We report the first method for the direct, regioselective Ru(ii)-catalyzed oxidative arylation of C-H bonds in diverse N-heterocycles with aryl silanes by exploiting solvent-controlled N-coordination. The reaction takes advantage of the attractive features of organosilanes as coupling partners, providing proof of concept for N-directed Ru(ii)-catalyzed C-H arylation. This novel, operationally-simple and versatile protocol utilizes the Ru(ii)/CuF reagent system in which CuF serves as a dual activator/oxidant in non-coordinating solvents to accommodate for ligand N-coordination. This first Ru(ii)-catalyzed N-directed Hiyama C-H arylation offers broad implications to achieve numerous C-H bond functionalizations by versatile ruthenium(ii) catalysis manifold.
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http://dx.doi.org/10.1039/c7ob00818j | DOI Listing |
Chem Rec
January 2025
Department of Pharmacy, Banasthali Vidyapith, Rajasthan, India.
Seven-membered nitrogen-containing heterocycles, particularly azepine-based compounds, represent an intriguing class of molecules with vast arrays of applications. These compounds have garnered considerable attention in synthetic and medicinal chemistry due to their non-planar, non-aromatic features, which offer structural flexibility and diversity to design new drugs with improved pharmacological properties. This review summarizes the recent advances in the synthesis of azepine derivatives, including eco-friendly methodologies that align with the principles of green chemistry, which emphasize atom economy, sustainability, and waste reduction.
View Article and Find Full Text PDFInt J Mol Sci
December 2024
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov Str., 8, Kazan 420088, Russia.
Alkaloids are predominantly nitrogen-containing heterocyclic compounds that are usually isolated from plants, and sometimes from insects or animals. Alkaloids are one of the most important types of natural products due to their diverse biological activities and potential applications in modern medicine. Cyclic imines were chosen as starting compounds for the synthesis of alkaloids due to their high synthetic potential.
View Article and Find Full Text PDFOrg Lett
January 2025
Department of Organic Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. China.
A Cu-catalyzed relay process for the preparation of diazidated quinazolinone and polycyclic imidazole derivatives in which readily available alkene-tethered substrates undergo an addition/cyclization/C(sp)-H functionalization of alkene sequences with high efficiency is described. Various functionalized N-heteropolycyclic compounds were readily prepared in good yields with a broad substrate scope. Moreover, the direct azidation of the α-C(sp)-H bond of the corresponding N-heterocycles has been demonstrated on the basis of mechanistic studies, which provide an alternative late-stage functionalization approach for the derivatization of N-heterocyclic scaffolds.
View Article and Find Full Text PDFJ Org Chem
January 2025
Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning, Guangxi 530004, China.
Among the known aromatic -heterocycles, pyrroles are significant and versatile privileged components in pharmacologically relevant molecules. Herein, we demonstrate a protocol for the selective construction of alkynylated pyrroles in a diversity-oriented fashion through divergent C2/C5 site-selective alkynylation of pyrrole derivatives by employing a palladium catalyst with two different solvent systems. In the presence of 1,4-dioxane, the C2-alkynylation process via chelation-assisted palladation is favored.
View Article and Find Full Text PDFScience
January 2025
Department of Chemistry and Biochemistry, University of Oklahoma, 101 Stephenson Parkway, Norman, OK, USA.
Given the prevalence of nitrogen-containing heterocycles in commercial drugs, selectively incorporating a single nitrogen atom is a promising scaffold hopping approach to enhance chemical diversity in drug discovery libraries. We harness the distinct reactivity of sulfenylnitrenes, which insert a single nitrogen atom to transform readily available pyrroles, indoles, and imidazoles into synthetically challenging pyrimidines, quinazolines, and triazines, respectively. Our additive-free method for skeletal editing employs easily accessible, benchtop-stable sulfenylnitrene precursors over a broad temperature range (-30 to 150°C).
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