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We report an efficient method for regioselective O-arylation of the 6-hydroxy group of carbohydrates. The reaction involves a nucleophilic aromatic substitution reaction (SAr) using electron-deficient arenes under mild conditions. Regioselectively monoarylated carbohydrate derivative was produced smoothly in the reaction by fine-tuning with the base. The pentafluoropyridine (P1) in combination with N, N-diisopropylethylamine (DIPEA) was successfully converted to regioselective O-arylated products of different positional hydroxy group free sugar derivatives with various functional groups.
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http://dx.doi.org/10.1016/j.carres.2025.109447 | DOI Listing |
Org Lett
March 2025
School of Chemistry, University of Nottingham, Nottingham NG7 2RD, U.K.
We report a new C-O arylation strategy for the synthesis of 2-arylphenols from bio-abundant guaiacols. Functionalization of the strong C-O bond is achieved through a sequence of arylative dearomatization, mediated selectively by an electrophilic bismuth(V) arylating agent, followed by 1,2-reduction and deoxygenative rearomatization. This methodology represents a rare example of complexity-generating deoxygenation applied to lignin-derived biorefinery feedstocks and provides independence from the regioselectivity rules established for the bismuth(V)-mediated arylation of simple phenols.
View Article and Find Full Text PDFCarbohydr Res
June 2025
Department of Chemistry, Indian Institute of Technology Hyderabad, Kandi, 502284, Sangareddy, Telangana, India. Electronic address:
We report an efficient method for regioselective O-arylation of the 6-hydroxy group of carbohydrates. The reaction involves a nucleophilic aromatic substitution reaction (SAr) using electron-deficient arenes under mild conditions. Regioselectively monoarylated carbohydrate derivative was produced smoothly in the reaction by fine-tuning with the base.
View Article and Find Full Text PDFJ Org Chem
June 2024
Department of Chemistry and Chemical Biology, Indian Institute of Technology (Indian School of Mines), Dhanbad 826004, India.
An air-stable, robust, and well-defined copper(II)-7-azaindole--oxide-based catalyst [Cu(7-AINO)] (abbreviated as Cu(II)-7-AINO) has been demonstrated as an efficient catalyst for various Ullmann-type coupling reactions. This easily prepared and cost-effective catalyst facilitates the arylation and heteroarylation of diverse -, -, and -nucleophiles, including azoles, aminoazoles, (hetero)arylthiols, and phenols. Notably, they also exhibit substantial compatibility with a wide range of functional groups.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2022
School of Chemistry, University of Nottingham, Nottingham, NG7 2RD, UK.
We report that O-selective arylation of 2- and 4-pyridones with arylboronic acids is affected by a modular, bismacycle-based system. The utility of this umpolung approach to pyridyl ethers, which is complementary to conventional methods based on S Ar or cross-coupling, is demonstrated through the concise synthesis of Ki6783 and picolinafen, and the formal synthesis of cabozantib and golvatinib. Computational investigations reveal that arylation proceeds in a concerted fashion via a 5-membered transition state.
View Article and Find Full Text PDFA facile and efficient synthesis of 7-iodobenzo[]furan derivatives a highly regioselective tandem α-arylation/intramolecular -arylation of 5-substituted-1,2,3-triiodobenzenes and benzylketones is described. Remarkably, the α-arylation coupling reactions initiate exclusively at the least sterically-hindered position of the triiodoarene, which results in a highly chemoselective transformation. The highest yields were observed in reactions between electron-poor 1,2,3-triiodoarenes and electron-rich benzylketones, yet the optimized reaction conditions were found to be tolerant to a wide range of different functional groups.
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