A palladium-catalyzed cross-coupling methodology has been developed by utilizing aryl alkyl selenides and organoboranes. In this deseleniative process, the organoselenium moiety acts as a pseudohalide, facilitating the cleavage of the C-Se bond through the synergistic action of palladium(0) and stoichiometric copper(I) thiophene-2-carboxylate. When conducted under microwave irradiation, the reaction methodology demonstrates broad substrate compatibility, scalability to gram-scale synthesis, and moderate to good yields. By employing commercially available boronic acids, this approach enhances practicality and potential applications in organic synthesis.
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http://dx.doi.org/10.1039/d5ob00054h | DOI Listing |
Org Lett
March 2025
Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
The asymmetric hydrogenation (AH) of cyclic -alkyl imines offers an elegant and efficient method to afford chiral amines, especially for -nicotine and its derivatives. However, this approach remains an ongoing challenge due to undesirable coordination of pyridyl-containing substrates to the active metal catalyst. Herein, we disclose a manganese-catalyzed AH that allows access to -nicotine and other chiral α-(hetero)aryl pyrrolidines and provides an example of a base-metal catalyst that displays superior performance to its noble metal counterparts.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
March 2025
Ruhr-Universitat Bochum, Faculty of Chemistry and Biochemistry, Universitätsstraße 150, 44780, Bochum, GERMANY.
Keteniminyl anions hold significant promise for advancing ketenimine chemistry, yet their isolation has remained elusive until now. Drawing inspiration from recent advances in ligand exchange reactions at carbon, we report the successful synthesis of isolable alkali metal keteniminyl anions through substitution of the phosphine ligand in metalated ylides or the N2 ligand in a diazomethanides with isocyanides. The exchange reactions were found to proceed more rapidly with aryl isocyanides than with the more electron-rich alkyl-substituted derivatives and were also more efficient when starting from the diazo compounds.
View Article and Find Full Text PDFNat Commun
March 2025
Shenzhen Key Laboratory of Cross-Coupling Reactions & Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen, China.
The (hetero)aryl sulfoximines are important structures for developing bioactive molecules, whose synthesis relies on oxidation of (hetero)aryl sulfilimines. However, asymmetric approaches for assembling (hetero)aryl sulfilimines are still rare. Here we show that combination of CuI and NOBIN-derived amide ligands offers an effective catalytic system for enantioselective coupling of (hetero)aryl iodides with sulfenamides.
View Article and Find Full Text PDFInorg Chem
March 2025
School of Chemistry and Chemical Engineering, Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Shanda Nanlu 27, 250100 Jinan, People's Republic of China.
In this article, two cobalt complexes bearing bidentate ligands, [Si,C]-chelate cobalt(I) complex [(Si,C)Co(PMe)] () and [P,C]-chelate cobalt(I) complex [(P,C)Co(PMe)] () were synthesized by activating Csp-H of the corresponding 2-(diphenylsilylenoaminomethyl) pyridine () PyN(Me)SiL (L = PhC(NBu)) or 2-(diphenylphosphinoaminomethyl) pyridine () PyN(Me)PPh with CoMe(PMe). The catalytic performance of complexes and for alkene hydrosilylation was studied. Because of the different electronic properties of the phosphine and the silylene pincer ligand, the catalytic effect of phosphine complex is superior to that of silylene complex as indicated by faster conversion and higher selectivity for most of the selected substrates.
View Article and Find Full Text PDFChem Asian J
March 2025
Indian Institute of Technology Roorkee Department of Chemistry, Deptartment of Chemistry, Room 303D, Department of Chemistry, IIT Roorkee, 247667, Roorkee, INDIA.
An external-photocatalyst-free visible light-induced regioselective C-3 sulfenylation of imidazo[1,2-a]pyridines using Bunte salts has been accomplished via C(sp2)-H functionalization. This protocol allows the coupling of a wide range of imidazoheterocycles with alkyl-, benzyl-, and aryl Bunte salts under ambient air as the sole oxidant. The radical scavenging, UV-visible spectroscopic studies, and Stern‒Volmer experiments revealed that the reaction occurs through energy transfer followed by a radical SET pathway.
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