β-Alkoxyketones are important building blocks in organic synthesis. By utilizing CBZ6, with an oxidative potential of -2.16 V (vs the saturated calomel electrode), as a redox-neutral photocatalyst, alkoxyacylation of olefins was accomplished under the irradiation of visible light via a cationic intermediate. It involves the addition of an acyl radical to olefin to form a radical intermediate and the following oxidation of the radical intermediate to the benzyl cationic intermediate that is captured by alkoxy anions. This process provides concise and practical access to the β-functionalized ketones.
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http://dx.doi.org/10.1021/acs.orglett.3c03583 | DOI Listing |
Acta Crystallogr C Struct Chem
February 2025
Department Chemie, Ludwig-Maximilians Universität, Butenandtstrasse 5-13 (Haus D), D-81377 München, Germany.
Acyl fluorides and acyl cations represent typical reactive intermediates in organic reactions, such as Friedel-Crafts acylation. However, the comparatively stable phenyl-substituted compounds have not been fully characterized yet, offering a promising backbone. Attempts to isolate the benzoacylium cation have only been carried out starting from the acyl chloride with weaker chloride-based Lewis acids.
View Article and Find Full Text PDFOrg Lett
January 2025
Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China.
A 1,1-hydroboration of alkynylgermanes with unique -Ge/B stereochemistry under transition-metal-free conditions is reported. Mechanistic studies suggest that a pathway involving α-boration followed by a stepwise 1,2-Ge/H shift on the intermediate structurally lies between an alkyne-Ge π complex and a typical vinyl cation. The resulting Ge/B bimetallic modules, along with a /Ge/B trimetallic variant, can be conveniently transformed into trisubstituted olefins through iterative divergent cross-coupling.
View Article and Find Full Text PDFChemistry
January 2025
Justus-Liebig Universität, Institut für Organische Chemie, Heinrich-Buff-Ring 17, 35392, Giessen, GERMANY.
Aryl diazenes, particularly azobenzenes (AB), represent a versatile class of compounds with significant historical and practical relevance, ranging from dyes to molecular machines, solar thermal and electrochemical storage. Their oxygen-substituted counterparts, azoxybenzenes (AOB), share structural similarities but have been less explored, especially in energy storage applications. This study investigates the redox properties of AOB, comparing them to AB, and evaluates their potential as redox-active materials for energy storage systems.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Department of Applied Chemistry, Anhui Province Engineering Laboratory for Green Pesticide Development and Application, and Anhui Province Key Laboratory of Crop Integrated Pest Management, Anhui Agricultural University, Hefei 230036, China.
A high-performance anionic stereogenic-at-cobalt(III) complex/oxone catalytic system was developed for various enantioselective intramolecular halocyclizations of olefins using halide salts as halogen sources, delivering structurally diverse halogenated heterocyclic compounds with outstanding stereoselectivity (up to 97 : 3 e.r.).
View Article and Find Full Text PDFSoft Matter
January 2025
School of Chemistry and University of Sydney Nano Institute, The University of Sydney, Sydney, NSW, 2006, Australia.
Self-assembly of amphiphilic molecules can take place in extremely concentrated salt solutions, such as inorganic molten salt hydrates or hydrous melts. The intermolecular interactions governing the organization of amphiphilic molecules under such extreme conditions are not yet fully understood. In this study, we investigated the specific effects of ions on the self-assembly of the non-ionic surfactant CH(OCHCH)OH (CE) under extreme salt concentrations, using calcium nitrate tetrahydrate as a reference.
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