دورية أكاديمية
[ 18 F]Difluorocarbene for positron emission tomography.
| العنوان: | [ 18 F]Difluorocarbene for positron emission tomography. |
|---|---|
| المؤلفون: | Sap JBI; University of Oxford, Chemistry Research Laboratory, Oxford, UK., Meyer CF; University of Oxford, Chemistry Research Laboratory, Oxford, UK.; Discovery Chemistry Janssen Research and Development, Toledo, Spain., Ford J; University of Oxford, Chemistry Research Laboratory, Oxford, UK., Straathof NJW; University of Oxford, Chemistry Research Laboratory, Oxford, UK., Dürr AB; University of Oxford, Chemistry Research Laboratory, Oxford, UK., Lelos MJ; School of Biosciences, Cardiff University, Cardiff, UK., Paisey SJ; Wales Research and Diagnostic PET Imaging Centre (PETIC), School of Medicine, Cardiff University, Cardiff, UK., Mollner TA; University of Oxford, Chemistry Research Laboratory, Oxford, UK., Hell SM; University of Oxford, Chemistry Research Laboratory, Oxford, UK., Trabanco AA; Discovery Chemistry Janssen Research and Development, Toledo, Spain., Genicot C; Global Chemistry, UCB Biopharma Sprl, Braine-L'Alleud, Belgium., Am Ende CW; Pfizer Inc., Medicine Design, Groton, CT, USA., Paton RS; Department of Chemistry, Colorado State University, Fort Collins, CO, USA., Tredwell M; Wales Research and Diagnostic PET Imaging Centre (PETIC), School of Medicine, Cardiff University, Cardiff, UK.; School of Chemistry, Cardiff University, Cardiff, UK., Gouverneur V; University of Oxford, Chemistry Research Laboratory, Oxford, UK. veronique.gouverneur@chem.ox.ac.uk. |
| المصدر: | Nature [Nature] 2022 Jun; Vol. 606 (7912), pp. 102-108. Date of Electronic Publication: 2022 Mar 28. |
| نوع المنشور: | Journal Article |
| اللغة: | English |
| بيانات الدورية: | Publisher: Nature Publishing Group Country of Publication: England NLM ID: 0410462 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1476-4687 (Electronic) Linking ISSN: 00280836 NLM ISO Abbreviation: Nature Subsets: MEDLINE |
| أسماء مطبوعة: | Publication: Basingstoke : Nature Publishing Group Original Publication: London, Macmillan Journals ltd. |
| مواضيع طبية MeSH: | Fluorine Radioisotopes*/chemistry , Hydrocarbons, Fluorinated*/chemistry , Positron-Emission Tomography*/methods , Radiopharmaceuticals*/chemistry, Boronic Acids/chemistry ; Molecular Imaging |
| مستخلص: | The advent of total-body positron emission tomography (PET) has vastly broadened the range of research and clinical applications of this powerful molecular imaging technology 1 . Such possibilities have accelerated progress in fluorine-18 ( 18 F) radiochemistry with numerous methods available to 18 F-label (hetero)arenes and alkanes 2 . However, access to 18 F-difluoromethylated molecules in high molar activity is mostly an unsolved problem, despite the indispensability of the difluoromethyl group for pharmaceutical drug discovery 3 . Here we report a general solution by introducing carbene chemistry to the field of nuclear imaging with a [ 18 F]difluorocarbene reagent capable of a myriad of 18 F-difluoromethylation processes. In contrast to the tens of known difluorocarbene reagents, this 18 F-reagent is carefully designed for facile accessibility, high molar activity and versatility. The issue of molar activity is solved using an assay examining the likelihood of isotopic dilution on variation of the electronics of the difluorocarbene precursor. Versatility is demonstrated with multiple [ 18 F]difluorocarbene-based reactions including O-H, S-H and N-H insertions, and cross-couplings that harness the reactivity of ubiquitous functional groups such as (thio)phenols, N-heteroarenes and aryl boronic acids that are easy to install. The impact is illustrated with the labelling of highly complex and functionalized biologically relevant molecules and radiotracers. (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.) |
