A novel Co(III)-catalyzed oxidative annulation of aromatic aldehydes with internal alkynes for accessing isocoumarins is described, which is achieved by oxidation, weak chelation-assisted C-H bond functionalization, and annulation cascades with excellent functional group compatibility, high atom economy, and step efficiency. By using environmentally benign and inexpensive poly(ethylene glycol)-400 (PEG-400), the Co/Cu/PEG-400 system could be recycled and reused.
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http://dx.doi.org/10.1021/acs.joc.9b00580 | DOI Listing |
Int J Mol Sci
January 2025
Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences, S. Kovalevskoy Street, 22, Ekaterinburg 620137, Russia.
The synthetic approach based on a sequence of Buchwald-Hartwig cross-coupling and annulation through intramolecular oxidative cyclodehydrogenation has been used for the construction of novel 4-alkyl-4-thieno[2',3':4,5]pyrrolo[2,3-]quinoxaline derivatives. For the first time, these polycyclic compounds were evaluated for antimycobacterial activity, including extensively drug-resistant strains. A reasonable bacteriostatic effect against HRv was demonstrated.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, University of Houston, Houston, Texas 77204-5003, United States.
Monoanionic, bidentate-auxiliary-directed, cobalt-catalyzed C-H bond functionalization has become a very useful tool in organic synthesis. A comprehensive investigation into isolated organometallic intermediates and their reactivity within the catalytic cycle is lacking. We report here mechanistic studies of cobalt-catalyzed, aminoquinoline-directed C(sp)-H bond functionalization.
View Article and Find Full Text PDFOrg Lett
January 2025
China Guangxi Key Laboratory of Pharmaceutical Precision Detection and Screening, Guangxi Key Laboratory of Bioactive Molecules Research and Evaluation, and Key Laboratory of Micro-Nanoscale Bioanalysis and Drug Screening of Guangxi Education Department, Pharmaceutical College, Guangxi Medical University, Nanning 530021, China.
Herein, a one-pot domino catalyzed three-component process is described, which is initiated by a palladium/zinc cooperatively catalyzed cycloaddition between trimethylenemethane (TMM) and unactivated alkyl/aryl imines, followed by one-pot isomerization and Zn(OTf)-catalyzed DDQ oxidation, furnishing valuable substituted pyrroles. We disclose that the palladium/zinc cooperative catalysis affords a dual-Zn(OTf)-stabilized azapalladacycle, wherein the Pd-N bond is polarized by Zn(OTf), facilitating a unique outer-sphere allylic amination. Moreover, subsequent DDQ dehydrogenation can be feasibly promoted by zinc catalysis.
View Article and Find Full Text PDFChem Sci
November 2024
Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry, Center for Molecular Materials, Faculty of Chemistry, Universität Bielefeld Universitätsstrasse 25 D-33615 Bielefeld Germany http://www.ghadwalgroup.de.
The first carbocyclic gallylene [(ADC)Ga(GaI)] and bis-gallylene [(ADC)Ga] (ADC = PhC{N(Dipp)C}; Dipp = 2,6-iPrCH) featuring a central CGa ring annulated between two 1,3-imidazole rings are prepared by KC reductions of [(ADC)GaI]. Treatment of [(ADC)Ga] with Fe(CO) affords complex [(ADC)GaFe(CO)] in which each Ga(i) atom serves as a two-electron donor. [(ADC)Ga] activates white phosphorus (P) and the C -F bond of aryl fluorides (ArF) to yield compounds [(ADC)Ga(P)] and -/-[(ADC)GaF(Ar)], respectively.
View Article and Find Full Text PDFChemistry
January 2025
Shanghai Institute of Organic Chemistry, State Key Laboratory of Organometallic Chemistry, 354 Fenglin Lu,, 200032, Shanghai, CHINA.
The unprecedent gold-catalyzed intermolecular 1,2-difunctionalization of nitriles with aryl iodides via Au(I)/Au(III) redox catalysis has been developed, providing an expedient route to the synthesis of benzoxazoles and 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 and this annulation is initiated by oxidative addition, rather than the nucleophilic attack of the phenol moiety in o-iodophenol towards the nitrile.
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