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The electrophilic organofluorophosphonium catalyst [(C6F5)3PF][B(C6F5)4] is shown to effect benzylation or alkylation by aryl and alkyl CF3 groups with subsequent hydrodefluorination, thus resulting in a net transformation of CF3 into CH2-aryl fragments. In the case of alkyl CF3 groups, Friedel-Crafts alkylation by the difluorocarbocation proceeded without cation rearrangement, in contrast to the corresponding reactions of alkyl monofluorides.
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http://dx.doi.org/10.1002/anie.201510494 | DOI Listing |
Org Biomol Chem
September 2025
Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
Herein, we report a simple, microwave-assisted and open-air strategy for gram-scale C3-alkylation of indoles, along with an economically viable strategy for epoxide opening followed by α-alkylation, using the [RuCl(bpy){-PhPCHCONCHPPh-}-κ-(,,,,)] complex (hereafter referred to as [PNP-Ru]). This transformation proceeds an alcohol dehydrogenation (oxidation) mechanism, with water being the sole byproduct in both reactions, underscoring the environmentally benign and sustainable nature of the methodology. The protocol efficiently delivers both mono- and bis(indolyl) derivatives in good to excellent yields.
View Article and Find Full Text PDFOrg Lett
September 2025
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, P. R. China.
2-Alkylindoles are privileged motifs that serve as versatile intermediates and building blocks in synthetic and medicinal chemistry. Herein, we report a photoinduced, EDA-complex-enabled C2-benzylic C(sp)-H alkylation of indoles with bromides through radical cross-coupling. This developed protocol provides facile access to 2-alkylindoles from structurally varied 2-methylindoles and bromides under mild reaction conditions with simple operation.
View Article and Find Full Text PDFChem Commun (Camb)
September 2025
Department of Chemistry, Biochemistry and Pharmaceutical Sciences, University of Bern, CH-3012 Bern, Switzerland.
Iron complexes bearing chiral salicyloxazoline (Salox) ligands catalyze the enantioselective intramolecular C-H bond amination of alkyl azides, reaching 58-76% ee for benzylic C-H bonds. Further, for the first time aliphatic C-H bond amination is demonstrated (∼40% ee). This class of catalysts even activates primary aliphatic C-H bonds, albeit with moderate ee.
View Article and Find Full Text PDFNat Synth
January 2025
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC, USA.
The application of molecular imaging has advanced personalized medicine and generated a profound impact on patient care. Positron emission tomography and magnetic resonance imaging are among the most widely used imaging modalities, often requiring the isotopic labelling of bioactive molecules to generate the desired imaging probes. Unfortunately, radiochemistry often limits the development of novel agents due to complicated syntheses and the incompatibility of complex molecules.
View Article and Find Full Text PDFPharmaceuticals (Basel)
August 2025
Department of Pharmacy, University "G. D'Annunzio" of Chieti-Pescara, 66100 Chieti, Italy.
Third-generation aromatase inhibitors (CYP19A1) are the mainstay of treatment for estrogen-receptor-positive breast cancer. This is because estrogen is required for cancer growth in approximately 70% of patients with this condition. Although potent and effective, aromatase inhibitors induce resistance and secondary effects, requiring treatment to be discontinued.
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