Development of Customized [18F]Fluoride Elution Techniques for the Enhancement of Copper-Mediated Late-Stage Radiofluorination

Mossine, Andrew V.; Brooks, Allen F.; Ichiishi, Naoko; Makaravage, Katarina J.; Sanford, Melanie S.; Scott, Peter J.  H.

doi:10.1038/s41598-017-00110-1

Title: Development of Customized [18F]Fluoride Elution Techniques for the Enhancement of Copper-Mediated Late-Stage Radiofluorination

Journal Article · Wed Mar 22 00:00:00 EDT 2017 · Scientific Reports

DOI:https://doi.org/10.1038/s41598-017-00110-1· OSTI ID:1425386

^[1]; Brooks, Allen F. ^[1]; Ichiishi, Naoko ^[2]; Makaravage, Katarina J. ^[2]; Sanford, Melanie S. ^[2]; Scott, Peter J. H. ^[3]

Univ. of Michigan Medical School, Ann Arbor, MI (United States). Dept. of Radiology
Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemistry
Univ. of Michigan Medical School, Ann Arbor, MI (United States). Dept. of Radiology and Interdepartmental Program in Medicinal Chemistry

In a relatively short period of time, transition metal-mediated radiofluorination reactions have changed the PET radiochemistry landscape. These reactions have enabled the radiofluorination of a wide range of substrates, facilitating access to radiopharmaceuticals that were challenging to synthesize using traditional fluorine-18 radiochemistry. However, the process of adapting these new reactions for automated radiopharmaceutical production has revealed limitations in fitting them into the confines of traditional radiochemistry systems. In particular, the presence of bases (e.g. K₂CO₃) and/or phase transfer catalysts (PTC) (e.g. kryptofix 2.2.2) associated with fluorine-18 preparation has been found to be detrimental to reaction yields. We hypothesized that these limitations could be addressed through the development of alternate techniques for preparing [18F]fluoride. This approach also opens the possibility that an eluent can be individually tailored to meet the specific needs of a metal-catalyzed reaction of interest. In this communication, we demonstrate that various solutions of copper salts, bases, and ancillary ligands can be utilized to elute [¹⁸F]fluoride from ion exchange cartridges. The new procedures we present here are effective for fluorine-18 radiochemistry and, as proof of concept, have been used to optimize an otherwise base-sensitive copper-mediated radiofluorination reaction.

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Research Organization:: Univ. of Michigan, Ann Arbor, MI (United States)

Sponsoring Organization:: USDOE; National Institutes of Health (NIH); Merck and Company, Inc., Kenilworth, NJ (United States)

Grant/Contract Number:: SC0012484; R01EB021155

OSTI ID:: 1425386

Journal Information:: Scientific Reports, Vol. 7, Issue 1; ISSN 2045-2322

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 42 works

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References (46)

