Onium salts have proved to be efficient sources of carbon-centered radicals. They can undergo homolytic reduction by single electron transfer (SET) and participate in subsequent synthetic transformations. This review aims to provide an overview on the behavior of onium salts including diazonium, sulfonium, selenonium, telluronium, phosphonium and iodonium cations toward various reductive methods such as radiolysis, electrolysis, photolysis or the use of SET reagents. Mechanistic and synthetic aspects are presented. Applications in polymers and materials science are not covered.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.2533/chimia.2012.425 | DOI Listing |
Org Biomol Chem
January 2025
Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg, 199034, Russian Federation.
The Schiff condensation between 4-methylbenzaldehyde and 2-aminopyridine, catalyzed by chloronium, bromonium, and iodonium triflates, as well as sulfonium, selenonium, and telluronium triflates, was investigated. H NMR monitoring revealed that the catalytic activity increased significantly with heavier σ-hole-bearing heteroatoms. DFT calculations showed that the maximum electrostatic potential at the σ-hole was a more reliable predictor of the catalytic activity of these organoelement species.
View Article and Find Full Text PDFChemistry
January 2025
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, No. 381, Wushan Road, Tianhe district, Guangzhou, 510641, China.
α-Diazoesters belong to significantly important carbenoid precursors in synthetic chemistry. Diazomethylation-based difunctionalization of alkenes is highly valuable but remain nontrivial. Herein, we reported a general and modular approach for the direct 1,2-oxydiazomethylation of alkenes through visible-light photoredox catalysis.
View Article and Find Full Text PDFOrg Biomol Chem
October 2024
School of Pharmacy, Changzhou University, Changzhou, 213164, China.
Treatment of alkyl α-(-heteroaryl)-α-diazoacetates with alkylating reagents affords diazoacetate N-heteroarenium salts. These novel 'onium' diazo compounds are mostly yellow solids, displaying increased thermal and acid stability. Their tetrafluoroborates undergo rhodium catalyzed [2 + 1] and Doyle-Kirmse reactions under mild conditions, suggesting the -quaternization an effective means of elimination of -coordination caused catalyst toxicity.
View Article and Find Full Text PDFDalton Trans
August 2024
Universidad Rey Juan Carlos, Departamento de Biología y Geología, Física y Química Inorgánica, Móstoles-28933-Madrid, Spain.
New and simple ligand design strategies for the preparation of versatile metal-based catalysts capable of operating under greener and eco-friendly conditions in several industrially attractive processes are in high demand for society development. We present the first nucleophilic addition of an organolithium to ketenimines which incorporates a stereogenic centre in an N-donor atom to prepare new enantiopure NNN-donor scorpionates. We have also verified its potential utility as a valuable scaffold for chirality induction through the preparation of inexpensive, non-toxic and asymmetric zinc complexes.
View Article and Find Full Text PDFInorg Chem
August 2024
Department of Chemistry, Graduate School of Science, Kobe University, 1-1 Rokkodai, Nada, Kobe, Hyogo 657-8501, Japan.
Ionic plastic crystals (IPCs), characterized by nearly spherical molecular ions, exhibit remarkable solid-state characteristics including high ionic conductivity. However, most IPCs are organic onium salts. Incorporating organometallic half-sandwich complexes into IPCs is challenging owing to their low-symmetry structures.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!