Disclosed herein is a cross-dehydrogenative-coupling reaction of -heterocycles including 1,2,4-triazine-3,5(2, 4)-diones and quinoxaline-2(1)-ones with -methylanilines to form C(sp)-C(sp) under visible-light illumination and ambient air at room temperature. In this process, easily available Ru(bpy)Cl·6HO serves as the catalyst, and air acts as the green oxidant. This method features high atom economy, environmental friendliness, and convenient operation and provides an efficient and practical access to aminomethyl-substituted -heterocycles with extensive functional group compatibility in 40-86% yields.
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http://dx.doi.org/10.1021/acs.joc.1c01207 | DOI Listing |
Angew Chem Int Ed Engl
November 2024
Department of Chemistry, Technical University of Denmark, 2800 Kgs., Lyngby, Denmark.
Alkyl phosphonates are important motifs in medicinal chemistry, yet their efficient synthesis by direct C(sp)-H functionalization remains a challenge. Here, we report straightforward access to benzylic phosphonates by direct C(sp)-H functionalization in a cross-dehydrogenative-coupling reaction between non-specialized alkylarenes and unfunctionalized phosphites. Notably, the C-H substrates are used as the limiting reagents.
View Article and Find Full Text PDFJ Org Chem
December 2024
School of Chemistry and Materials Engineering, Liupanshui Normal University, Liupanshui 553004, China.
An efficient and convenient method for the synthesis of C3-hydroxytrifluoroalkylated indoles and pyrroles was described in this paper. The copper-catalyst-free site-specific cross-dehydrogenative coupling reaction of various indoles and pyrroles with hexafluoroisopropanol proceeded smoothly by using MnO as oxidant to furnish a hydroxytrifluoroalkylated electron-rich -heterocycle in satisfactory to excellent yields. Various groups, including the synthetically useful functional groups Cl, NO, and CN, were tolerated well.
View Article and Find Full Text PDFJ Org Chem
November 2024
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Hong Kong, P. R. China.
A novel and straightforward method for the iron-catalyzed regioselective cross-dehydrogenative coupling of -quinone methides (-QMs) with formamides has been developed, facilitated by the activation of the C(sp)-H bonds of the formyl and alkenyl substituents via a radical strategy. This method does not require the preactivation of the substrates, and it can accommodate a wide range of -QMs and formamides under the optimized reaction conditions, resulting in the formation of the expected C-7 acetamides-functionalized -quinone methides with moderate to good yields. The control experiments revealed that the reaction follows the fundamental equation of second-order kinetics.
View Article and Find Full Text PDFJ Org Chem
November 2024
Engineering Research Center of Tropical Medicine Innovation and Transformation of Ministry of Education, International Joint Research Center of Human-machine Intelligent Collaborative for Tumor Precision Diagnosis and Treatment of Hainan Province, Hainan Provincial Key Laboratory of Research and Development on Tropical Herbs, School of Pharmaceutical Sciences, Hainan Medical University, Haikou 571199, Hainan Province, P.R. China.
An efficient synthesis of α-carbonyl-α'-sulfenyl sulfoxonium ylides through a KIO-promoted cross-dehydrogenative coupling reaction of aryl thiols and α-carbonyl sulfoxonium ylides in an aqueous medium at room temperature has been described. The α-carbonyl sulfoxonium ylides and aryl thiols adorned with various functional groups were well-tolerated and afforded moderate to high yields of α-carbonyl-α-sulfenyl sulfoxonium ylide derivatives. Finally, by converting synthesized ylide into other valuable compounds, we demonstrated the practicality of this synthetic method.
View Article and Find Full Text PDFRSC Adv
September 2024
Faculty of Chemistry, Hanoi University of Science, Vietnam National University (VNU) Vietnam
In a new approach, a series of 3-aroylimidazo[1,2-]pyridine derivatives were prepared in high yields. This approach revealed the direct Fe-catalyzed functionalization of imidazo[1,2-]pyridine derivatives with aryl aldehydes an aerobic oxidative cross-dehydrogenative coupling process. This transformation occurred in the presence of air, and FeBr served as a homogeneous Lewis catalyst.
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