Titania-catalyzed radiofluorination of tosylated precursors in highly aqueous medium

Sergeev, Maxim E.; Morgia, Federica; Lazari, Mark; Wang, Jr., Christopher; van Dam, R. Michael

doi:10.1021/jacs.5b02659

Title: Titania-catalyzed radiofluorination of tosylated precursors in highly aqueous medium

Journal Article · Fri Apr 10 00:00:00 EDT 2015 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5b02659· OSTI ID:1345980

Sergeev, Maxim E. ^[1]; Morgia, Federica ^[1]; Lazari, Mark ^[1]; Wang, Jr., Christopher ^[1]; van Dam, R. Michael ^[1]

David Geffen School of Medicine at Univ. of California, Los Angeles, CA (United States)

Nucleophilic radiofluorination is an efficient synthetic route to many positron-emission tomography (PET) probes, but removal of water to activate the cyclotron-produced [¹⁸F]fluoride has to be performed prior to reaction, which significantly increases overall radiolabeling time and causes radioactivity loss. In this paper, we demonstrate the possibility of ¹⁸F-radiofluorination in highly aqueous medium. The method utilizes titania nanoparticles, 1:1 (v/v) acetonitrile–thexyl alcohol solvent mixture, and tetra-n-butylammonium bicarbonate as a phase-transfer agent. Efficient radiolabeling is directly performed with aqueous [¹⁸F]fluoride without the need for a drying/azeotroping step to significantly reduce radiosynthesis time. High radiochemical purity of the target compound is also achieved. Finally, the substrate scope of the synthetic strategy is demonstrated with a range of aromatic, aliphatic, and cycloaliphatic tosylated precursors.

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Research Organization:: Univ. of California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: SC0001249

OSTI ID:: 1345980

Journal Information:: Journal of the American Chemical Society, Vol. 137, Issue 17; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 30 works

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References (58)

