- Unexpected Behavior of the Heaviest Halogen Astatine in the Nucleophilic Substitution of Aryliodonium Salts
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Aryliodonium salts have become precursors of choice for the synthesis of18F-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 with125I?and211At?, 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?1with125I?and211At?, 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.
- Guérard, Fran?ois,Lee, Yong-Sok,Baidoo, Kwamena,Gestin, Jean-Fran?ois,Brechbiel, Martin W.
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supporting information
p. 12332 - 12339
(2016/08/24)
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- The electrosynthesis of diaryliodonium salts
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A simple, one-step procedure for the synthesis of diaryliodonium salts is described. It is shown that the electrochemical oxidation of an aryl iodide at a carbon felt anode in acetic acid/25% acetic anhydride/5% sulfuric acid in the presence of an arene leads to a diaryliodonium salt in good yield. The method allows the preparation of unsymmetrical, as well as symmetrical diaryliodonium salts. (C) 2000 Elsevier Science Ltd.
- Peacock,Pletcher
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p. 8995 - 8998
(2007/10/03)
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