A general and efficient method for the coupling of a wide range of amides with alkynyl bromides is described here. This novel amidation reaction involves a catalytic protocol using copper(II) sulfate-pentahydrate and 1,10-phenanthroline to direct the sp-C-N bond formation, leading to a structurally diverse array of ynamides including macrocyclic ynamides via an intramolecular amidation. Given the surging interest in ynamide chemistry, this atom economical synthesis of ynamides should invoke further attention from the synthetic organic community.
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http://dx.doi.org/10.1021/jo060230h | DOI Listing |
J Org Chem
January 2025
Department of Chemistry, Indian Institute of Technology Indore, Indore 453552, Madhya Pradesh, India.
Herein, we report the -generated transient bromoiodane-mediated brominative annulation of 2-alkynyl arylimidate for the synthesis of 4-bromoisoquinolines at room temperature. Using a simple hypervalent iodine reagent PIDA as a mild oxidant and potassium bromide as the halogen source, a broad range of valuable 4-bromoisoquinolines can be synthesized in excellent yields. The reaction features readily available chemicals, mild metal-free conditions, and high functional group tolerance, providing an efficient alternative for the construction of halogenated isoquinolines.
View Article and Find Full Text PDFChemistry
November 2024
College of Chemistry and Chemical Engineering, Henan University, Kaifeng, 475004, P.R. China.
Polyfluoroaryl ethers represent an important framework of biologically active molecules and materials. Owing to the strong bond dissociation energy of C-F bond, selectivity and other issues, transition metal-catalyzed synthesis of polyfluoroaryl ethers from perfluoroarenes via the activation of C-F bond is challenging and underdeveloped, as compared to the well-documented C-O bond formation starting from aryl iodides, aryl bromides or aryl chlorides. Herein, an unprecedented Pd-catalyzed defluorinative etherification for the synthesis of polyfluoroaryl ether skeletons using hydrobenzoxazoles as phenol surrogate, has been reported.
View Article and Find Full Text PDFChem Sci
October 2024
Institute of Organic Chemistry, RWTH Aachen University Landoltweg 1 Aachen 52056 Germany
Alkynes are a crucial class of materials with application across the wide range of chemical disciplines. The alkynylation of alkyl halides presents an ideal strategy for assembling these materials. Current methods rely on the intrinsic electrophilic nature of alkyl halides to couple with nucleophilic acetylenic systems, but these methods faces limitations in terms of applicability and generality.
View Article and Find Full Text PDFJ Org Chem
November 2024
School of Pharmacy, Changzhou University, Changzhou, Jiangsu 213164, P. R. China.
J Org Chem
September 2024
Corteva Agriscience, Reactive Chemicals SME, Indianapolis, Indiana 46268, United States.
Herein, we disclose a palladium-catalyzed cross-coupling of aryl bromides and chlorides with trimethylsilylalkynes under mild reaction conditions. This method utilizes commercially available and air stable palladium precatalysts and avoids the use of copper cocatalysts. Moreover, it allows for the synthesis of a wide range of disubstituted alkynes in high yields with excellent functional group tolerance.
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