A new three-component coupling reaction of benzyne is described that uses two intermolecular carbopalladation reactions to produce 1,2-functionalized benzene derivatives.
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http://dx.doi.org/10.1021/ja0615526 | DOI Listing |
J Org Chem
January 2025
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China.
The synthesis of perfluoroalkylated fullerenes (PFAFs) holds significant importance due to their enhanced molecular stability, increased lipophilicity, and high electron affinity. Herein, we report a copper-catalyzed multicomponent reaction conducted under aerobic conditions, which enables the production of highly soluble PFAFs with half-wave reduction potentials similar to those of C. Furthermore, the challenges posed by C-F coupling in carbon signal assignment were addressed through fluorine-decoupled carbon spectroscopy, facilitating precise structural characterization of the perfluoroalkyl moieties.
View Article and Find Full Text PDFACS Cent Sci
January 2025
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
Multicomponent reactions (MCRs), highly sought-after methods to produce atom-, step-, and energy-economic organic syntheses, have been developed extensively. However, catalytic asymmetric MCRs, especially those involving radical species, remain largely unexplored owing to the difficulty in stereoselectively regulating the extraordinarily high reactivity of open-shell radical species. Herein, we report a conceptually novel catalytic asymmetric three-component radical cascade reaction of readily accessible glycine esters, α-bromo carbonyl compounds and 2-vinylcyclopropyl ketones via synergistic photoredox/Brønsted acid catalysis, in which three sequential C-C (σ/π/σ) bond-forming events occurred through a radical addition/ring-opening/radical-radical coupling protocol, affording an array of valuable enantioenriched unnatural α-amino acid derivatives bearing two contiguous stereogenic centers and an alkene moiety in moderate to good yield with high diastereoselectivity, excellent enantioselectivity and good -dominated geometry under mild reaction conditions.
View Article and Find Full Text PDFJ Org Chem
January 2025
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua 321004, P. R. China.
-Difluorohomoallyl amines, an important class of -difluoroalkenes, are prevalent moieties in many bioactive compounds. However, limited methods are suitable for the synthesis of this type of compound containing secondary amines. Here, we display a photocatalytic multicomponent protocol for the synthesis of -difluoroalkenes containing secondary amines, which makes use of readily available materials: arylamines, alkyl aldehydes, and α-trifluoromethyl alkenes.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Henan Key Laboratory of Natural Medicine Innovation and Transformation, Henan University, Kaifeng, Henan 475004, PR China.
Recent advancements in green and sustainable platforms, particularly visible light-driven photocatalysis, have spurred significant progress in radical chemistry, enabling the efficient synthesis of important molecules from simple and readily available feedstocks under mild conditions. However, the rapid orbital flipping and high reactivity of radicals pose substantial challenges for achieving precise enantiocontrol in stereocenter formation via radical coupling. In this study, we present a generic and efficient strategy that modulates this elusive approach, facilitating enantiocontrollable protonation through 1,3-boron migration.
View Article and Find Full Text PDFJ Chem Ecol
January 2025
Canterbury Research Centre, The New Zealand Institute for Plant and Food Research Limited, Lincoln, 8152, New Zealand.
The identification of sex pheromones in native New Zealand moths has been limited, largely due to their minimal pest impact on agricultural ecosystems. The kōwhai moth, Uresiphita polygonalis maorialis, a native crambid, is known for its herbivory on Sophora spp. and Lupinus arboreus leaves.
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