The Hallmarks of Cancer Hanahan, Douglas; Weinberg, Robert A. Cell, Vol. 100, Issue 1 https://doi.org/10.1016/S0092-8674(00)81683-9	journal	January 2000
Recent Developments and Trends in 18F-Radiochemistry: Syntheses and Applications Schirrmacher, Ralf; Wangler, Carmen; Schirrmacher, Esther Mini-Reviews in Organic Chemistry, Vol. 4, Issue 4 https://doi.org/10.2174/157019307782411699	journal	November 2007
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
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
Review of recent advances in nucleophilic C–F bond-forming reactions at sp3 centers Wu, Jimmy Tetrahedron Letters, Vol. 55, Issue 31 https://doi.org/10.1016/j.tetlet.2014.06.006	journal	July 2014
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
High yield and high specific activity synthesis of [ ¹⁸ F]fallypride in a batch microfluidic reactor for micro-PET imaging Javed, Muhammad Rashed; Chen, Supin; Lei, Jack Chem. Commun., Vol. 50, Issue 10 https://doi.org/10.1039/C3CC47616B	journal	January 2014
An enzymatic route to 5-deoxy-5-[18F]fluoro-d-ribose, a [ ¹⁸ F]-fluorinated sugar for PET imaging Onega, Mayca; Domarkas, Juozas; Deng, Hai Chem. Commun., Vol. 46, Issue 1 https://doi.org/10.1039/B919364B	journal	January 2010
Engineering Fluorometabolite Production: Fluorinase Expression in Salinispora tropica Yields Fluorosalinosporamide ^† Eustáquio, Alessandra S.; O’Hagan, David; Moore, Bradley S. Journal of Natural Products, Vol. 73, Issue 3 https://doi.org/10.1021/np900719u	journal	March 2010
Polymer-immobilized fluorinase: Recyclable catalyst for fluorination reactions Sergeev, Maxim E.; Morgia, Federica; Javed, Muhammad R. Journal of Molecular Catalysis B: Enzymatic, Vol. 92 https://doi.org/10.1016/j.molcatb.2013.03.009	journal	August 2013
Enzymatic radiofluorination: Fluorinase accepts methylaza-analog of SAM as substrate for FDA synthesis Sergeev, Maxim E.; Morgia, Federica; Javed, Muhammad R. Journal of Molecular Catalysis B: Enzymatic, Vol. 97 https://doi.org/10.1016/j.molcatb.2013.07.015	journal	December 2013
Application of Palladium-Mediated 18F-Fluorination to PET Radiotracer Development: Overcoming Hurdles to Translation Kamlet, Adam S.; Neumann, Constanze N.; Lee, Eunsung PLoS ONE, Vol. 8, Issue 3 https://doi.org/10.1371/journal.pone.0059187	journal	March 2013
Fluorination of Boronic Acids Mediated by Silver(I) Triflate Furuya, Takeru; Ritter, Tobias Organic Letters, Vol. 11, Issue 13 https://doi.org/10.1021/ol901113t	journal	June 2009
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
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
Titelbild: Umkodierung des genetischen Codes mit Selenocystein (Angew. Chem. 1/2014) Bröcker, Markus J.; Ho, Joanne M. L.; Church, George M. Angewandte Chemie, Vol. 126, Issue 1 https://doi.org/10.1002/ange.201310509	journal	December 2013
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
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
Radiofluorination using aluminum-fluoride (Al18F) McBride, William J.; Sharkey, Robert M.; Goldenberg, David M. EJNMMI Research, Vol. 3, Issue 1 https://doi.org/10.1186/2191-219X-3-36	journal	January 2013
Review on Modified TiO ₂ Photocatalysis under UV/Visible Light: Selected Results and Related Mechanisms on Interfacial Charge Carrier Transfer Dynamics Kumar, S. Girish; Devi, L. Gomathi The Journal of Physical Chemistry A, Vol. 115, Issue 46 https://doi.org/10.1021/jp204364a	journal	November 2011
High surface area crystalline titanium dioxide: potential and limits in electrochemical energy storage and catalysis Fröschl, T.; Hörmann, U.; Kubiak, P. Chemical Society Reviews, Vol. 41, Issue 15 https://doi.org/10.1039/c2cs35013k	journal	January 2012
Multilayer water adsorption on rutile TiO2(110): A first-principles study Zhang, Changjun; Lindan, Philip J. D. The Journal of Chemical Physics, Vol. 118, Issue 10 https://doi.org/10.1063/1.1543983	journal	March 2003
The surface science of titanium dioxide Diebold, Ulrike Surface Science Reports, Vol. 48, Issue 5-8 https://doi.org/10.1016/S0167-5729(02)00100-0	journal	January 2003
Adsorption of Water on Reconstructed Rutile TiO ₂ (011)-(2×1): TiO Double Bonds and Surface Reactivity Di Valentin, Cristiana; Tilocca, Antonio; Selloni, Annabella Journal of the American Chemical Society, Vol. 127, Issue 27 https://doi.org/10.1021/ja0511624	journal	July 2005
