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A general synthesis of 1-vinyltetrahydro--carbolines (THBCs) has been achieved via palladium(0)-catalyzed cyclocondensation between allenyltryptamines and aryl iodides. Aza-spiroindolenines could also be accessed from the -unsubstituted indole substrates by simply tweaking the reaction conditions. DDQ-mediated oxidation of THBCs easily afforded -carbolines, which could be synthetically transformed into 1-aroyl--carbolines of pharmacological interest. Formal total syntheses of and have also been achieved.
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http://dx.doi.org/10.1021/acs.joc.0c02651 | DOI Listing |
Org Lett
September 2025
State Key Laboratory of Precision and Intelligent Chemistry, Department of Chemistry, University of Science and Technology of China, Hefei 230026, P. R. China.
A novel palladium-catalyzed asymmetric aminomethylative pyridonation of conjugated dienes with -acetals and 2-hydroxypyridines was established, which provided a direct and reliable method for the synthesis of a wide range of γ-aminated N-substituted 2-pyridones with good to excellent enantioselectivities. The simple BF was identified as an effective cocatalyst to improve the reaction efficiency, and DFT calculations revealed that proton transfer between the aminomethylated allylic palladium species and 2-hydroxypyridine promoted by BF is crucial for obtaining good reactivity.
View Article and Find Full Text PDFJ Org Chem
September 2025
School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China.
A palladium-catalyzed cyclization and carbonylation of -propargylamides with amines has been developed, which incorporates an amide unit into 3,4-dihydroisoquinolin-1(2)-one scaffolds. By using benzene-1,3,5-triyl triformate (TFBen) as the safe and convenient CO source, the reaction proceeded smoothly to afford a variety of amide-containing 3,4-dihydroisoquinolin-1(2)-one derivatives in high yields.
View Article and Find Full Text PDFJ Org Chem
September 2025
Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Zhejiang Key Laboratory of Organosilicon Material Technology, College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, Zhejiang 311121, China.
A photoinduced palladium-catalyzed radical C(sp)-H phosphinoylation of tetrahydroisoquinoline was reported. Easily accessible and inexpensive Cl-phosphine oxides were employed as phosphorus radical sources. The key steps in this strategy involve the generation of phosphorus and carbon radicals using the excited palladium complex.
View Article and Find Full Text PDFOrg Lett
September 2025
School of Pharmacy and Food Engineering, Wuyi University, Jiangmen 529090, P. R. China.
3-Fluoropyrroles are privileged scaffolds in pharmaceutical and agrochemical applications, yet their synthesis remains challenging. Herein, we report a palladium(0)-catalyzed [4+1] cycloaddition/dehydration strategy for the efficient construction of 3-fluoropyrroles from readily available 3,3-difluoropent-4-en-2-ones and primary amines. This transformation proceeds via C-F bond activation to generate a key π-allyl-Pd(II) intermediate, followed by intramolecular addition/dehydration to furnish the heterocyclic core.
View Article and Find Full Text PDFOrg Lett
September 2025
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, China.
A palladium-catalyzed construction of amino β-lactone derivatives is described herein. This method applies readily available aryl amines and alkenyl carboxylic acids as starting materials, providing the amino β-lactone under mild reaction conditions in one step. The deuterium labeling experiment revealed that the β-H elimination process after aminopalladation was effectively suppressed under the excess amount of I, thus enabling further oxidation and reductive elimination to afford the target amino β-lactones.
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