8.1 INTRODUCTION

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246 Handbook of Radiopharmaceuticals

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453. Roger, G., Dollé, F., De Bruin, B. etal. (2004). Radiosynthesis and pharmacological evaluation of [

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456. Brown, G.D., Luthra, S.K., Brock, C.S. etal. (2002). Antitumor imidazotetrazines.

40. 1 radiosyntheses of [4-

C-Carbonyl]- and [3-N-11C-methyl]-8-carbamoyl-3methylimidazo[5,1-d]-1,2,3,5-tetrazin-4(3H)-one (temozolomide) for positron emission tomography (PET) studies. J. Med. Chem. 45 (25): 5448–5457.

457. Kato, K., Gustavsson, S.Å., and Långström, B. (2008). Asymmetric nitroaldol reaction using nitromethane labeled with

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460. Kato, K., Zhang, M.R., Minegishi, K. etal. (2011). Nitroaldol reaction of nitro[ methane to form 2-(hydroxymethyl)-2-nitro[2-

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465. Dollé, F., Hinnen, F., Valette, H. etal. (1997). Synthesis of two optically active calcium channel antagonists labelled with carbon-11 for in vivo cardiac PET imaging. Bioorg. Med. Chem. 5 (4): 749–764.

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468. da Silva, E.S., Gómez-Vallejo, V., López-Gallego, F., and Llop, J. (2018). Biocatalysis in radiochemistry: enzymatic incorporation of PET radionuclides into molecules of biomedical interest. J. Labelled Compd. Radiopharm. 61 (4): 332–354.

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248 Handbook of Radiopharmaceuticals

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 249

Chapter 8

Fluorine-18 Radiochemistry

Allen F. Brooks

Department of Radiology, University of Michigan, Ann Arbor, MI, 48109, USA

Katarina J. Makaravage

Department of Chemistry, University of Michigan, Ann Arbor, MI, 48109, USA

Jay Wright

Department of Radiology, University of Michigan, Ann Arbor, MI, 48109, USA

Melanie S. Sanford

Department of Chemistry, University of Michigan, Ann Arbor, MI, 48109, USA

Peter J. H. Scott

Department of Radiology, University of Michigan, Ann Arbor, MI, 48109, USA

8.1 INTRODUCTION

Between the publication of the rst edition of the Handbook of Radiopharmaceuticals and this new edition, interest in uorine-18, its applications, and utilization have continued to grow. This is reected in the increasing number of publications and patents containing uorine-18 as a key feature of the work (Figure8.1). Cyclotron produced uorine-18

Handbook of Radiopharmaceuticals: Methodology and Applications, Second Edition. Edited by Michael R. Kilbourn and Peter J.H. Scott. © 2021 John Wiley & Sons Ltd. Published 2021 by John Wiley & Sons Ltd.

3500

3000

2500

2000

500

3000

2500

2000

1996 2001 2006 2011 2016

1960–2017 Publications

000

500

1960

1970 1980 1990

1997–2017 Scientific Literature Publications 1997–2017 Patents

500

000

500

Figure 8.1 Fluorine-18 scientic and patent literature. Source: Data from Scopus.

is readily available primarily from commercial nuclear pharmacies (which require it for

[

F]uorodeoxyglucose ([18F]FDG) production) and academic medical research centers, which has been a factor in this growth as more sites and researchers can start programs with smaller investments in infrastructure. Alongside this increased interest, the trend toward the utilization of nucleophilic [

like [

F]F2, has continued. This is due to the amount of high-molar-activity [18F]uoride that can be conveniently produced in easy-to-handle aqueous solutions. For example, the bulk of new methodology research and positron emission tomography (PET) tracer development with uorine-18 has utilized small medical cyclotrons to produce [ uoride ([

F]F−) via proton irradiation of [18O]H2O according to the 18O(p,n)18F nuclear reaction. New uorine-18 radiochemistry has been extensively reviewed in recent years[1–20], and this chapter will focus on highlighting key new methods utilizing [ as a reagent for the production of uorine-18 PET imaging agents.

At the time of the previous edition of the Handbook, the two main approaches to

radiolabeling with [

F]uoride were nucleophilic substitution reactions (SN2) of aliphatic compounds and nucleophilic aromatic substitution (S challenging substrates (e.g. electron-rich arenes) or molecules previously labeled with a

252 Handbook of Radiopharmaceuticals

2000 2010

700

600

500

400

300

200

100

F]F− sources such as [18F]KF, over [18F]F+ sources

Ar) of aromatic compounds. For

F]F−

carbon-11 methyl group, an alternative approach involving the use of prosthetic groups such as the [

F]uoroethyl tosylate group[21] or N-succinimidyl 4-[18F]uorobenzoate[22, 23] were employed. These approaches are still used extensively in uorine-18 radiochemistry, but they only allow for the labeling of a limited set of potential molecules of interest for study by PET imaging.

In the past 15 years, extensive work has been done to improve the chemical space

that can be labeled with uorine-18. A signicant challenge is improving the reactivity

of [

F]KF to a level comparable to reagents such as anhydrous HF and F+ sources. To facilitate this, many productive collaborations between radiochemists and organometallic chemists have developed, and the results have disrupted many of the established notions, dogma, and limitations of uorine-18 chemistry previously accepted.

