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A straightforward multi-component method is developed to construct multifunctionalized (oxo)indoles under Pd(II) catalysis via intramolecular or intermolecular reaction pathways between electron-rich arenes, diazo compounds, and nitrosoarenes. Under the catalysis of palladium, metal carbene, generated from diazo compound, reacts with electron-rich arene to form zwitterionic intermediate, which is trapped by activated nitrosobenzene to give the desired product. It is worth noting that indole and nitrosobenzene have a competitive relationship and react with diazo compounds to produce different two-component products. Therefore, in multi-component reactions of diazo compounds, electron-rich arene, and nitrosobenzene, obtaining a single multifunctional indole product with high chemical selectivity remains a visible challenge.
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http://dx.doi.org/10.1007/s11030-025-11279-3 | DOI Listing |
Org Biomol Chem
September 2025
Department of Chemistry, Indian Institute of Technology, Madras, Tamil Nadu, 600036, India.
A synthetic method has been developed for the diastereoselective domino synthesis of indolyl-pyrrolo[2,1-]isoindoles from phthalimide-derived -sulfonyl-1,2,3-triazoles and indoles. The reaction proceeds ring chain isomerization of triazoles to give α-imino diazo compounds. Then, denitrogenative generation of α-imino Rh(II) carbenes followed by intramolecular oxygen insertion and nucleophilic addition of indoles delivers the indolyl-pyrrolo[2,1-]isoindoles.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.
Bicyclo[1.1.1]pentanes (BCPs) play crucial roles as saturated bioisosteric replacements of planar benzene rings.
View Article and Find Full Text PDFChem Commun (Camb)
September 2025
CSIR-Central Drug Research Institute Lucknow, 226031, India.
α-Diazo compounds have long been recognized as versatile reagents in organic synthesis, traditionally employed in metallocarbene chemistry. Recent advances have expanded their scope beyond conventional carbene-based transformations, leading to diverse applications in heterocycle synthesis and functionalization strategies. This review highlights the evolution of α-diazo compounds as key reagents in modern synthetic methodologies, focusing on their unique reactivity patterns, including cycloadditions, homologations, ring expansions, and carbene-free functionalizations.
View Article and Find Full Text PDFInt J Mol Sci
August 2025
Department of Applied Chemistry and Organic and Natural Compounds Engineering, Politehnica University Timisoara, Vasile Pârvan 6 Blvd., 300223 Timisoara, Romania.
This paper explores a synthetic pathway for naphtopyrazolotriazines utilizing amines as versatile starting materials. The approach leverages the reactivity of amines to construct the triazine core, fused with naphtho and pyrazolo cycles, through a series of controlled diazo coupling and cyclization reactions. By employing amines, this method allows for the introduction of varied substituents, enabling the tailoring of electronic and steric properties to suit specific potential applications.
View Article and Find Full Text PDFOrg Lett
September 2025
Department of Green Energy and Technology, Pondicherry University, Pondicherry 605014, India.
A discovery of the quadruple relay process by merging carbene insertive epoxide ring opening, semipinacol rearrangement, decarbonylation, and Paal-Knorr cyclization reactions to produce highly functionalized furans using chalcone epoxides and diazo compounds has been disclosed for the first time. This unprecedented novel process also produced a variety of α-aryl-β-ketomalonates in high yields with very good functional group tolerance. Interestingly, this novel domino process creates three consecutive bonds (two C-C bonds and one C-O bond) during the furan ring construction.
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