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A new phosphinoyl radical precursor, -phosphinoylaminophthalimide (PAPI), was developed. The precursor exhibits several practical advantages: facile synthesis from commercially available starting materials, cost-effectiveness at scale, and excellent air and moisture stability under ambient storage conditions. Phosphinoyl radical was generated under basic and oxidative conditions, and captured by isonitrile and olefin, yielding phosphinoyl-substituted phenanthridines and α-phosphinoyl ketones, respectively. This methodology enables phosphinoyl radical-mediated operationally simple synthesis of organophosphorus compounds.
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http://dx.doi.org/10.1039/d5ob00736d | DOI Listing |
Org Biomol Chem
July 2025
School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Xiasha West Higher Education District, Hangzhou, 310018, China.
A new phosphinoyl radical precursor, -phosphinoylaminophthalimide (PAPI), was developed. The precursor exhibits several practical advantages: facile synthesis from commercially available starting materials, cost-effectiveness at scale, and excellent air and moisture stability under ambient storage conditions. Phosphinoyl radical was generated under basic and oxidative conditions, and captured by isonitrile and olefin, yielding phosphinoyl-substituted phenanthridines and α-phosphinoyl ketones, respectively.
View Article and Find Full Text PDFJ Org Chem
June 2025
Division of Molecular Catalysis and Synthesis, Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou 450001, P. R. China.
A dual NHC/photoredox-catalyzed radical phosphinoylacylation of alkenes has been developed with organic dye Eosin Y as organophotocatalyst under green light irradiation. In this reaction, readily available acyl fluorides and secondary phosphine oxides are used as radical precursors to simultaneously construct C-C and C-P bonds. A wide range of β-phosphinoyl ketones are smoothly accessed in moderate to good yields under these mild reaction conditions.
View Article and Find Full Text PDFJ Org Chem
January 2025
Faculty of Science, Kunming University of Science and Technology, Jingming South Road 727, Chenggong District, Kunming 650500, P. R. China.
A novel silver-catalyzed cascade radical isonitrile insertion and defluorinative cyclization have been developed to synthesize CFH- and phosphinoyl-containing quinolines from -isocyanyl α-trifluoromethylstyrenes. The reaction proceeded under redox-neutral conditions and allowed the construction of a highly attractive quinoline ring system, with the simultaneous formation of the CFH group and introduction of various phosphinoyl groups in a single transformation, showing operational simplicity, a wide substrate scope, good tolerance for functional groups, and remarkable atom-/stepeconomy. Mechanistic studies indicated that the reaction is likely to involve the participation of P-centered radicals and key carbanion intermediates.
View Article and Find Full Text PDFChem Commun (Camb)
July 2024
College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Institute of Molecular and Nano Science, Shandong Normal Un
A silver-catalyzed chemoselective cascade nucleophilic addition of a P-centered anion to isocyanides and cyclization reaction was developed for the efficient and practical synthesis of a wide range of 2-phosphinoyl indole and indol-3-ol derivatives. Unlike the well-documented synthesis of phosphorus-functionalized heterocycles a P-centered radical, an anionic reactivity profile of phosphine oxides is most likely involved in this domino transformation.
View Article and Find Full Text PDFOrg Lett
June 2024
Division of Molecular Catalysis and Synthesis, Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou 450001, P. R. China.
The radical 1,4-functionalizations of 1,3-enynes have emerged as a powerful strategy for the synthesis of multisubstituted allenes. However, the phosphorus-centered radical-initiated transformations remain largely elusive. Herein, visible-light photoredox catalytic regioselective radical hydrophosphinylation of 1,3-enynes with diaryl phosphine oxides as phosphinoyl radical precursors has been realized.
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