Standardization of fluorine-18 manufacturing processes: New scientific challenges for PET Hjelstuen, Ole K.; Svadberg, Anders; Olberg, Dag E. European Journal of Pharmaceutics and Biopharmaceutics, Vol. 78, Issue 3 https://doi.org/10.1016/j.ejpb.2011.01.002	journal	August 2011
Enhanced copper-mediated ¹⁸ F-fluorination of aryl boronic esters provides eight radiotracers for PET applications Preshlock, Sean; Calderwood, Samuel; Verhoog, Stefan Chemical Communications, Vol. 52, Issue 54 https://doi.org/10.1039/C6CC03295H	journal	January 2016
Copper-Mediated Aromatic Radiofluorination Revisited: Efficient Production of PET Tracers on a Preparative Scale Zlatopolskiy, Boris D.; Zischler, Johannes; Krapf, Philipp Chemistry - A European Journal, Vol. 21, Issue 15 https://doi.org/10.1002/chem.201405586	journal	February 2015
Late-Stage Fluorination: From Fundamentals to Application Campbell, Michael G.; Ritter, Tobias Organic Process Research & Development, Vol. 18, Issue 4 https://doi.org/10.1021/op400349g	journal	March 2014
Fluorine-18 Radiochemistry, Labeling Strategies and Synthetic Routes Jacobson, Orit; Kiesewetter, Dale O.; Chen, Xiaoyuan Bioconjugate Chemistry, Vol. 26, Issue 1 https://doi.org/10.1021/bc500475e	journal	December 2014
A General Copper-Mediated Nucleophilic ¹⁸ F Fluorination of Arenes Tredwell, Matthew; Preshlock, Sean M.; Taylor, Nicholas J. Angewandte Chemie International Edition, Vol. 53, Issue 30 https://doi.org/10.1002/anie.201404436	journal	June 2014
Concerted nucleophilic aromatic substitution with 19F− and 18F− Neumann, Constanze N.; Hooker, Jacob M.; Ritter, Tobias Nature, Vol. 534, Issue 7607 https://doi.org/10.1038/nature17667	journal	May 2016
Titania-Catalyzed Radiofluorination of Tosylated Precursors in Highly Aqueous Medium Sergeev, Maxim E.; Morgia, Federica; Lazari, Mark Journal of the American Chemical Society, Vol. 137, Issue 17 https://doi.org/10.1021/jacs.5b02659	journal	April 2015
Automated synthesis of 4-[18F]fluoroanisole, [18F]DAA1106 and 4-[18F]FPhe using Cu-mediated radiofluorination under “minimalist” conditions Zischler, Johannes; Krapf, Philipp; Richarz, Raphael Applied Radiation and Isotopes, Vol. 115 https://doi.org/10.1016/j.apradiso.2016.04.030	journal	September 2016
Copper-Mediated Radiofluorination of Arylstannanes with [ ¹⁸ F]KF Makaravage, Katarina J.; Brooks, Allen F.; Mossine, Andrew V. Organic Letters, Vol. 18, Issue 20 https://doi.org/10.1021/acs.orglett.6b02911	journal	October 2016
Facile Nucleophilic Fluorination Reactions Using tert -Alcohols as a Reaction Medium: Significantly Enhanced Reactivity of Alkali Metal Fluorides and Improved Selectivity Kim, Dong Wook; Lim, Seok Tae The Journal of Organic Chemistry, Vol. 73, Issue 3 https://doi.org/10.1021/jo7021229	journal	February 2008
¹⁸ F-Labeling of Arenes and Heteroarenes for Applications in Positron Emission Tomography Preshlock, Sean; Tredwell, Matthew; Gouverneur, Véronique Chemical Reviews, Vol. 116, Issue 2 https://doi.org/10.1021/acs.chemrev.5b00493	journal	January 2016
Fast Production of Highly Reactive No-Carrier-Added [ ¹⁸ F]Fluoride for the Labeling of Radiopharmaceuticals Lemaire, Christian F.; Aerts, Joël J.; Voccia, Samuel Angewandte Chemie International Edition, Vol. 49, Issue 18 https://doi.org/10.1002/anie.200906341	journal	April 2010
Switching Reversibility to Irreversibility in Glycogen Synthase Kinase 3 Inhibitors: Clues for Specific Design of New Compounds Perez, Daniel I.; Palomo, Valle; Pérez, Concepción Journal of Medicinal Chemistry, Vol. 54, Issue 12 https://doi.org/10.1021/jm1016279	journal	June 2011
Late-Stage Fluorination: Fancy Novelty or Useful Tool? Neumann, Constanze N.; Ritter, Tobias Angewandte Chemie International Edition, Vol. 54, Issue 11 https://doi.org/10.1002/anie.201410288	journal	February 2015
Fast and Easy Drying Method for the Preparation of Activated [ ¹⁸ F]Fluoride Using Polymer Cartridge Seo, Jai-Woong; Lee, Byoung-Se; Lee, Sang-Ju Bulletin of the Korean Chemical Society, Vol. 32, Issue 1 https://doi.org/10.5012/bkcs.2011.32.1.71	journal	January 2011
Enantioselective Radiosynthesis of Positron Emission Tomography (PET) Tracers Containing [ ¹⁸ F]Fluorohydrins Graham, Thomas J. A.; Lambert, R. Frederick; Ploessl, Karl Journal of the American Chemical Society, Vol. 136, Issue 14 https://doi.org/10.1021/ja5025645	journal	February 2014
