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A coupling reaction between diazo compounds and phenyl benzyl sulfide catalyzed by TfOH has been reported. This reaction can synthesize important α-arylthio carbonyl compounds via regioselective cleavage and reconfiguration of C-S bonds, and various functional groups were tolerant to the reaction conditions. Mechanistic studies have conclusively established that the pivotal intermediate in the reaction was meticulously investigated through spectroscopic evidence, complemented by rigorous control experiments.
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http://dx.doi.org/10.1021/acs.orglett.4c03246 | DOI Listing |
J Org Chem
September 2025
School of Chemistry and Chemical Engineering, Huaibei Normal University, Huaibei, Anhui 235000, P. R. China.
Radical cascade cyclization of alkenes involving the insertion of sulfur dioxide has proven to be a promising tool to access sulfonylnated heterocycle compounds, whereas cyclization of unactivated alkenes has been much less explored. Here, we developed a three-component cascade of unactive alkenes with sulfur dioxide and aryldiazonium tetrafluoroborates to generate sulfonylated tetrahydropyridines and azepines via the cleavage of alkenyl C-H bonds. Moreover, this protocol exhibited excellent chemical and regioselectivity and compatibility with broad functional groups.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 4100
While the conversion of simple cyclic ketones to lactams via carbon-carbon (C-C) bond cleavage can be accomplished through classical Beckmann and Schmidt rearrangements, these methods suffer from inherent limitations. Beyond regioselectivity challenges, they permit the incorporation of only a single nitrogen atom into the parent carbocyclic framework. Herein, an efficient approach to access medium-to-large sized lactams was developed through an alkyne migratory insertion enabled C-C bond activation of unstrained ketones.
View Article and Find Full Text PDFAcc Chem Res
August 2025
Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States.
ConspectusCu-dependent metalloenzymes catalyze a wide array of oxidative transformations using O as an oxidant under mild conditions. These include the hydroxylation of challenging organic substrates (e.g.
View Article and Find Full Text PDFCarbohydr Res
November 2025
Department of Chemistry, Louisiana State University, 232 Choppin Hall, Baton Rouge, LA, 70806, USA. Electronic address:
Identification and synthesis of highly conserved glycans is a priority for understanding chemical immunology as it applies to drug-resistant pathogens such as Gram-negative Acinetobacter baumannii. Herein, we report on our initial efforts aimed toward the synthesis of a highly conserved lipooligosaccharide core isolated originally from A. baumannii ATCC 19606.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A & 2B Raja SC Mullick Road, Kolkata, West Bengal 700032, India.
Heme oxygenase (HO) is responsible for the controlled breakdown of heme in most living organisms, which avoids heme toxicity and provides essential biochemical components like biliverdin and the signaling molecule CO. The reactive oxidant in HO is proposed to be a ferric hydroperoxide species, which attacks a specific meso carbon center of the heme. Both site-directed mutagenesis and density functional theory (DFT) calculations have suggested a dominant role of the hydrogen bonding present in the second sphere of the HO active site in the reactivity of HO.
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