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The direct cross-couplings of aryl nonaflates with aryl bromides could be successfully accomplished by utilizing nickel as the catalyst, magnesium as the metal mediator, and lithium chloride as the additive. The reactions proceeded efficiently in THF at room temperature to produce the desired biaryls in moderate to good yields, showing both a reasonable substrate scope and functional group tolerance. Additionally, an equally good performance could be realized when the reaction was subjected to scale-up synthesis. Preliminary study suggested that the reaction presumably proceeds through the in situ formation of an arylmagnesium reagent as the key reaction intermediate.
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http://dx.doi.org/10.1021/acs.joc.4c02777 | DOI Listing |
Acc Chem Res
September 2025
Department of Chemistry, FRQNT Centre for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke Street W, Montréal, Québec H3A 0B8, Canada.
ConspectusMolecular photochemistry, by harnessing the excited states of organic molecules, provides a platform fundamentally distinct from thermochemistry for generating reactive open-shell or spin-active species under mild conditions. Among its diverse applications, the resurgence of the Minisci-type reaction, a transformation historically reliant on thermally initiated radical conditions, has been fueled by modern photochemical strategies with improved efficiency and selectivity. Consequently, the photochemical Minisci-type reaction ranks among the most enabling methods for C()-H functionalizations of heteroarenes, which are of particular significance in medicinal chemistry for the rapid diversification of bioactive scaffolds.
View Article and Find Full Text PDFAcc Chem Res
August 2025
Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, Department of Chemistry, School of Science, and Research Center for Industries of the Future, Westlake University, Hangzhou, Zhejiang 310030, China.
ConspectusAsymmetric carbonyl addition reactions have long been recognized as a powerful platform for synthesizing chiral alcohols, garnering significant attention in synthetic chemistry. Over the past few decades, notable progress has been made in this field through the use of organometallic reagents and two-electron polar addition processes. However, these approaches often face challenges related to functional group compatibility, particularly when employing strongly basic alkyl nucleophiles, and the construction of vicinal stereocenters remains difficult due to the limited availability of chiral alkylmetal nucleophiles, whether presynthesized or formed .
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
State Key Laboratory of Bioactive Molecules and Druggability Assessment, Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs, College of Chemistry and Materials Science, and Guangdong Provincial Key Laboratory of Supramolecular Coordination
Palladium nanoclusters (Pd NCs) hold great promise in organic synthesis; however their controlled synthesis via direct reduction remains challenging due to kinetically favored formation of nanoparticles. In this study, we employ carbonylmetallate ligands to regulate the reduction reaction kinetics and successfully achieve three [Co(CO)] terminated Pd NCs. Magnetic studies, in conjunction with quantum chemical calculations, suggest that the Pd cluster exhibits a quartet ground state and open-shell character with 1S configuration, representing the first open-shell palladium containing one free electron.
View Article and Find Full Text PDFJ Enzyme Inhib Med Chem
December 2025
Institute of Pharmacognosy, University of Szeged, Szeged, Hungary.
Phenols are important structural elements of natural products and pharmaceuticals. Due to their versatile chemical transformability, phenols are frequently used building blocks in medicinal chemistry. Their aromatic nature allows directed C(sp)-H functionalisations, especially at the positions.
View Article and Find Full Text PDFNat Commun
May 2025
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, Singapore.
Metallaphotocatalysis, integrating interlocked photocatalytic cycles and transition-metal catalysis, harmonizes the ground state and excited state reactivities, enabling cross-couplings under mild conditions and expanding the scope of accessible transformations. However, homogeneous dual metallaphotocatalysts often suffer from limitations such as low catalyst stability, high metal loading, and challenges in catalyst recycling. In this study, we engineered a class of nickel-incorporated pyridyl-quinoline-linked covalent organic frameworks (Ni-PQCOFs) serving as robust and efficient heterogeneous metallaphotocatalysts.
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