A copper-catalyzed direct propargylation of polyfluoroarenes with secondary propargyl phosphates has been developed. The reaction proceeds under mild reaction conditions with high efficiency and regioselectivity and provides a concise and straightforward method for the synthesis of polyfluoroarylated derivatives of interest in both life and materials science.
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http://dx.doi.org/10.1021/acs.orglett.6b01642 | DOI Listing |
Chem Sci
January 2025
Department of Chemistry, Indian Institute of Technology Hauz Khas Delhi New Delhi 110016 India
The direct transformation of methane into C oxygenates such as acetic acid selectively using molecular oxygen (O) is a significant challenge due to the chemical inertness of methane, the difficulty of methane C-H bond activation/C-C bond coupling and the thermodynamically favored over-oxidation. In this study, we have successfully developed a porous aluminium metal-organic framework (MOF)-supported single-site mono-copper(ii) hydroxyl catalyst [MIL-53(Al)-Cu(OH)], which is efficient in directly oxidizing methane to acetic acid in water at 175 °C with a remarkable selectivity using only O. This heterogeneous catalyst achieved an exceptional acetic acid productivity of 11 796 mmol mol h in 9.
View Article and Find Full Text PDFJ Org Chem
January 2025
National Engineering Research Center of Pesticide, College of Chemistry, Nankai University, Tianjin 300071, China.
This study introduces a novel methodology for the direct construction of tetrasubstituted centers, utilizing secondary C(sp)-H and C(sp)-H substrates, specifically indolin-2-ones and indoles, through an innovative oxidative cross-coupling reaction. Facilitated by a straightforward copper salt catalyst, this reaction proceeds efficiently at a mild temperature of 40 °C under operationally streamlined conditions. Emphasizing sustainability, this method is notably enhanced by employing air (molecular oxygen) as an eco-friendly oxidant.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21, Nishi 10, Kita-ku, Sapporo, Hokkaido, 001-0021, Japan.
Fluorine-containing compounds have shown unparalleled impacts in the realm of functional molecules, and the ability to prepare novel structures has been crucial in unlocking new properties for applications in pharmaceutical and materials science. Herein, we report a copper-catalyzed, photoinduced defluorinative C-O coupling between trifluoromethylarenes and alcohols. This method allows for direct access to a wide selection of difluorobenzylether (ArCFOR) molecules, including a compound displaying liquid crystal behavior.
View Article and Find Full Text PDFOrg Lett
December 2024
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, Jiangxi 330031, China.
J Org Chem
December 2024
Department of Applied Chemistry, Kyungpook National University, 80 Daehakro, Bukgu, Daegu 41566, Republic of Korea.
In this study, 5-(2-bromoaryl)tetrazoles were reacted with 1,3-diketones in DMF in the presence of a catalytic amount of magnetic Cu-MOF-74 (FeO@SiO@Cu-MOF-74) and a base under microwave irradiation to yield the corresponding 1-aminoisoquinolines. The FeO@SiO@Cu-MOF-74 catalyst could be easily recovered from the reaction mixture and reused four times without any significant loss of catalytic activity. An initial copper-catalyzed C(sp)-C(sp) bond formation accompanied by -Claisen deacylative cyclocondensation (for acyclic 1,3-diketones) and direct cyclocondensation (for cyclohexane-1,3-diones) is proposed as a key reaction pathway for this process.
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