Pd0-mediated rapid C-[18F]fluoromethylation by the cross-coupling reaction of a [18f]fluoromethyl halide with an arylboronic acid ester: Novel method for the synthesis of a 18f- labeled molecular probe for positron emission tomography

Bulletin of the Chemical Society of Japan

Volumn 85, Issue 11, 2012, Pages 1233-1238

  Doi, Hisashi ^a   Goto, Miki ^a   Suzuki, Masaaki ^a  

^a RIKEN   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ARYLBORONIC ACIDS; CARBON FRAMEWORK; COUPLING EFFICIENCY; CROSS COUPLING REACTIONS; FLUOROMETHYLATION; ISOLATED YIELD; MOLECULAR PROBES; REACTION TEMPERATURE; TOTAL SYNTHESIS;

CHEMISTRY; SYNTHESIS (CHEMICAL);

POSITRON EMISSION TOMOGRAPHY;

EID: 84869388588     PISSN: 00092673     EISSN: 13480634     Source Type: Journal    
DOI: 10.1246/bcsj.20120151     Document Type: Article

References (38)

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30. As one of the important 18F-labeling methods with [18F]F, direct [18F]fluorination on phenyl ring structures has been carried out mainly by the replacement of good leaving groups such as halogeno, nitro, and trialkylammonium groups in the case of an electron-withdrawing group existing at the ortho- or para-position. Recently, transition-metal-mediated [18F]fluorination onto a phenyl ring without an electron-withdrawing group has been reported; see, E. Lee, A. S. Kamlet, D. C. Powers, C. N. Neumann, G. B. Boursalian, T. Furuya, D. C. Choi, J. M. Hooker, T. Ritter, Science 2011, 334, 639.
31. In our own research, the use of [Pd2(dba)3] and P(o- CH3C6H5)3 in an amide polar solvent such as DMF, NMP, and DMPU have been effective for trapping [11C]CH3I and are resistant to radiolysis. These are reasonable standards for selecting an effective Pd0 complex under the PET radiolabeling conditions.
32. A sampling solution (20 ̄L) obtained from the reaction mixture was directly analyzed by radio-HPLC, and the yield was calculated as the HPLC analytical yield from the peak area ratio of the desired [18F]fluoromethylated compound [18F]-2 to whole 18Fcontained products. Product [18F]-2 was identified by coinjection with an unlabeled reference compound of methyl 4(fluoromethyl) benzoic acid methyl ester.
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35. In the experiments of C-[18F]fluoromethylation in Table 1, we confirmed that [18F]FCH2Br (bp 1718 °C) was not volatized from the reaction mixture at 90 and 120 °C by inspecting the radioactivity of the reaction mixture at the reaction time of 5, 15, and 30min. Therefore, we concluded that the comparison of HPLC analytical yields was useful for the discussion to explore the optimized conditions.
36. The radioactivity level of 500MBq is applicable to animal and human clinical trials. According to [18F]FDG PET and PET/ CT practical guidelines 2010 by the Japanese Society of Nuclear Medicine (JSNM), [18F]FDG with 111259MBq per person is injected intravenously for medical examination. See the website of JSNM, http://www. jsnm. org/.
37. In our radiolabeling systems, the reaction of CH2Br2 and approximately 10 GBq [18F]fluoride ion usually produced approximately 1. 0 GBq [18F]FCH2Br within a processing time of 4445min.
38. T. Kuboyama, M. Nakahara, M. Yoshino, Y. Cui, T. Sako, Y. Wada, T. Imanishi, S. Obika, Y. Watanabe, M. Suzuki, H. Doi, Bioorg. Med. Chem. 2011, 19, 249.