Coumarin skeletons are significant structural units frequently used in the fields of synthetic chemistry, medicinal chemistry, and materials science. Herein, we report a hemilabile P,N-ligand-assisted gold-catalyzed difunctionalization of activated alkynes with organohalides. The reaction occurs effectively under mild conditions without requiring an external oxidant, producing a variety of 3-arylated and alkenylated coumarin derivatives in high to excellent yields. This method demonstrates a wide substrate tolerance and superb functional group compatibility and is also suitable for heteroaromatic substrates. Further mechanistic investigations strongly support the proposed mechanism of the reaction.
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http://dx.doi.org/10.1021/acs.orglett.5c00206 | DOI Listing |
Org Lett
March 2025
Yunnan Key Laboratory of Chiral Functional Substance Research and Application, Yunnan Minzu University, Kunming, Yunnan 650504, China.
Coumarin skeletons are significant structural units frequently used in the fields of synthetic chemistry, medicinal chemistry, and materials science. Herein, we report a hemilabile P,N-ligand-assisted gold-catalyzed difunctionalization of activated alkynes with organohalides. The reaction occurs effectively under mild conditions without requiring an external oxidant, producing a variety of 3-arylated and alkenylated coumarin derivatives in high to excellent yields.
View Article and Find Full Text PDFChemistry
February 2025
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, P. R. China.
The unprecedent gold-catalyzed intermolecular 1,2-difunctionalization of nitriles with o-iodophenols or o-iodoanilines via Au(I)/Au(III) redox catalysis has been developed, providing an expedient route to the synthesis of benzoxazoles or benzimidazoles with broad substrate scope and high functional compatibility. Mechanistic investigation reveals that the Au(III)-Ar species generated via oxidative addition of o-iodophenol to MeDalphosAu, serves as a key intermediate. Particularly, this annulation is initiated by oxidative addition, rather than the nucleophilic attack of the phenol moiety in o-iodophenol towards the nitrile.
View Article and Find Full Text PDFChem Commun (Camb)
August 2024
Natural Products and Medicinal Chemistry Division, CSIR-Indian Institute of Integrative Medicine, Canal Road, Jammu-180001, India.
A one-pot domino protocol employing gold(I) catalysis has been developed for the cascade trifluoromethyl-amination/sulfoximination of quinones. Togni I serves as the trifluoromethyl installing precursor, while amine or sulfoximine serves as the aminating source. Preliminary investigations suggest a mutual activation of Togni I and the amine precursor, facilitating the facile difunctionalization of quinones with excellent regioselectivity.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2023
Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal Bypass Road, Bhauri, Bhopal-, 462 066, India.
Herein, we disclose the first report of 1,2-difunctionalization of C-C multiple bonds using electrochemical gold redox catalysis. By adopting the electrochemical strategy, the inherent π-activation and cross-coupling reactivity of gold catalysis are harnessed to develop the oxy-alkynylation of allenoates under external-oxidant-free conditions. Detailed mechanistic investigations such as P NMR, control experiments, mass studies, and cyclic voltammetric (CV) analysis have been performed to support the proposed reaction mechanism.
View Article and Find Full Text PDFChem Commun (Camb)
June 2023
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
Dinuclear-gold-catalyzed radical difunctionalization of alkyl bromides with 1,7-enynes has been established dehalogenation and 1,5-HAT processes. This protocol was used to construct, in a facile and efficient manner, a wide range of cyclopenta[]quinolines bearing two quaternary carbon centers with good yields (28 examples, up to 84% yield). The good functional group compatibility and gram-scale preparation ability of the reaction proved its synthetic robustness.
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