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We describe a Xantphos-containing dinuclear palladium complex-enabled geminal aminoallylation of diazocarbonyl compounds, which selectively provides a range of quaternary α-amino esters. Direct N-H insertion, allylic alkylation of amino nucleophiles, and diene formation were not observed under standard conditions. Mechanistic studies indicated that a relayed pathway via allylation of the N-H insertion product or [2,3]-sigmatropic rearrangement of an ylide intermediate was unlikely.
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http://dx.doi.org/10.1021/acs.orglett.2c01399 | DOI Listing |
J Org Chem
September 2025
Key Laboratory of Chemical Engineering and Technology, State Ethnic Affairs Commission, North Minzu University, Yinchuan 750021, China.
The reaction mechanism of the excited-state copper-catalyzed cascade synthesis of α,β-unsaturated-γ-lactams from aroyl chlorides, acrylamides, and -hexanol has been systematically investigated using density functional theory (DFT) calculations. The reaction consists of four elementary steps: initiation of aroyl radical formation from aroyl chlorides by the excited-state Cu-Complex; subsequent radical relay between the aroyl radical and acrylamides leading to C-C bond formation; coupling of the C-N bond through the activation of N-H bond/coordination site migration facilitated by a Cu-Complex resulting in the formation of a five-membered ring scaffold; and then the functionalization of the γ-C of lactam to introduce alkoxy or hydride groups is achieved through electrophilic substitution. The single-carbon atom insertion is realized by the radical relay and copper-catalyzed radical polar cross-coupling strategy.
View Article and Find Full Text PDFSAGE Open Med Case Rep
August 2025
Department of Cardiovascular Medicine, Asahi General Hospital, Chiba, Japan.
Hemostasis of a large-diameter sheath is sometimes problematic, especially for patients with limited approach sites. Here, we describe an effective and safe endovascular method for hemostasis of the femoral artery via the dorsalis pedis artery. The patient was a 75-year-old man who was performing endovascular therapy via the left common femoral artery.
View Article and Find Full Text PDFBeilstein J Org Chem
July 2025
Institute of Medical Biology, Polish Academy of Sciences, 106 Lodowa St., 93-232 Łódź, Poland.
The in situ-generated thiocarbonyl -methanides (thiocarbonyl ylides), derived from cycloaliphatic thioketones, are efficiently trapped by enolizable 1-substitued 5-mercapto-1-tetrazoles and formation of the corresponding N-H or S-H insertion products, i.e., thioaminals or dithioacetals, respectively, was observed.
View Article and Find Full Text PDFOrg Lett
July 2025
Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, M. Aurèlia Capmany, 69, 17003 Girona, Catalonia, Spain.
In this study, we report a general and efficient method for iron-catalyzed intermolecular N-H insertion at the intercarbonylic position of malonate reagents. Using iodonium ylides and simple iron(II) triflate as the catalyst, the reaction enables the functionalization of a wide range of primary and secondary aromatic and aliphatic amines in excellent yields. The reaction operates under exceptionally mild conditions, without the need for an inert atmosphere or anhydrous solvents, and proceeds in remarkably short reaction times.
View Article and Find Full Text PDFJ Am Chem Soc
July 2025
Department of chemistry, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh 208016, India.
Herein, we report an efficient method for the synthesis of atropisomers with distal 1,3-C-N diaxes using the cobalt/Salox system via C-H and N-H annulation with benzamide and sterically hindered alkynes. This one-step, step-economical process operates at room temperature with oxygen from air as the sole oxidant, removing the need for metal oxidants, photocatalysts, or electricity. The reaction is compatible with a broad range of arylamides and alkynes, providing high yields and excellent enantioselectivity (up to >99% ee).
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