Synthesis of [ ¹⁸ F]Arenes via the Copper-Mediated [ ¹⁸ F]Fluorination of Boronic Acids Mossine, Andrew V.; Brooks, Allen F.; Makaravage, Katarina J. Organic Letters, Vol. 17, Issue 23 https://doi.org/10.1021/acs.orglett.5b02875	journal	November 2015
Oxalic Acid Supported Si– ¹⁸ F-Radiofluorination: One-Step Radiosynthesis of N -Succinimidyl 3-(Di- tert -butyl[ ¹⁸ F]fluorosilyl)benzoate ([ ¹⁸ F]SiFB) for Protein Labeling Kostikov, Alexey P.; Chin, Joshua; Orchowski, Katy Bioconjugate Chemistry, Vol. 23, Issue 1 https://doi.org/10.1021/bc200525x	journal	December 2011
Automation for Optimised Production of Fluorine-18-Labelled Radiopharmaceuticals I. Sachinidis, John; Poniger, Stan; J. Tochon-Danguy, Henri Current Radiopharmaceuticalse, Vol. 3, Issue 3 https://doi.org/10.2174/1874471011003030248	journal	July 2010
Optimization studies concerning the direct nucleophilic fluorination of butyrophenone neuroleptics Katsifis, A.; Hamacher, K.; Schnitter, J. Applied Radiation and Isotopes, Vol. 44, Issue 7 https://doi.org/10.1016/0969-8043(93)90005-U	journal	July 1993
Preparation of N.C.A. [17-18F]-fluoroheptadecanoic acid in high yields via aminopolyether supported, nucleophilic fluorination Coenen, Heinrich Hubert; Schüller, Manfred; Stöcklin, Gerhard Journal of Labelled Compounds and Radiopharmaceuticals, Vol. 23, Issue 5 https://doi.org/10.1002/jlcr.2580230502	journal	May 1986
N.C.A. [18F]-labelling of aliphatic compounds in high yields via aminopolyether - supported nucleophilic substitution Block, Dirk; Klatte, Bernd; Knöchel, Arndt Journal of Labelled Compounds and Radiopharmaceuticals, Vol. 23, Issue 5 https://doi.org/10.1002/jlcr.2580230503	journal	May 1986
Synthesis of α-bromocarbonyl compounds: recent advances Vekariya, Rajesh H.; Patel, Hitesh D. Tetrahedron, Vol. 70, Issue 26 https://doi.org/10.1016/j.tet.2014.04.027	journal	July 2014
Cu(OTf) ₂ -Mediated Fluorination of Aryltrifluoroborates with Potassium Fluoride Ye, Yingda; Schimler, Sydonie D.; Hanley, Patrick S. Journal of the American Chemical Society, Vol. 135, Issue 44 https://doi.org/10.1021/ja408607r	journal	October 2013
Moving Metal-Mediated ¹⁸ F-Fluorination from Concept to Clinic Sanford, Melanie S.; Scott, Peter J. H. ACS Central Science, Vol. 2, Issue 3 https://doi.org/10.1021/acscentsci.6b00061	journal	March 2016
An Efficient Method for Enhancing the Reactivity and Flexibility of [ ¹⁸ F]Fluoride Towards Nucleophilic Substitution Using Tetraethylammonium Bicarbonate : Enhanced Method for the Preparation of [ Brichard, Laurent; Aigbirhio, Franklin I. European Journal of Organic Chemistry, Vol. 2014, Issue 28 https://doi.org/10.1002/ejoc.201402587	journal	August 2014
A Philosophy for CNS Radiotracer Design Van de Bittner, Genevieve C.; Ricq, Emily L.; Hooker, Jacob M. Accounts of Chemical Research, Vol. 47, Issue 10 https://doi.org/10.1021/ar500233s	journal	September 2014
High Yielding [ ¹⁸ F]Fluorination Method by Fine Control of the Base Lee, Sang-Ju; Oh, Seung-Jun; Chi, Dae-Yoon Bulletin of the Korean Chemical Society, Vol. 33, Issue 7 https://doi.org/10.5012/bkcs.2012.33.7.2177	journal	July 2012
Synthesis, radiofluorination and first evaluation of (±)-[ ¹⁸ F]MDL 100907 as serotonin 5-HT _2A receptor antagonist for PET Mühlhausen, Ute; Ermert, Johannes; Herth, Matthias M. Journal of Labelled Compounds and Radiopharmaceuticals, Vol. 52, Issue 1 https://doi.org/10.1002/jlcr.1563	journal	January 2009
Radiofluorination of diaryliodonium tosylates under aqueous–organic and cryptand-free conditions Chun, Joong-Hyun; Telu, Sanjay; Lu, Shuiyu Organic & Biomolecular Chemistry, Vol. 11, Issue 31 https://doi.org/10.1039/c3ob40742j	journal	January 2013
Total Radiosynthesis: Thinking Outside ‘the Box' Liang, Steven H.; Vasdev, Neil Australian Journal of Chemistry, Vol. 68, Issue 9 https://doi.org/10.1071/CH15406	journal	January 2015
Targeted Fluorination with the Fluoride Ion by Manganese-Catalyzed Decarboxylation Huang, Xiongyi; Liu, Wei; Hooker, Jacob M. Angewandte Chemie International Edition, Vol. 54, Issue 17 https://doi.org/10.1002/anie.201500399	journal	March 2015
