The direct functionalization of C-H bonds has revolutionized the field of synthetic organic chemistry by enabling efficient and atom-economical modification of arenes by avoiding prefunctionalization. However, the inherent challenges of inertness and regioselectivity in different C-H bonds, particularly for distal positions, necessitate innovative approaches. In this aspect, photoredox catalysis by utilizing both transition metal and organic photocatalysts has emerged as a powerful tool for addressing these challenges under mild reaction conditions. This review provides a comprehensive overview of recent progress in regioselective C-H functionalization in arenes photocatalysis. Emphasizing the strategies for achieving , , and -selectivity, we explore the mechanistic insights, catalyst designs, and the novel methodologies that have expanded the scope of C-H bond functionalization. This discussion aims to offer valuable perspectives for advancing the field and developing more efficient and sustainable synthetic methodologies.
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http://dx.doi.org/10.1039/d4sc07491b | DOI Listing |
Angew Chem Int Ed Engl
January 2025
The University of Manchester, School of Chemistry & Manchester Institute of Biotechnology, 131 Princess Street, M1 7DN, Manchester, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.
Amide bond formation is fundamental in nature and is widely used in the synthesis of pharmaceuticals and other valuable products. Current methods for amide synthesis are often step and atom inefficient, requiring the use of protecting groups, deleterious reagents and organic solvents that create significant waste. The development of cleaner and more efficient catalytic methods for amide synthesis remains an urgent unmet need.
View Article and Find Full Text PDFChem Asian J
January 2025
National Chemical Laboratory CSIR, Chemical Engineering Division, Dr. Homi Bhabha Road, 411008, Pune, INDIA.
Regioselective C-H difluoroalkylation of diverse 2-pyridones with ethyl bromodifluoroacetates and bromodifluoroacetamides is accomplished by using a (dppf)NiCl2 catalyst under mild conditions. This efficient protocol could deliver a variety of C-3 difluoroalkylated pyridones with the tolerance of a range of highly susceptible functionalities, such as -Cl, -Br, -I, -COMe, -CN, -NMe2 and -NO2, including heteroarenes like pyridinyl, furanyl, thiophenyl and carbazolyl moieties. A preliminary mechanistic study suggests the radical pathway for the reaction involving fluoroalkyl radical intermediate.
View Article and Find Full Text PDFOrg Lett
January 2025
Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, People's Republic of China.
A three-component coupling strategy for 1,4-dicarbofunctionalization of 1,3-butadiene with C-H bearing substrates has been developed using photoinduced Pd catalysis, with aryl bromide serving as the hydrogen atom transfer (HAT) reagent. This photocatalytic coupling process achieves functionalized oxindole motifs in good yield and regioselectivity under mild reaction conditions. The versatility and synthetic utility of this method are demonstrated through the addition of a variety of C-H-bearing partners and various oxindole substrates to both substituted and unsubstituted butadiene.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Chemistry, Malaviya National Institute of Technology Jaipur, Jaipur 302017, Rajasthan, India.
J Am Chem Soc
January 2025
Department of Chemistry, University of Texas at Austin, Austin 78712, Texas, United States.
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