| References: | Reardon, S. Whole-body PET scanner produces 3D images in seconds. Nature 570, 285–287 (2019). (PMID: 3121368210.1038/d41586-019-01833-z) Ajenjo, J., Destro, G., Cornelissen, B. & Gouverneur, V. Closing the gap between 19 F and 18 F chemistry. EJNMMI Radiopharm. Chem. 6, 33 (2021). (PMID: 34564781846454410.1186/s41181-021-00143-y) Sap, J. B. et al. Late-stage difluoromethylation: concepts, developments and perspective. Chem. Soc. Rev. 50, 8214–8247 (2021). (PMID: 3407597910.1039/D1CS00360G) Buchner, E. & Curtius, T. Ueber die Einwirkung von Diazoessigäther auf aromatische Kohlenwasserstoffe. Ber. Dtsch. Chem. Ges. 18, 2377–2379 (1885). (PMID: 10.1002/cber.188501802119) Staudinger, H. & Kupfer, O. Über reaktionen des methylens. III. Diazomethan. Ber. Dtsch. Chem. Ges. 45, 501–509 (1912). (PMID: 10.1002/cber.19120450174) Hopkinson, M. N., Richter, C., Schedler, M. & Glorius, F. An overview of N-heterocyclic carbenes. Nature 510, 485–496 (2014). (PMID: 2496564910.1038/nature13384) Geri, J. B. et al. Microenvironment mapping via Dexter energy transfer on immune cells. Science 367, 1091–1097 (2020). (PMID: 32139536733666610.1126/science.aay4106) Marinelli, M., Santini, C. & Pellei, M. Recent advances in medicinal applications of coinage-metal (Cu and Ag) N-heterocyclic carbene complexes. Curr. Top. Med. Chem. 16, 2995–3017 (2016). (PMID: 2715036810.2174/1568026616666160506145408) Smith, C. A. et al. N-heterocyclic carbenes in materials chemistry. Chem. Rev. 119, 4986–5056 (2019). (PMID: 3093851410.1021/acs.chemrev.8b00514) Campbell, M. G. et al. Bridging the gaps in 18 F PET tracer development. Nat. Chem. 9, 1–3 (2017). (PMID: 10.1038/nchem.2693) Deng, X. et al. Chemistry for positron emission tomography: recent advances in 11 C‐, 18 F‐, 13 N‐, and 15 O‐labeling reactions. Angew. Chem. Int. Ed. 58, 2580–2605 (2019). (PMID: 10.1002/anie.201805501) McCluskey, S. P., Plisson, C., Rabiner, E. A. & Howes, O. Advances in CNS PET: the state-of-the-art for new imaging targets for pathophysiology and drug development. Eur. J. Nucl. Med. Mol. Imaging 47, 451–489 (2020). (PMID: 3154128310.1007/s00259-019-04488-0) Prchalová, E., Štěpánek, O., Smrček, S. & Kotora, M. Medicinal applications of perfluoroalkylated chain-containing compounds. Future Med. Chem. 6, 1201–1229 (2014). (PMID: 2507813810.4155/fmc.14.53) Huiban, M. et al. A broadly applicable [ 18 F]trifluoromethylation of aryl and heteroaryl iodides for PET imaging. Nat. Chem. 5, 941–944 (2013). (PMID: 2415337210.1038/nchem.1756) Levin, M. D. et al. A catalytic fluoride-rebound mechanism for C(sp 3 )–CF van der Born, D. et al. A universal procedure for the [ 18 F]trifluoromethylation of aryl iodides and aryl boronic acids with highly improved specific activity. Angew. Chem. Int. Ed. 53, 11046–11050 (2014). (PMID: 10.1002/anie.201406221) Mizuta, S. et al. Catalytic decarboxylative fluorination for the synthesis of tri-and difluoromethyl arenes. Org. Lett. 15, 2648–2651 (2013). (PMID: 2368795810.1021/ol4009377) Verhoog, S. et al. Silver-mediated 18 F-labeling of aryl–CF Shi, H. et al. Synthesis of 18 F‐difluoromethylarenes from aryl (pseudo) halides. Angew. Chem. Int. Ed. 55, 10786–10790 (2016). (PMID: 10.1002/anie.201604106) Yuan, G. et al. Metal-free 18 F-labeling of aryl–CF Sap, J. B. et al. Synthesis of 18 F-difluoromethylarenes using aryl boronic acids, ethyl bromofluoroacetate and [ 18 F]fluoride. Chem. Sci. 10, 3237–3241 (2019). (PMID: 30996907642959110.1039/C8SC05096A) Zhao, Q. et al. Radiosynthesis of [ 18 F]arylSCF Trump, L. et al. Late‐stage 18 F‐difluoromethyl labeling of N‐heteroaromatics with high molar activity for PET imaging. Angew. Chem. Int. Ed. 58, 13149–13154 (2019). (PMID: 10.1002/anie.201907488) Ni, C. & Hu, J. Recent advances in the synthetic application of difluorocarbene. Synthesis 46, 842–863 (2014). (PMID: 10.1055/s-0033-1340856) Fier, P. S. & Hartwig, J. F. Synthesis of difluoromethyl ethers with difluoromethyltriflate. Angew. Chem. Int. Ed. 52, 2092–2095 (2013). (PMID: 10.1002/anie.201209250) Xie, Q. et al. Efficient difluoromethylation of alcohols using TMSCF Birchall, J. M., Haszeldine, R. N. & Roberts, D. W. Cyclopropane chemistry. Part II. Cyclopropanes as sources of difluorocarbene. J. Chem. Soc. Perkin Trans. I 1071–1078 (1973). Jia, Y., Yuan, Y., Huang, J., Jiang, Z. & Yang, Z. Synthesis of difluorinated heterocyclics through metal-free [8+1] and [4+1] cycloaddition of difluorocarbene. Org. Lett. 23, 2670–2675 (2021). (PMID: 3372404510.1021/acs.orglett.1c00577) Feng, Z., Min, Q. & Zhang, X. Access to difluoromethylated arenes by Pd-catalyzed reaction of arylboronic acids with bromodifluoroacetate. Org. Lett. 18, 44–47 (2016). (PMID: 2665427310.1021/acs.orglett.5b03206) Deng, X., Lin, J. & Xiao, J. Pd-catalyzed transfer of difluorocarbene. Org. Lett. 18, 4384–4387 (2016). (PMID: 2751786510.1021/acs.orglett.6b02141) Feng, Z., Min, Q., Fu, X., An, L. & Zhang, X. Chlorodifluoromethane-triggered formation of difluoromethylated arenes catalysed by palladium. Nat. Chem. 9, 918–923 (2017). (PMID: 2883716610.1038/nchem.2746) Fu, X. et al. Controllable catalytic difluorocarbene transfer enables access to diversified fluoroalkylated arenes. Nat. Chem. 11, 948–956 (2019). (PMID: 3154867010.1038/s41557-019-0331-9) Smail, T. & Rowland, F. S. Insertion reactions of mono-and difluorocarbene with hydrogen halides. J. Phys. Chem. 74, 1866–1871 (1970). (PMID: 10.1021/j100704a007) Prakash, G. S. et al. Long‐lived trifluoromethanide anion: a key intermediate in nucleophilic trifluoromethylations. Angew. Chem. Int. Ed. 53, 11575–11578 (2014). (PMID: 10.1002/anie.201406505) Hine, J. & Porter, J. J. The formation of difluoromethylene from difluoromethyl phenyl sulfone and sodium methoxide. J. Am. Chem. Soc. 82, 6178–6181 (1960). (PMID: 10.1021/ja01508a050) Xing, L. et al. Fluorine in drug design: a case study with fluoroanisoles. ChemMedChem 10, 715–726 (2015). (PMID: 2575513210.1002/cmdc.201402555) Khotavivattana, T. et al. 18 F‐labeling of aryl–SCF Dahl, K., Halldin, C. & Schou, M. New methodologies for the preparation of carbon-11 labeled radiopharmaceuticals. Clin. Transl. Imaging 5, 275–289 (2017). (PMID: 28596949543713610.1007/s40336-017-0223-1) Pipal, R. W. et al. Metallaphotoredox aryl and alkyl radiomethylation for PET ligand discovery. Nature 589, 542–547 (2021). (PMID: 3323828910.1038/s41586-020-3015-0) Mullard, A. Deuterated drugs draw heavier backing. Nat. Rev. Drug Discov. 15, 219–222 (2016). (PMID: 2703282110.1038/nrd.2016.63) Cai, Z. et al. Synthesis and in vivo evaluation of [ 18 F]UCB-J for PET imaging of synaptic vesicle glycoprotein 2A (SV Zheng, J., Winkeler, A., Peyronneau, M.-A., Dollé, F. & Boisgard, R. Evaluation of PET imaging performance of the TSPO radioligand [ 18 F]DPA-714 in mouse and rat models of cancer and inflammation. Mol. Imaging Biol. 18, 127–134 (2016). (PMID: 2619401010.1007/s11307-015-0877-x) Keller, T. et al. Radiosynthesis and preclinical evaluation of [ 18 F]F-DPA, a novel pyrazolo[1,5a]pyrimidine acetamide TSPO radioligand, in healthy Sprague Dawley rats. Mol. Imaging Biol. 19, 736–745 (2017). (PMID: 28083825557495810.1007/s11307-016-1040-z) Kuchar, M. & Mamat, C. Methods to increase the metabolic stability of 18 F-radiotracers. Molecules 20, 16186–16220 (2015). (PMID: 26404227633212310.3390/molecules200916186) Lelos, M. J. & Dunnett, S. B. Generating Excitotoxic Lesion Models of Huntington’s Disease 209–220 (Springer, 2018). Zhou, W. et al. Transition-metal difluorocarbene complexes. Chem. Commun. 57, 9316–9329 (2021). (PMID: 10.1039/D1CC04029D) Li, X. et al. Copper-mediated aerobic (phenylsulfonyl)difluoromethylation of arylboronic acids with difluoromethyl phenyl sulfone. Chem. Commun. 52, 3657–3660 (2016). (PMID: 10.1039/C5CC10550A) The International Council for Harmonisation of Technical Requirements for Pharmaceuticals for Human Use. Quality guidelines. ICH https://www.ich.org/page/quality-guidelines (2019). |
| معلومات مُعتمدة: | F-1502 United Kingdom PUK_ Parkinson's UK |
| المشرفين على المادة: | 0 (Boronic Acids) 0 (Fluorine Radioisotopes) 0 (Hydrocarbons, Fluorinated) 0 (Radiopharmaceuticals) 0 (difluorocarbene) |
| تواريخ الأحداث: | Date Created: 20220328 Date Completed: 20220603 Latest Revision: 20240214 |
| رمز التحديث: | 20240214 |
| DOI: | 10.1038/s41586-022-04669-2 |
| PMID: | 35344982 |
| قاعدة البيانات: | MEDLINE |
Find this article in full text from Springer Verlag. 
Full Text Finder | تدمد: | 1476-4687 |
|---|---|
| DOI: | 10.1038/s41586-022-04669-2 |