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A visible-light-induced β-acyl difunctionalization of alkenes with acyl oxime esters and various nucleophiles was developed to achieve molecular complexity from readily available raw materials via oxidative radical-polar crossover. A variety of nucleophiles, including H-sulfoximines, indoles, indazole, and trimethoxybenzene, were all effectively applicable to the sustainable reaction system. The novel synthetic strategy features mild reaction conditions, a broad substrate scope (39 examples), easy scale-up, and excellent regioselectivity.
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http://dx.doi.org/10.1021/acs.orglett.3c03121 | DOI Listing |
J Org Chem
September 2025
College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. China.
1,3-difunctionalized skeletons are important feedstocks and frequently appear in pharmaceuticals. However, effective and straightforward approaches to these scaffolds remain challenging. Herein, we reported a mild and efficient strategy for 1,3-hydroxyiodation, employing molecular iodine as both the promoter and iodinating agent.
View Article and Find Full Text PDFOrg Lett
September 2025
Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, State Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan, Hubei 430079
Structurally diverse 1,2-sulfinate-sulfonate esters are shown to be conveniently prepared through visible light-induced sulfonation and sulfinylation of difunctionalized alkenes using alcohols and NaHSO. The reactions proceed under mild conditions in the presence of photocatalysts and HCOH as an additive, exhibiting good functional group tolerance and a broad scope. Furthermore, this method is scalable and has been successfully applied to synthesize 1,2-disulfonic acid esters.
View Article and Find Full Text PDFOrg 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 Biomol Chem
September 2025
Department of Medicinal Chemistry, Institute of Medical Sciences, Banaras Hindu University, Varanasi-221005, India.
The stereoselective formation of glycosidic bonds remains a key challenge in carbohydrate chemistry, with far-reaching implications for glycoscience, drug development, and materials research. We report a novel method for glycosylation of glycal-derived substrates mediated by Ru(II) catalysis. Glycosylation selectivity is modulated by the presence or absence of external nucleophiles in the reaction medium.
View Article and Find Full Text PDFNat Chem
September 2025
The Institute for Advanced Studies, TaiKang Center for Life and Medical Sciences, State Key Laboratory of Metabolism and Regulation in Complex Organisms, Wuhan University, Wuhan, China.
Precision in site-selective functionalization of molecules bearing multiple potentially reactive positions is a longstanding challenge in organic synthesis. Although migratory difunctionalization offers a powerful strategy for programmed functional group installation along carbon chains, its implementation with multisubstituted alkenes has been impeded by the increased complexity of site-selectivity. Here we report a head-tail carboboration of multisubstituted alkenes with exceptional site-selectivity, enabled by ligand steric exclusion in a nickel-catalysed chain-walking system.
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