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A high-valent Ir(III)-catalyzed C-H bond functionalization is carried out for the first time on water for the synthesis of a biologically relevant chromone moiety. The C-H activation and annulation of salicylaldehydes with diazo-compounds provided the desired chromones. The synthesis of C3-substitution-free chromones has also been demonstrated by a one-pot decarboxylation by employing tert-butyl diazoester. C3 and C5 C-H activations of the product chromone are also carried out under different conditions for further diversification.
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http://dx.doi.org/10.1021/acs.joc.9b00418 | DOI Listing |
Adv Sci (Weinh)
April 2025
Anti-infective Agent Creation Engineering Research Centre of Sichuan Province, Sichuan Industrial Institute of Antibiotics, School of Pharmacy, Chengdu University, Chengdu, 610106, China.
Isoflavonoids represent a privileged scaffold among various bioactive natural products, rendering their structural diversification through green synthesis and subsequent biological evaluations a compelling research area. In this study, an NHC organocatalytic radical acylalkylation of 1,3-enynes using salicylaldehydes is presented, followed by a cascade intramolecular annulation, yielding a series of fluorinated isoflavone derivatives with substantial yields under environmental-friendly conditions. This approach, distinguished by its excellent modularity and high functional group tolerance, represents an unprecedented organocatalytic 1,3,4-trifunctionalization of 1,3-enynes designed for the green synthesis of bioactive isoflavones in a single step.
View Article and Find Full Text PDFJ Org Chem
December 2024
Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, China.
A one-pot, three-component synthesis of indole-benzofuran bis-heterocycles from terminal alkynes, salicylaldehydes, and indoles has been developed via copper-catalyzed tandem annulation. This catalytic system utilizes readily available starting materials, enabling predictable synthesis of indole-benzofuran bis-heterocycles with broad substrate versatility, excellent regiocontrol, and gram-scale amenability. The reaction proceeds via a sequential pathway involving A3 coupling, 1,4-conjugate addition, and 5-- cyclization.
View Article and Find Full Text PDFJ Org Chem
December 2024
Molecular Horizons Research Institute, School of Chemistry and Molecular Bioscience, University of Wollongong, Northfields Ave, Wollongong, NSW 2522, Australia.
A two-step formal (4 + 1) annulation-dehydration reaction offers a convenient route to C2-arylated indoles and benzofurans. This reaction exploits the bifunctional reactivity of electron-deficient benzyl chlorides with -sulfonyl-2-aminobenzaldehydes or salicylaldehyde derivatives. The reaction tolerates both electron-withdrawing and donating groups on the substituted aldehydes, as well as variation of electron-withdrawing groups at the position of the benzyl chloride reagent.
View Article and Find Full Text PDFOrg Lett
November 2024
State Key Laboratory of Natural Medicines, Department of Organic Chemistry, China Pharmaceutical University, Nanjing 210009, P. R. China.
Herein we reported a novel strategy for constructing benzoxepine fused succinimide derivatives via a phosphine-catalyzed [3 + 4] cyclization of α-substituted allenes and salicylaldehyde Schiff bases. This methodology serves as a conduit for the construction of benzoxepine derivatives in good yields under mild conditions by an unprecedented mode involving the β'-carbon of allenes. Density functional theory calculations were conducted to study the possible mechanism.
View Article and Find Full Text PDFJ Org Chem
February 2024
Department of Chemistry, University of Calcutta, 92 A. P. C. Road, Kolkata 700009, India.
Herein, we report a highly efficient Ag(I)-catalyzed indolyzation with Friedel-Crafts alkylation through a cascade cyclization strategy for accessing valuable hybrid heterocycles for the first time. This general strategy consists of forming four C-C/C-N/C-O bonds toward dual annulation reactions of 2-alkynylanilines with methyl benzoate-2-carboxaldehydes and aromatic amines, as well as with salicylaldehydes and malononitrile. Variably substituted new indolo-4-phthalimidines and indolo-4-chromenes were synthesized with excellent yields (85-93%) under mild reaction conditions.
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