AI Article Synopsis
- Aryliodonium salts are effective precursors for creating (18) F-labeled nuclear imaging tracers, but their reactivity with heavy halides like radioiodide and astatide is not well understood.
- A study discovered that astatide is more reactive than iodide in radiohalogenation, which contradicts previous halogen reactivity trends.
- Kinetic analysis and quantum calculations showed different activation energies for iodide and astatide reactions, with astatination occurring via a monomeric iodonium complex, suggesting aryliodonium salts could be better alternatives to stannane chemistry for heavy radiohalogen labeling in nuclear medicine.
Article Abstract
Aryliodonium salts have become precursors of choice for the synthesis of (18) F-labeled tracers for nuclear imaging. However, little is known on the reactivity of these compounds with heavy halides, that is, radioiodide and astatide, at the radiotracer scale. In the first comparative study of radiohalogenation of aryliodonium salts with (125) I(-) and (211) At(-) , initial experiments on a model compound highlight the higher reactivity of astatide compared to iodide, which could not be anticipated from the trends previously observed within the halogen series. Kinetic studies indicate a significant difference in activation energy (Ea =23.5 and 17.1 kcal mol(-1) with (125) I(-) and (211) At(-) , respectively). Quantum chemical calculations suggest that astatination occurs via the monomeric form of an iodonium complex whereas iodination occurs via a heterodimeric iodonium intermediate. The good to excellent regioselectivity of halogenation and high yields achieved with diversely substituted aryliodonium salts indicate that this class of compounds is a promising alternative to the stannane chemistry currently used for heavy radiohalogen labeling of tracers in nuclear medicine.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5013196 | PMC |
| http://dx.doi.org/10.1002/chem.201600922 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Development of the P-Arylation of Dithieno[3,2-b : 2',3'-d]phosphole with Aryl Iodonium Salts.
Chempluschem
July 2023
Department of Chemistry, York University, 4700 Keele Street, Toronto, ON M3J 1P3, Canada.
P-Arylation of dithieno[3,2-b : 2',3'-d]phosphole toward cationic phenyl phospholium species using diaryliodonium reagents was explored. Multiple conditions were tested to optimize the reaction, including variation of solvent, temperature, stoichiometry, time, and aryliodonium species employed. Initial use of diphenyliodonium chloride led to an unexpected dithienophosphole Cu(I) chloride complex that was characterized crystallographically.
View Article and Find Full Text PDFFate of bis-(4-tert-butyl phenyl)-iodonium under photolithography relevant irradiation and the environmental risk properties of the formed photoproducts.
Environ Sci Pollut Res Int
April 2022
Department of Chemical & Environmental Engineering, The University of Arizona, 1133 James E. Rogers Way, P.O. Box 210011, Tucson, AZ, 85721, USA.
Aryl-iodonium salts are utilized as photoacid generators (PAGs) in semiconductor photolithography and other photo-initiated manufacturing processes. Despite their utilization and suspected toxicity, the fate of these compounds within the perimeter of semiconductor fabrication plants is inadequately understood; the identification of photolithography products is still needed for a comprehensive environmental impact assessment. This study investigated the photolytic transformation of a representative iodonium PAG cation, bis-(4-tert-butyl phenyl)-iodonium, under conditions simulating industrial photolithography.
View Article and Find Full Text PDFWet carbonate-promoted radical arylation of vinyl pinacolboronates with diaryliodonium salts yields substituted olefins.
Commun Chem
July 2020
Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology (Ministry of Education), Department of Chemistry, and the Graduate School at Shenzhen, Tsinghua University, 100084, Beijing, China.
Since the landmark work of Heck, Negishi and Suzuki on Pd-catalyzed crossing coupling reactions, innovative discovery of new reactions forming C-C bonds and constructing functional olefins via nonmetal catalysts remains an imperative area in organic chemistry. Herein, we report a transition-metal-free arylation method of vinyl pinacolboronates with diaryliodonium salts to form C(sp)-C(sp) bond and provide trans-arylvinylboronates. The resulting vinylboronates can further react with the remaining aryl iodides (generated from diaryliodonium salts) via Suzuki coupling to afford functional olefins, offering an efficient use of aryliodonium salts.
View Article and Find Full Text PDFCopper-catalyzed remote C-H arylation of polycyclic aromatic hydrocarbons (PAHs).
Beilstein J Org Chem
March 2020
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, 29 Wangjiang Road, Chengdu 610064, P.R. China.
The regioselective C-H arylation of substituted polycyclic aromatic hydrocarbons (PAHs) is a desired but challenging task. A copper-catalyzed C7-H arylation of 1-naphthamides has been developed by using aryliodonium salts as arylating reagents. This protocol does not need to use precious metal catalysts and tolerates wide variety of functional groups.
View Article and Find Full Text PDFAryliodonium Ylides as Novel and Efficient Additives for Radical Chemistry: Example in Camphorquinone (CQ)/Amine Based Photoinitiating Systems.
Molecules
August 2019
Institut de Science des Matériaux de Mulhouse IS2M, UMR CNRS 7361, UHA, 15 rue Jean Starcky, 68057 Mulhouse CEDEX, France.
Diaryliodonium salts are well-established compounds in free radical chemistry and are already used as photoinitiators (free radical or cationic polymerization), but the presence of counter anions is a strong drawback. Indeed, a counter anion is always required (e.g.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!