Evaluation of aromatic radiobromination by nucleophilic substitution using diaryliodonium salt precursors
Abstract
Radiobromine‐labeled compounds can be used for positron emission tomography (PET) imaging (ie, 76 Br) and for radiation therapy (ie, 77 Br). However, the commonly used electrophilic substitution reaction using no‐carrier‐added radiobromide does not always afford the desired product due to the high reactivity of the brominating intermediate. A nucleophilic substitution by bromide, such as radiobromination of iodonium precursors, provides an alternative route for the synthesis of bromo‐radiopharmaceuticals. The applicability of aromatic radiobromination by nucleophilic substitution using diaryliodonium salt precursors was evaluated using iodonium model compounds and [ 76 Br]/[ 77 Br]bromide. Radiobromination was observed under all conditions tested, in up to quantitative yields. A QMA cartridge treatment method and a base‐free method have been developed, and no extra base is needed for either methods. The base‐free conditions are mild and afford much cleaner reactions. Up to 20% water is tolerated in the reactions without reducing the radiochemical yields. No‐carrier‐added and carrier‐added reactions afforded similar results. 4‐Bromobenzaldehyde and 4‐bromobenzoate have been radiosynthesized reliably and in good yields. These results indicate that this method is robust and efficient and thus will provide a route for radiobromination of electron‐deficient arenes and an alternative route for the synthesis of bromo‐radiopharmaceuticals for biological evaluations.
- Authors:
-
[1];
- Washington Univ., St. Louis, MO (United States)
- Univ. of Illinois at Urbana-Champaign, IL (United States)
- Publication Date:
- Research Org.:
- Washington Univ., St. Louis, MO (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); National Institutes of Health (NIH)
- OSTI Identifier:
- 1533183
- Alternate Identifier(s):
- OSTI ID: 1401796
- Grant/Contract Number:
- SC0008432; CA025836
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Labelled Compounds and Radiopharmaceuticals
- Additional Journal Information:
- Journal Volume: 60; Journal Issue: 9; Journal ID: ISSN 0362-4803
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 60 APPLIED LIFE SCIENCES; biochemistry & molecular biology; pharmacology & pharmacy; chemistry; Auger electron radiation; bromine-76; bromine-77; diaryliodonium salts; labeling methods; PET imaging; radiobromination
Citation Formats
Zhou, Dong, Kim, Sung Hoon, Chu, Wenhua, Voller, Thomas, and Katzenellenbogen, John A. Evaluation of aromatic radiobromination by nucleophilic substitution using diaryliodonium salt precursors. United States: N. p., 2017.
Web. doi:10.1002/jlcr.3519.
Zhou, Dong, Kim, Sung Hoon, Chu, Wenhua, Voller, Thomas, & Katzenellenbogen, John A. Evaluation of aromatic radiobromination by nucleophilic substitution using diaryliodonium salt precursors. United States. https://doi.org/10.1002/jlcr.3519
Zhou, Dong, Kim, Sung Hoon, Chu, Wenhua, Voller, Thomas, and Katzenellenbogen, John A. Wed .
"Evaluation of aromatic radiobromination by nucleophilic substitution using diaryliodonium salt precursors". United States. https://doi.org/10.1002/jlcr.3519. https://www.osti.gov/servlets/purl/1533183.
@article{osti_1533183,
title = {Evaluation of aromatic radiobromination by nucleophilic substitution using diaryliodonium salt precursors},
author = {Zhou, Dong and Kim, Sung Hoon and Chu, Wenhua and Voller, Thomas and Katzenellenbogen, John A.},
abstractNote = {Radiobromine‐labeled compounds can be used for positron emission tomography (PET) imaging (ie, 76 Br) and for radiation therapy (ie, 77 Br). However, the commonly used electrophilic substitution reaction using no‐carrier‐added radiobromide does not always afford the desired product due to the high reactivity of the brominating intermediate. A nucleophilic substitution by bromide, such as radiobromination of iodonium precursors, provides an alternative route for the synthesis of bromo‐radiopharmaceuticals. The applicability of aromatic radiobromination by nucleophilic substitution using diaryliodonium salt precursors was evaluated using iodonium model compounds and [ 76 Br]/[ 77 Br]bromide. Radiobromination was observed under all conditions tested, in up to quantitative yields. A QMA cartridge treatment method and a base‐free method have been developed, and no extra base is needed for either methods. The base‐free conditions are mild and afford much cleaner reactions. Up to 20% water is tolerated in the reactions without reducing the radiochemical yields. No‐carrier‐added and carrier‐added reactions afforded similar results. 4‐Bromobenzaldehyde and 4‐bromobenzoate have been radiosynthesized reliably and in good yields. These results indicate that this method is robust and efficient and thus will provide a route for radiobromination of electron‐deficient arenes and an alternative route for the synthesis of bromo‐radiopharmaceuticals for biological evaluations.},
doi = {10.1002/jlcr.3519},
journal = {Journal of Labelled Compounds and Radiopharmaceuticals},
number = 9,
volume = 60,
place = {United States},
year = {Wed May 17 00:00:00 EDT 2017},
month = {Wed May 17 00:00:00 EDT 2017}
}
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