One-pot synthesis of high molar activity 6-[18F]fluoro-l-DOPA by Cu-mediated fluorination of a BPin precursor

Mossine, Andrew V.; Tanzey, Sean S.; Brooks, Allen F.; Makaravage, Katarina J.; Ichiishi, Naoko; Miller, Jason M.; Henderson, Bradford D.; Skaddan, Marc B.; Sanford, Melanie S.; Scott, Peter J. H.

doi:10.1039/c9ob01758e

One-pot synthesis of high molar activity 6-[¹⁸F]fluoro-l-DOPA by Cu-mediated fluorination of a BPin precursor

Journal Article · Tue Sep 17 00:00:00 EDT 2019 · Organic and Biomolecular Chemistry

DOI:https://doi.org/10.1039/c9ob01758e· OSTI ID:1802363

^[1]; ^[2]; ^[3]; ^[4]; ^[4]; Miller, Jason M. ^[2]; Henderson, Bradford D. ^[3]; Skaddan, Marc B. ^[5]; ^[4]; ^[2]

Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Radiology; OSTI
Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Radiology. Dept. of Medicinal Chemistry
Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Radiology
Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemistry
AbbVie Translational Imaging, North Chicago, IL (United States)

A one-pot two-step synthesis of 6-[¹⁸F]fluoro-L-DOPA ([¹⁸F]FDOPA) has been developed involving Cu-mediated radiofluorination of a pinacol boronate ester precursor. The method is fully automated, provides [¹⁸F]FDOPA in good activity yield (104 ± 16 mCi, 6 ± 1%), excellent radiochemical purity (>99%) and high molar activity (3799 ± 2087 Ci mmol^-1), n = 3, and has been validated to produce the radiotracer for human use.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012484

OSTI ID:: 1802363

Alternate ID(s):: OSTI ID: 1562735

Journal Information:: Organic and Biomolecular Chemistry, Journal Name: Organic and Biomolecular Chemistry Journal Issue: 38 Vol. 17; ISSN 1477-0520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (39)