Water Adsorption on TiO2 Hammer, B.; Wendt, S.; Besenbacher, F. Topics in Catalysis, Vol. 53, Issue 5-6 https://doi.org/10.1007/s11244-010-9454-3	journal	February 2010
Adsorption of water and ammonia on TiO2-anatase cluster models Onal, Isik; Soyer, Sezen; Senkan, Selim Surface Science, Vol. 600, Issue 12 https://doi.org/10.1016/j.susc.2006.04.004	journal	June 2006
Striatal and extrastriatal microPET imaging of D2/D3 dopamine receptors in rat brain with [18F]fallypride and [18F]desmethoxyfallypride Constantinescu, Cristian C.; Coleman, Robert A.; Pan, Min-Liang Synapse, Vol. 65, Issue 8 https://doi.org/10.1002/syn.20904	journal	March 2011
D2/D3 dopamine receptor binding with [F-18]fallypride in thalamus and cortex of patients with schizophrenia Buchsbaum, M.; Christian, B.; Lehrer, D. Schizophrenia Research, Vol. 85, Issue 1-3 https://doi.org/10.1016/j.schres.2006.03.042	journal	July 2006
Facile S _N 2 Reaction in Protic Solvent: Quantum Chemical Analysis Oh, Young-Ho; Ahn, Doo-Sik; Chung, Sang-Yoon The Journal of Physical Chemistry A, Vol. 111, Issue 40 https://doi.org/10.1021/jp0743929	journal	October 2007
Efficient Radiosynthesis of 3′-Deoxy-3′- ¹⁸ F-Fluorothymidine Using Electrowetting-on-Dielectric Digital Microfluidic Chip Javed, Muhammad Rashed; Chen, Supin; Kim, Hee-Kwon Journal of Nuclear Medicine, Vol. 55, Issue 2 https://doi.org/10.2967/jnumed.113.121053	journal	December 2013
The adsorption and reaction of alcohols on TiO2 and Pd/TiO2 catalysts Bahruji, Hasliza; Bowker, Michael; Brookes, Catherine Applied Catalysis A: General, Vol. 454 https://doi.org/10.1016/j.apcata.2013.01.005	journal	March 2013
Self-assembled monolayers and titanium dioxide: From surface patterning to potential applications Paz, Yaron Beilstein Journal of Nanotechnology, Vol. 2 https://doi.org/10.3762/bjnano.2.94	journal	January 2011
Comparing Surface Binding of the Maleic Anhydride Anchor Group on Single Crystalline Anatase TiO ₂ (101), (100), and (001) Surfaces Johansson, E. M. J.; Plogmaker, S.; Walle, L. E. The Journal of Physical Chemistry C, Vol. 114, Issue 35 https://doi.org/10.1021/jp104897k	journal	August 2010
Effects of clustering structure on volumetric properties of amino acids in (DMSO+water) mixtures Huang, Aimin; Liu, Chunli; Ma, Lin The Journal of Chemical Thermodynamics, Vol. 49 https://doi.org/10.1016/j.jct.2012.01.015	journal	June 2012
The structure of a DMSO–water mixture from Car–Parrinello simulations Kirchner, Barbara; Hutter, Jürg Chemical Physics Letters, Vol. 364, Issue 5-6 https://doi.org/10.1016/S0009-2614(02)01377-5	journal	October 2002
The Secret of Dimethyl Sulfoxide−Water Mixtures. A Quantum Chemical Study of 1DMSO− n Water Clusters Kirchner, Barbara; Reiher, Markus Journal of the American Chemical Society, Vol. 124, Issue 21 https://doi.org/10.1021/ja017703g	journal	May 2002
Positron Annihilation in and Adiabatic Compressibility of Water-Organic Solutions. The System Water-Dimethylsulfoxide Jerie, K.; Baranowski, A.; Rozenfeld, B. Acta Physica Polonica A, Vol. 79, Issue 4 https://doi.org/10.12693/APhysPolA.79.507	journal	April 1991
Combined experimental and theoretical investigation of interactions between kaolinite inner surface and intercalated dimethyl sulfoxide Zhang, Shuai; Liu, Qinfu; Cheng, Hongfei Applied Surface Science, Vol. 331 https://doi.org/10.1016/j.apsusc.2015.01.019	journal	March 2015
Single Kaolinite Nanometer Layers Prepared by an In Situ Polymerization–Exfoliation Process in the Presence of Ionic Liquids Letaief, Sadok; Leclercq, Jérôme; Liu, Yun Langmuir, Vol. 27, Issue 24 https://doi.org/10.1021/la203492m	journal	December 2011
Effect of Fluorination on the Surface Properties of Titania P25 Powder: An FTIR Study Minella, Marco; Faga, Maria Giulia; Maurino, Valter Langmuir, Vol. 26, Issue 4 https://doi.org/10.1021/la902807g	journal	October 2009
Photocatalytic Transformation of Organic Compounds in the Presence of Inorganic Anions. 1. Hydroxyl-Mediated and Direct Electron-Transfer Reactions of Phenol on a Titanium Dioxide−Fluoride System Minero, C.; Mariella, G.; Maurino, V. Langmuir, Vol. 16, Issue 6 https://doi.org/10.1021/la9903301	journal	March 2000
Photocatalytic Transformation of Organic Compounds in the Presence of Inorganic Ions. 2. Competitive Reactions of Phenol and Alcohols on a Titanium Dioxide−Fluoride System ^† Minero, C.; Mariella, G.; Maurino, V. Langmuir, Vol. 16, Issue 23 https://doi.org/10.1021/la0005863	journal	November 2000
