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As a non-invasive imaging technology, positron emission tomography (PET) plays a crucial role in personalized medicine, including early diagnosis, patient screening, and treatment monitoring. The advancement of PET research depends on the discovery of new PET agents, which requires the development of simple and efficient radiolabeling methods in many cases. As bioisosteres for halogen and carbonyl moieties, nitriles are important functional groups in pharmaceutical and agrochemical compounds. Here, we disclose a mild organophotoredox-catalyzed method for efficient cyanation of a broad spectrum of electron-rich arenes, including abundant and readily available veratroles and pyrogallol trimethyl ethers. Notably, the transformations not only are compatible with various affordable C and C-cyanide sources, but also could be applied to carbon-11 synthons to incorporate [C]nitriles into arenes. The aryl [C]nitriles can be further derivatized to [C]carboxylic acids, [C]amides, and [C]alkyl amines. The newly developed reaction can serve as a powerful tool for generating new PET agents.
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http://dx.doi.org/10.1016/j.chempr.2022.12.007 | DOI Listing |
Org Lett
August 2025
Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United States.
This Letter describes the photocatalytic C(sp)-H amination of electron-rich arenes with azoles via an electron donor-acceptor (EDA) pathway. The acceptor in this system is proposed to be a pyridin-1-ium salt generated from the combination of pyridine and either LiOTf or HOTf. The reactions proceed with irradiation using 370 nm LEDs, and the pyridine/acid acceptor can serve as a catalyst under aerobic conditions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
In this work, 3,6-dimethoxycalix[3]acridine (3,6-DMO-C[3]A), as a new macrocyclic arene, was synthesized and then applied to the construction of a new kind of N,O-alternant belt[3]arene (NOAB[3]A) by the conversion approach from macrocycle to belt. NOAB[3]A has a regularly hexagonal structure and electron-rich cavity, and it can be successfully utilized as an electron donor to construct supramolecular thermally activated delayed fluorescence (STADF) materials with multi-color emissions by its complexation with electron acceptors with different electron-deficient abilities. Notably, due to the formation of STADF accompanied by fluorescence enhancement and redshift when NOAB[3]A combines with the cyanide-containing aromatic compounds, the belt[3]arene can also be directly used for highly selective, sensitive, and visual detection of 2-cyanopyrazine (2-CP) vapor at trace level.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 9190401, Israel.
Bioconjugation of peptides and proteins has become an indispensable tool in fundamental biological research and drug development. Herein, we report a copper-mediated efficient cysteine/selenocysteine-specific bioconjugation through direct C-H functionalization of electron-rich arenes under biocompatible reaction conditions. In this method, a series of commercial electron-rich arenes, including natural products and drug molecules, are conjugated to cysteine/selenocysteine-containing peptides and proteins.
View Article and Find Full Text PDFACS Catal
August 2025
University of Texas at Austin, Austin, Texas 78712, United States.
Alkyl boronic acids and esters are versatile synthetic intermediates that generally require several steps to synthesize. Three-component alkene arylboration reactions allow for the rapid synthesis of alkyl boronic esters. Herein, we report the base-free aerobic Pd-catalyzed three-component alkene arylboration, which allows direct access, in a single step, to alkyl boronic esters from readily available precursors: aryl boronic acids, alkenes, and bis(pinacol)diboron.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
The direct C─H amination of arenes is a powerful strategy for synthesizing arylamines, yet existing methods often suffer from limited substrate scope, poor selectivity, or scalability issues, particularly for electron-deficient arenes. Here, we introduce a continuous flow electrochemical C─H amination via a pyridination-aminolysis sequence, enabling the efficient functionalization of arenes with diverse electronic properties. The method operates under continuous flow electrochemical conditions, avoiding the need for divided cells, strong chemical oxidants, or homogeneous transition-metal catalysts.
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