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
Chemistry for Positron Emission Tomography: Recent Advances in ¹¹ C-, ¹⁸ F-, ¹³ N-, and ¹⁵ O-Labeling Reactions Deng, Xiaoyun; Rong, Jian; Wang, Lu Angewandte Chemie International Edition, Vol. 58, Issue 9 https://doi.org/10.1002/anie.201805501	journal	January 2019
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
Highly Enantioselective Synthesis of No-Carrier-Added 6-[18F]Fluoro-L-dopa by Chiral Phase-Transfer Alkylation Lemaire, Christian; Gillet, Steve; Guillouet, Stéphane European Journal of Organic Chemistry, Vol. 2004, Issue 13 https://doi.org/10.1002/ejoc.200400059	journal	July 2004
Base/Cryptand/Metal-Free Automated Nucleophilic Radiofluorination of [ ¹⁸ F]FDOPA from Iodonium Salts: Importance of Hydrogen Carbonate Counterion : Base/Cryptand/Metal-Free Automated Nucleophilic Radiofluorination of [ Maisonial-Besset, Aurélie; Serre, Audrey; Ouadi, Ali European Journal of Organic Chemistry, Vol. 2018, Issue 48 https://doi.org/10.1002/ejoc.201801608	journal	December 2018
A new nucleophilic asymmetric synthesis of 6-[18F]fluoro-DOPA Tierling, T.; Hamacher, K.; Coenen, H. H. Journal of Labelled Compounds and Radiopharmaceuticals, Vol. 44, Issue S1 https://doi.org/10.1002/jlcr.2580440151	journal	May 2001
Automated production at the curie level of no-carrier-added 6-[ ¹⁸ F]fluoro- l -dopa and 2-[ ¹⁸ F]fluoro- l -tyrosine on a FASTlab synthesizer : Nca automated production of [ Lemaire, C.; Libert, L.; Franci, X. Journal of Labelled Compounds and Radiopharmaceuticals, Vol. 58, Issue 7 https://doi.org/10.1002/jlcr.3291	journal	May 2015
Automated synthesis of PET radiotracers by copper-mediated ¹⁸ F-fluorination of organoborons: Importance of the order of addition and competing protodeborylation Mossine, Andrew V.; Brooks, Allen F.; Bernard-Gauthier, Vadim Journal of Labelled Compounds and Radiopharmaceuticals, Vol. 61, Issue 3 https://doi.org/10.1002/jlcr.3583	journal	February 2018
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
Hydrophilic interaction liquid chromatography (HILIC)—a powerful separation technique Buszewski, Bogusław; Noga, Sylwia Analytical and Bioanalytical Chemistry, Vol. 402, Issue 1 https://doi.org/10.1007/s00216-011-5308-5	journal	August 2011
18F-DOPA: the versatile radiopharmaceutical Taïeb, David; Imperiale, Alessio; Pacak, Karel European Journal of Nuclear Medicine and Molecular Imaging, Vol. 43, Issue 6 https://doi.org/10.1007/s00259-016-3354-0	journal	March 2016
Remote, semiautomated production of 6-[18F]fluoro-l-dopa for human studies with PET Luxen, Andre; Perlmutter, Milton; Bida, Gerald T. International Journal of Radiation Applications and Instrumentation. Part A. Applied Radiation and Isotopes, Vol. 41, Issue 3 https://doi.org/10.1016/0883-2889(90)90191-I	journal	January 1990
Automated synthesis of n.c.a. [18F]FDOPA via nucleophilic aromatic substitution with [18F]fluoride Shen, B.; Ehrlichmann, W.; Uebele, M. Applied Radiation and Isotopes, Vol. 67, Issue 9 https://doi.org/10.1016/j.apradiso.2009.03.003	journal	September 2009
Copper-Catalyzed Aerobic Oxidations of Organic Molecules: Pathways for Two-Electron Oxidation with a Four-Electron Oxidant and a One-Electron Redox-Active Catalyst McCann, Scott D.; Stahl, Shannon S. Accounts of Chemical Research, Vol. 48, Issue 6 https://doi.org/10.1021/acs.accounts.5b00060	journal	May 2015
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
A Transmetalation Reaction Enables the Synthesis of [ ¹⁸ F]5-Fluorouracil from [ ¹⁸ F]Fluoride for Human PET Imaging Hoover, Andrew J.; Lazari, Mark; Ren, Hong Organometallics, Vol. 35, Issue 7 https://doi.org/10.1021/acs.organomet.6b00059	journal	February 2016
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
Copper-Mediated Oxidative Fluorination of Aryl Stannanes with Fluoride Gamache, Raymond F.; Waldmann, Christopher; Murphy, Jennifer M. Organic Letters, Vol. 18, Issue 18 https://doi.org/10.1021/acs.orglett.6b02125	journal	August 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