Late Stage Benzylic C–H Fluorination with [ ¹⁸ F]Fluoride for PET Imaging Huang, Xiongyi; Liu, Wei; Ren, Hong Journal of the American Chemical Society, Vol. 136, Issue 19 https://doi.org/10.1021/ja5039819	journal	May 2014
Use of Bromine and Bromo-Organic Compounds in Organic Synthesis Saikia, Indranirekha; Borah, Arun Jyoti; Phukan, Prodeep Chemical Reviews, Vol. 116, Issue 12 https://doi.org/10.1021/acs.chemrev.5b00400	journal	May 2016
Chemistry with [18F]Fluoride Ion Cai, Lisheng; Lu, Shuiyu; Pike, Victor W. European Journal of Organic Chemistry, Vol. 2008, Issue 17 https://doi.org/10.1002/ejoc.200800114	journal	June 2008
A General Copper-Mediated Nucleophilic ¹⁸ F Fluorination of Arenes Tredwell, Matthew; Preshlock, Sean M.; Taylor, Nicholas J. Angewandte Chemie, Vol. 126, Issue 30 https://doi.org/10.1002/ange.201404436	journal	June 2014
Targeted Fluorination with the Fluoride Ion by Manganese-Catalyzed Decarboxylation Huang, Xiongyi; Liu, Wei; Hooker, Jacob M. Angewandte Chemie, Vol. 127, Issue 17 https://doi.org/10.1002/ange.201500399	journal	March 2015
Fast Production of Highly Reactive No-Carrier-Added [ ¹⁸ F]Fluoride for the Labeling of Radiopharmaceuticals Lemaire, Christian F.; Aerts, Joël J.; Voccia, Samuel Angewandte Chemie, Vol. 122, Issue 18 https://doi.org/10.1002/ange.200906341	journal	April 2010
A new procedure for labeling alkylbenzenes with [18F]fluoride Hwang, Dah-Ren; Dence, Carmen S.; Gong, Jialing International Journal of Radiation Applications and Instrumentation. Part A. Applied Radiation and Isotopes, Vol. 42, Issue 11 https://doi.org/10.1016/0883-2889(91)90008-o	journal	January 1991
Improved synthesis of [18F]4-fluorophenacyl bromide: The use of polymer supported perbromide Dence, Carmen S.; McCarthy, Timothy J.; Welch, Michael J. Applied Radiation and Isotopes, Vol. 44, Issue 6 https://doi.org/10.1016/0969-8043(93)90054-e	journal	June 1993
Evaluation of fluorine-18-labeled alkylating agents as potential synthons for the labeling of oligonucleotides de Vries, Erik F. J.; Vroegh, Joke; Elsinga, Philip H. Applied Radiation and Isotopes, Vol. 58, Issue 4 https://doi.org/10.1016/s0969-8043(03)00022-8	journal	April 2003
Neither azeotropic drying, nor base nor other additives: a minimalist approach to ¹⁸ F-labeling Richarz, R.; Krapf, P.; Zarrad, F. Org. Biomol. Chem., Vol. 12, Issue 40 https://doi.org/10.1039/c4ob01336k	journal	January 2014
Late-stage [ ¹⁸ F]fluorination: new solutions to old problems Brooks, Allen F.; Topczewski, Joseph J.; Ichiishi, Naoko Chem. Sci., Vol. 5, Issue 12 https://doi.org/10.1039/c4sc02099e	journal	January 2014
Green approaches to late-stage fluorination: radiosyntheses of ¹⁸ F-labelled radiopharmaceuticals in ethanol and water Stewart, Megan N.; Hockley, Brian G.; Scott, Peter J. H. Chemical Communications, Vol. 51, Issue 79 https://doi.org/10.1039/c5cc05919d	journal	January 2015
Cryptate mediated nucleophilic 18F-fluorination without azeotropic drying Wessmann, S. H.; Henriksen, G.; Wester, H. -J. Nuklearmedizin, Vol. 50, Issue 1 https://doi.org/10.3413/nukmed-0425-11-08	journal	October 2011

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An azeotropic drying-free approach for copper-mediated radiofluorination without addition of base Zhang, Xiang; Basuli, Falguni; Swenson, Rolf E. Journal of Labelled Compounds and Radiopharmaceuticals, Vol. 62, Issue 3 https://doi.org/10.1002/jlcr.3705	journal	February 2019
A Design of Experiments (DoE) Approach Accelerates the Optimization of Copper-Mediated 18F-Fluorination Reactions of Arylstannanes Bowden, Gregory D.; Pichler, Bernd J.; Maurer, Andreas Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-019-47846-6	journal	August 2019
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C–H ¹⁸ F-fluorination of 8-methylquinolines with Ag[ ¹⁸ F]F Lee, So Jeong; Brooks, Allen F.; Ichiishi, Naoko Chemical Communications, Vol. 55, Issue 20 https://doi.org/10.1039/c9cc00641a	journal	January 2019
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One-pot synthesis of high molar activity 6-[ ¹⁸ F]fluoro- l -DOPA by Cu-mediated fluorination of a BPin precursor Mossine, Andrew V.; Tanzey, Sean S.; Brooks, Allen F. Organic & Biomolecular Chemistry, Vol. 17, Issue 38 https://doi.org/10.1039/c9ob01758e	journal	January 2019
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