3-indolylmethanamine products were obtained in 79% yield with 99% ee.
View Article and Find Full Text PDFRedox Biol
August 2024
Department of Biomedicine, Aarhus University, 8000, Aarhus C, Denmark. Electronic address:
Stimulator of Interferon Genes (STING) is essential for the inflammatory response to cytosolic DNA. Despite that aberrant activation of STING is linked to an increasing number of inflammatory diseases, the development of inhibitors has been challenging, with no compounds in the pipeline beyond the preclinical stage. We previously identified endogenous nitrated fatty acids as novel reversible STING inhibitors.
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