The oxidative palladium-catalyzed cross-coupling of pyrimidines containing pyridotriazol-1-yloxy (OPt) as either a urea or an amide functional group with arylboronic acids in the presence of Cs(2)CO(3) in DME containing 0.6-1.0% H(2)O is described for the preparation of heteroaryl ethers. The bromo substitution in the case of 3-(5-bromo-pyrimidin-2-yloxy)-3H-[1,2,3]triazolo[4,5-b]pyridine 1 could serve as a handle for further elaborations such as Suzuki coupling for attaching varied aryl groups.
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Org Lett
November 2024
Université de Strasbourg, Université de Haute-Alsace, CNRS, UMR 7042-LIMA, ECPM, 25 Rue Becquerel, Strasbourg 67087, France.
Herein, we report the metal-free synthesis of polyfluoroalkyl aryl ethers via nucleophilic substitution of fluorosulfonates, obtained in one pot by bubbling of sulfuryl fluoride (SOF). Polyfluoroalkyl aryl ethers are present in a variety of biologically active compounds, but previous methods for accessing them required metal catalysts or harsh conditions. With this method, their synthesis is possible under mild conditions and with a short reaction time (30 min) from commercially available starting materials and in yields of ≤97%.
View Article and Find Full Text PDFJ Org Chem
September 2024
College of Chemistry, National Engineering Research Center of Pesticide, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China.
Herein, we report the synthesis of 1,1-diarylmethanes via palladium-catalyzed benzylic C(sp)-O arylation of benzyl alcohol derivatives. An efficient, straightforward approach to synthesizing Pd(0)(xantphos) was developed through in situ reduction of Pd(II) to Pd(0) with the bidentate tertiary phosphine xantphos, which proved to be a highly active precatalyst in the Suzuki-Miyaura cross-coupling reaction of benzyl heteroaryl ethers.
View Article and Find Full Text PDFOrg Lett
August 2024
Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Science, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
Herein we report a photoredox/nickel-catalyzed cross-coupling of aryl bromides with 1,1,1,3,3,3-hexafluoroisopropanol for the construction of hexafluoroisopropyl aryl ethers. The mild reaction conditions employed allow for the applicability of a wide range of aryl and heteroaryl bromides. Late-stage functionalization and preliminary mechanistic studies have been demonstrated.
View Article and Find Full Text PDFChem Sci
May 2024
Department of Chemistry, Dalhousie University 6274 Coburg Road, P.O. 15000 Halifax Nova Scotia B3H 4R2 Canada
Nickel-catalyzed cross-couplings of (hetero)aryl electrophiles with a diversity of nucleophiles (nitrogen, oxygen, carbon, and others) have evolved into competitive alternatives to well-established palladium- and copper-based protocols for the synthesis of (hetero)aryl products, including (hetero)anilines and (hetero)aryl ethers. A survey of the literature reveals that the use of cage phosphine (CgP) 'DalPhos' (DALhousie PHOSphine) bisphosphine-type ligands operating under thermal conditions currently offers the most broad substrate scope in nickel-catalyzed cross-couplings of this type, especially involving (hetero)aryl chlorides and phenol-derived electrophiles. The development and application of these DalPhos ligands is described in a ligand-specific manner that is intended to serve as a guide for the synthetic chemistry end-user.
View Article and Find Full Text PDFMolecules
April 2024
Dipartimento di Scienze Chimiche, Fisiche, Matematiche e Naturali, Università degli Studi di Sassari, Via Vienna 2, 07100 Sassari, Italy.
Aryl and heteroaryl iodides have been efficiently converted into the corresponding thioacetates in cyclopentyl methyl ether (CPME), a green solvent, under Cu catalysis. The chemoselectivity of the reaction is mainly controlled by electronic factors, enabling the conversion of both electron-rich and electron-deficient substrates into the corresponding thioacetates in good to excellent yields. The products can be easily deprotected to the corresponding thiolates to carry out additional synthetic transformations in situ.
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