 

A standard procedure is often undertaken to process [18F]uoride obtained as a solution

in [

O]H2O from a cyclotron. Typically, [18F]uoride is trapped on a quaternary methylammonium (QMA) ion-exchange resin that has been preconditioned with carbonate or bicarbonate, allowing recovery of [ solution such as aqueous K

2CO3

acetonitrile containing Kryptox 222 (K

[

F]KF˙K

reagent is azeotropically dried in order to allow for solubility and reactivity

2.2.2

in the radiouorination step to follow. While this approach is general, a pitfall is that S reactions with uoride are prone to undesirable competing elimination reactions.

Furthermore, the use of additional base in the preconditioning of the QMA and elution of uoride can exacerbate this problem (e.g. accelerate deleterious deprotection processes). Moreover, carbonate and bicarbonate are not compatible with many catalysts or reagents, as they form unproductive mixtures. For example, copper species can form unreactive copper carbonates, inhibiting the desired radiouorination process and decreasing overall radiochemical yield (RCY). In addition, K precursors and poison reaction mixtures. As the eld has developed new methodologies over the past 15 years, PET radiochemists have given careful thought to how [ prepared as a reagent for radiolabeling in order to overcome these challenges.

The preparation of new [ of research. Reports dating back to the 1990s overcame limitations associated with the use of carbonate and its ability to degrade precursors, reagents, and/or products through the use of other anions (e.g. triate, oxalate) to condition and elute QMA cartridges. Recent work on elution scope has demonstrated that basic elution can be achieved provided that a sucient amount of solvent anion is generated. This can simply be achieved using bases with conjugate pKa constants high enough to form ions of the solvent (e.g. hydroxide in the case of H using less basic salts like KOTf, this results in [ ated in a broader set of reaction conditions, such as copper-mediated radiouorination (CMRF)[24]. For example, the Scott group was recently interested in preparing [

O]H2O. The [18F]uoride is then eluted with a basic

to generate [18F]KF. The [18F]KF is then combined with

), a phase-transfer reagent, and the resulting

2.2.2

as a nitrogen base can also degrade potential

2.2.2

F]uoride is

F]uoride sources to improve reactivity is not a new avenue

O). When utilized in conjunction with preconditioning

F]uoride reagents that can be toler-

F]AgF

Chapter 08: Fluorine-18 Radiochemistry 253

to enable access to new CH activation methods for radiouorination[25]. Several reports

of [

F]AgF were present in the literature prior to this[26–30] but required specialized equipment and conditions. Instead, by preconditioning the QMA with an anion that forms a soluble silver salt, such as triate, acetate, or nitrate (using the corresponding potassium or sodium salt), [

F]AgF can be conveniently produced[31]. In this example, changing the preconditioning agent enabled the production of a reactive silver salt that would otherwise have formed an unproductive carbonate/bicarbonate under standard elution conditions. In analogy, solvent protonation can also enable the production of different ions and the production of [ acid led to the protonation of H

[

F]HF[32]. The ability to prepare dierent forms of [18F]uoride oers scope to develop

F uoride sources. This was demonstrated in a recent report describing

F]HF, in which elution with methanesulfonic acid or triuoroacetic

O, ethanol, or N,N-Dimethylformamide (DMF) to produce

further radiouorination methods in the future.

Choice of solvent is also essential in the design of ecient radiouorination processes. Until recently, it has been accepted that the use of protic solvents would inhibit any nucleophilic radiouorination since uoride forms hydrogen bonds with them. This likely originates from nucleophilic

F uorination chemistry, which in many cases has been demonstrated to occur with increased eciency in the absence of hydrogen-bond donors (such as adventitious moisture)[33–37].

However, Stewart and co-workers described how the azeotropic drying of [

F]uoride can be conducted with ethanol instead of acetonitrile without reduction in subsequent reaction yield, oering a greener and cheaper alternative for uorine-18 processing[38]. In this report, the authors demonstrated that several precursors, including the mannose triate precursor of [

F]FDG, could be labeled in a solvent composed of ethanol and H2O (85:15). The use of ethanol over acetonitrile in the azeotropic drying step is of particular interest as it replaces a class II solvent, simplifying quality control analysis provided none are utilized in the production method (e.g. during the reaction, high-performance liquid chromatography (HPLC) purication, and/or solid-phase extraction), as was later disclosed by the Scott laboratory[39]. Furthermore, Sergeev and co-workers demonstrated that highly aqueous solvent mixtures could be utilized for the radiouorination of sulfonates in the presence of titanium catalysts. The sulfonate was postulated to coordinate to the surface of TiO both S

particles, which could also desolvate the [18F]uoride and thus facilitate

2 and SNAr reactions[40]. The use of sulfonate precursor molecules for SN2 was further explored in protic solvents by the Chi laboratory, where reaction was achieved through the formation of ionic liquids from protic solvents[41]. In their early work, 1-butyl3-methylimidazolium triate was utilized, and [ carbonate elution. Notably, the S

2 radiouorination of mesylates in this medium did not

F]uoride was prepared with cesium

require the removal of water prior to the reaction. Later, the same group also reported that if tert-butyl alcohol was utilized as a solvent and cesium carbonate was used for elution, no additive was required to convert the starting sulfonates to the corresponding

[

F]uorinated products[42]. In spite of the preference for aprotic media in a majority of radiouorination methods, protic solvents can also be utilized in uorine-18 chemistry, providing the precursor and reaction conditions are judiciously selected[43].

254 Handbook of Radiopharmaceuticals

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