Aryl carboxylic esters were synthesized by Pd-catalyzed carbonylation of aryl p-fluorobenzenesulfonates or -tosylates. A unique Josiphos ligand was discovered through high-throughput catalyst screening, which was the key for the successful carbonylation of various substrates. This catalyst is effective and works well for both electron-rich and electron-poor aryl arenesulfonates. Isolated yields of up to 90% were obtained for aryl p-fluorobenzenesulfonates and -tosylates. [reaction: see text]
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http://dx.doi.org/10.1021/ol062208g | DOI Listing |
J Org Chem
January 2025
Department of Chemistry, Jadavpur University, Kolkata 700032, India.
We have developed a novel protocol for carbonylative homocoupling of arylboronic acids using dithiocarbamate esters as the carbonyl alternative. A series of arylboronic acids underwent smooth reaction with dithiocarbamate ester (MeNCSMe) in the presence of Pd(PPh)Cl catalyst, Cu(OAc)·HO additive, and NaCO in DCE solvent, producing the biaryl ketones efficiently. The mechanism has been studied with the help of several control experiments that reveal the probability of thioamide intermediacy.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
College of Chemistry and Chemical Engineering, Hunan Provincial Key Laboratory of Micro and Nano Material Interface Science, Central South University, Changsha 410083, Hunan, P. R. China.
The first vinyl-linked PPh-based covalent-organic frameworks (Pd@TMBen-PPh and Pd@TMBen-4F-PPh) were facilely constructed direct three-component Knoevenagel condensation, which could serve as outstanding heterogeneous catalysts for the Pd-catalyzed carbonylation coupling reaction owing to the synergistic effect of the flexible PPh-ligated Pd complexes and the rigid framework.
View Article and Find Full Text PDFJ Org Chem
December 2024
School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China.
A novel Cu/Pd-catalyzed domino radical cyclization and C-H carbonylation of α-bromocarbonyls has been developed, which enables the rapid incorporation of CO unit into polycyclic quinolin-2(1)-one scaffolds. By using Mo(CO) as the CO source, the reaction proceeded smoothly to furnish various polycyclic carbonyl-containing quinolin-2(1)-one derivatives in high yields. Notably, this method could be used in the late-stage modification of biologically active molecules such as estrone.
View Article and Find Full Text PDFJ Phys Chem A
December 2024
Centre for Computational Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China.
The application of machine learning (ML) to predict reaction yields has shown remarkable accuracy when based on high-throughput computational and experimental data. However, the accuracy significantly diminishes when leveraging literature-derived data, highlighting a gap in the predictive capability of the current ML models. This study, focusing on Pd-catalyzed carbonylation reactions, reveals that even with a data set of 2512 reactions, the best-performing model reaches only an of 0.
View Article and Find Full Text PDFChem Commun (Camb)
November 2024
Organometallic Synthesis and Catalysis Lab, Organic Chemistry Division, CSIR-National Chemical Laboratory (CSIR-NCL), Dr. Homi Bhabha Road, Pune - 411 008, India.
We report the first regioselective C2-C7 oxidative coupling of indoles using a palladium catalyst upon the strategic installation of -pyridinyl and C3-carbonyl, which delivers 2,7-biindoles with a broad scope (25 examples; up to 93% yield). Isolation of the catalytic intermediate reveals the initial activation of the C(7)-H bond, followed by the C(2)-H bond in indoles, and the reaction proceeds a Pd(II)/Pd(0) pathway.
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