A Review on Adsorption of Fluoride from Aqueous Solution Habuda-Stanić, Mirna; Ravančić, Maja; Flanagan, Andrew Materials, Vol. 7, Issue 9 https://doi.org/10.3390/ma7096317	journal	September 2014
Editorial (Letter from the Editor-in-Chief of Current Radiopharmaceuticals) Kitson, Sean Current Radiopharmaceuticalse, Vol. 2, Issue 1 https://doi.org/10.2174/1874471010902010001	journal	January 2009
Micro-chemical synthesis of molecular probes on an electronic microfluidic device Keng, P. Y.; Chen, S.; Ding, H. Proceedings of the National Academy of Sciences, Vol. 109, Issue 3 https://doi.org/10.1073/pnas.1117566109	journal	December 2011
Highly efficient production of [18F]fallypride using small amounts of base concentration Seok Moon, Byung; Hyung Park, Jun; Jin Lee, Hong Applied Radiation and Isotopes, Vol. 68, Issue 12 https://doi.org/10.1016/j.apradiso.2010.06.016	journal	December 2010
Fully Automated Production of Diverse 18F-Labeled PET Tracers on the ELIXYS Multireactor Radiosynthesizer Without Hardware Modification Lazari, M.; Collins, J.; Shen, B. Journal of Nuclear Medicine Technology, Vol. 42, Issue 3 https://doi.org/10.2967/jnmt.114.140392	journal	July 2014
The development of whole blood titanium levels after instrumented spinal fusion – Is there a correlation between the number of fused segments and titanium levels? Ipach, Ingmar; Schäfer, Ralf; Mittag, Falk BMC Musculoskeletal Disorders, Vol. 13, Issue 1 https://doi.org/10.1186/1471-2474-13-159	journal	August 2012
Levels of systemic metal ions in patients with intramedullary nails Patton, Michael S.; Lyon, Thomas D. B.; Ashcroft, George P. Acta Orthopaedica, Vol. 79, Issue 6 https://doi.org/10.1080/17453670810016911	journal	January 2008
Multielement analysis of whole blood by high resolution inductively coupled plasma mass spectrometry Rodushkin, I.; Ödman, Fredrik; Branth, Stefan Fresenius' Journal of Analytical Chemistry, Vol. 364, Issue 4 https://doi.org/10.1007/s002160051346	journal	June 1999
Enhanced radiosyntheses of [11C]raclopride and [11C]DASB using ethanolic loop chemistry Shao, Xia; Schnau, Paul L.; Fawaz, Maria V. Nuclear Medicine and Biology, Vol. 40, Issue 1 https://doi.org/10.1016/j.nucmedbio.2012.09.008	journal	January 2013
Kit-like 18F-labeling of RGD-19F-Arytrifluroborate in high yield and at extraordinarily high specific activity with preliminary in vivo tumor imaging Liu, Zhibo; Li, Ying; Lozada, Jerome Nuclear Medicine and Biology, Vol. 40, Issue 6 https://doi.org/10.1016/j.nucmedbio.2013.05.002	journal	August 2013
Quantification of dopamine D2/3 receptors in rat brain using factor analysis corrected [18F]Fallypride images Millet, Philippe; Moulin-Sallanon, Marcelle; Tournier, Benjamin B. NeuroImage, Vol. 62, Issue 3 https://doi.org/10.1016/j.neuroimage.2012.05.075	journal	September 2012
High-Affinity Dopamine D ₂ /D ₃ PET Radioligands ¹⁸ F-Fallypride and ¹¹ C-FLB457: A Comparison of Kinetics in Extrastriatal Regions Using a Multiple-Injection Protocol Vandehey, Nicholas T.; Moirano, Jeffrey M.; Converse, Alexander K. Journal of Cerebral Blood Flow & Metabolism, Vol. 30, Issue 5 https://doi.org/10.1038/jcbfm.2009.270	journal	December 2009
Validation of the Octamouse for Simultaneous ¹⁸ F-Fallypride Small-Animal PET Recordings from 8 Mice Rominger, Axel; Mille, Erik; Zhang, Shanshan Journal of Nuclear Medicine, Vol. 51, Issue 10 https://doi.org/10.2967/jnumed.110.078451	journal	September 2010
Fluorinated benzamide neuroleptics—III. Development of (S)-N-[(1-allyl-2-pyrrolidinyl)methyl]-5-(3-[18F]fluoropropyl)-2,3-dimethoxybenzamide as an improved dopamine D-2 receptor tracer Mukherjee, Jogeshwar; Yang, Zhi-Ying; Das, Malay K. Nuclear Medicine and Biology, Vol. 22, Issue 3 https://doi.org/10.1016/0969-8051(94)00117-3	journal	April 1995
Design and Optimization of Coin-Shaped Microreactor Chips for PET Radiopharmaceutical Synthesis Elizarov, A. M.; van Dam, R. M.; Shin, Y. S. Journal of Nuclear Medicine, Vol. 51, Issue 2, p. 282-287 https://doi.org/10.2967/jnumed.109.065946	journal	February 2010
Batch-reactor microfluidic device: first human use of a microfluidically produced PET radiotracer Lebedev, Artem; Miraghaie, Reza; Kotta, Kishore Lab Chip, Vol. 13, Issue 1 https://doi.org/10.1039/C2LC40853H	journal	January 2013

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