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Fluorinated organic molecules constitute compounds with well-known and potential applications in the chemical industry and many related areas. Accordingly, the synthesis of fluorinated compounds has emerged as one of the central tasks of modern organic synthesis. As valuable and versatile synthons, enaminones have displayed amazingly broad application in the designation of novel organic reactions. Notably, the reactions of enaminones with fluorine reagents for the synthesis of fluoro-functionalized products have undergone important advances, providing useful and practical access to various fluorinated compounds. In this review, we summarize for the first time the state of the art in the fluoro-functionalized reactions of enaminones for the synthesis of fluoro-functionalized molecules, in the category of key transformation modes of enaminones, including C-F bond functionalization, C-C bond functionalization, and cascade annulation, covering works reported since 2017.
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http://dx.doi.org/10.1039/d5cc04020e | DOI Listing |
Org Lett
September 2025
Henan Provincial Engineering and Technology Research Center for Precise Synthesis of Fluorine-Containing Drugs. College of Chemistry and Chemical Engineering, Anyang Normal University, Anyang, 455000, P. R. China.
In this work, we report a novel I-mediated ring-opening -difunctionalization of cyclopropyl alcohols with enaminones for the first time. The selective [3 + 2] annulation instead of [3 + 3] annulation under metal-free conditions enables a straightforward and efficient synthesis of structurally important 2,4-diacylpyrroles. Notably, this methodology dispenses with metal catalysts, proceeds under mild reaction conditions, and features not only simple operation but also suitability for gram-scale preparation and late-stage functionalization of complex bioactive molecules.
View Article and Find Full Text PDFOrg Lett
September 2025
Jiangxi Province Key Laboratory of Natural and Biomimetic Drugs Research, College of Chemistry and Materials, Jiangxi Normal University, Nanchang 330022, China.
The annulation reaction of β-methyl enaminones with alkynones leading to the synthesis of methylene-functionalized 1,2-dihydropyridines (1,2-DHPs) has been realized. In the presence of only CsCO, 1,2-DHPs have been synthesized with a broad scope and generally high efficiency via the novel transformation of the γ-C(sp)-H bond in enaminones. In addition, the application of the method has been demonstrated by the one-step transformation of the 1,2-DHP products into fused tricyclic scaffolds featuring an indole-pyridine hybrid via dual C-H activation.
View Article and Find Full Text PDFJ Org Chem
August 2025
Jiangsu Key Lab of Green Synthetic Chemistry for Functional Materials, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu 221116, P. R. China.
An NHC (N-heterocyclic carbene) catalyzed [3 + 3] annulation of δ-acetoxy allenoates and enaminones has been developed. This strategy provides a facile and convenient approach for the synthesis of 1,4-dihydropyridine and 3,4-dihydropyridine-based hexahydroquinoline derivatives (51 examples, up to 77% yield). This protocol features a broad substrate scope, good functional group tolerance, and mild reaction conditions.
View Article and Find Full Text PDFChem Commun (Camb)
August 2025
College of Chemistry and Materials, Jiangxi Normal University, Nanchang 330022, China.
Fluorinated organic molecules constitute compounds with well-known and potential applications in the chemical industry and many related areas. Accordingly, the synthesis of fluorinated compounds has emerged as one of the central tasks of modern organic synthesis. As valuable and versatile synthons, enaminones have displayed amazingly broad application in the designation of novel organic reactions.
View Article and Find Full Text PDFOrg Biomol Chem
August 2025
Key Laboratory of Medicinal Chemistry for Natural Resources, Ministry of Education, Yunnan Key Laboratory of Research and Development for Natural Products, Yunnan Characteristic Plant Extraction Laboratory, School of Pharmacy, Yunnan University, Kunming, 650500, P. R. China.
A simple, exogenous-base-free, and NBS-mediated -selenocyanation/cyclization reaction of enaminones with KSeCN under mild conditions has been developed, providing a facile synthetic route to 2-aminoselenazole products. This efficient protocol is postulated to proceed an initial NBS-oxidated polarity reversal of the reactive SeCN anion to form -selenocyanosuccinimide as an electrophilic selenium source, which can induce the -selenocyanation of enaminones and enamino esters, followed by a nucleophilic cyclization promoted by the generated HBr.
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