¹⁸ F-Deoxyfluorination of Phenols via Ru π-Complexes Beyzavi, M. Hassan; Mandal, Debashis; Strebl, Martin G. ACS Central Science, Vol. 3, Issue 9 https://doi.org/10.1021/acscentsci.7b00195	journal	August 2017
Aerobic Copper-Catalyzed Organic Reactions Allen, Scott E.; Walvoord, Ryan R.; Padilla-Salinas, Rosaura Chemical Reviews, Vol. 113, Issue 8 https://doi.org/10.1021/cr300527g	journal	June 2013
Modern Carbon–Fluorine Bond Forming Reactions for Aryl Fluoride Synthesis Campbell, Michael G.; Ritter, Tobias Chemical Reviews, Vol. 115, Issue 2 https://doi.org/10.1021/cr500366b	journal	August 2014
Nickel-Mediated Oxidative Fluorination for PET with Aqueous [ ¹⁸ F] Fluoride Lee, Eunsung; Hooker, Jacob M.; Ritter, Tobias Journal of the American Chemical Society, Vol. 134, Issue 42 https://doi.org/10.1021/ja3084797	journal	October 2012
Derisking the Cu-Mediated ¹⁸ F-Fluorination of Heterocyclic Positron Emission Tomography Radioligands Taylor, Nicholas J.; Emer, Enrico; Preshlock, Sean Journal of the American Chemical Society, Vol. 139, Issue 24 https://doi.org/10.1021/jacs.7b03131	journal	June 2017
Copper-Catalyzed [ ¹⁸ F]Fluorination of (Mesityl)(aryl)iodonium Salts Ichiishi, Naoko; Brooks, Allen F.; Topczewski, Joseph J. Organic Letters, Vol. 16, Issue 12 https://doi.org/10.1021/ol501243g	journal	June 2014
Dopamine visualized in the basal ganglia of living man Garnett, E. S.; Firnau, G.; Nahmias, C. Nature, Vol. 305, Issue 5930 https://doi.org/10.1038/305137a0	journal	September 1983
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
Spirocyclic hypervalent iodine(III)-mediated radiofluorination of non-activated and hindered aromatics Rotstein, Benjamin H.; Stephenson, Nickeisha A.; Vasdev, Neil Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5365	journal	July 2014
Development of Customized [18F]Fluoride Elution Techniques for the Enhancement of Copper-Mediated Late-Stage Radiofluorination Mossine, Andrew V.; Brooks, Allen F.; Ichiishi, Naoko Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-00110-1	journal	March 2017
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
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
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
Persistent hyperinsulinaemic hypoglycaemia in infancy Shah, Pratik; Demirbilek, Huseyin; Hussain, Khalid Seminars in Pediatric Surgery, Vol. 23, Issue 2 https://doi.org/10.1053/j.sempedsurg.2014.03.005	journal	April 2014
Dopamine Visualized in the Basal Ganglia of Living man Garnett, E. S.; Firnau, G.; Nahmias, C. Journal of Computer Assisted Tomography, Vol. 8, Issue 1 https://doi.org/10.1097/00004728-198402000-00054	journal	January 1984
A Fluoride-Derived Electrophilic Late-Stage Fluorination Reagent for PET Imaging Lee, E.; Kamlet, A. S.; Powers, D. C. Science, Vol. 334, Issue 6056 https://doi.org/10.1126/science.1212625	journal	November 2011
Improved GMP-compliant multi-dose production and quality control of 6-[18F]fluoro-L-DOPA Luurtsema, G.; Boersma, H. H.; Schepers, M. EJNMMI Radiopharmacy and Chemistry, Vol. 1, Issue 1 https://doi.org/10.1186/s41181-016-0009-1	journal	April 2016
Three-Step, "One-Pot" Radiosynthesis of 6-Fluoro-3,4-Dihydroxy-L-Phenylalanine by Isotopic Exchange Wagner, F. M.; Ermert, J.; Coenen, H. H. Journal of Nuclear Medicine, Vol. 50, Issue 10 https://doi.org/10.2967/jnumed.109.063297	journal	September 2009
A Practical Method for the Preparation of 18F-Labeled Aromatic Amino Acids from Nucleophilic [18F]Fluoride and Stannyl Precursors for Electrophilic Radiohalogenation Zarrad, Fadi; Zlatopolskiy, Boris; Krapf, Philipp Molecules, Vol. 22, Issue 12 https://doi.org/10.3390/molecules22122231	journal	December 2017
Aspects of 6-[18F]fluoro-L-DOPA preparation: Deuterochloroform as a substitute solvent for Freon 11 Füchtner, F.; Zessin, J.; Mäding, P. Nuklearmedizin, Vol. 47, Issue 01 https://doi.org/10.3413/nukmed-0112	journal	January 2008

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