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Title: Site-selective 18 F fluorination of unactivated C–H bonds mediated by a manganese porphyrin

Abstract

The first direct C–H 18F fluorination reaction of unactivated aliphatic sites using no-carrier-added [18F]fluoride is reported. Under the influence of a manganese porphyrin/iodosylbenzene system, a variety of unactivated aliphatic C–H bonds can be selectively converted to C–18F bonds. The mild conditions, broad substrate scope and generally inaccessible regiochemistry make this radio-fluorination a powerful alternate to established nucleophilic substitution for the preparation of 18F labeled radio tracers.

Authors:
 [1];  [1];  [2];  [3];  [4];  [2]; ORCiD logo [1]
  1. Department of Chemistry, Princeton University, USA
  2. Athinoula A. Martinos Center for Biomedical Imaging, Massachusetts General Hospital, Harvard Medical School, USA, Division of Nuclear Medicine and Molecular Imaging
  3. Department of Process Chemistry, Merck Research Laboratories, Rahway, USA
  4. Imaging Research, Merck Research Laboratories, USA
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Catalytic Hydrocarbon Functionalization (CCHF); Univ. of Virginia, Charlottesville, VA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1413343
Alternate Identifier(s):
OSTI ID: 1506083
Grant/Contract Number:  
DE SC0001298; SC0001298
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 9 Journal Issue: 5; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
62 RADIOLOGY AND NUCLEAR MEDICINE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Liu, Wei, Huang, Xiongyi, Placzek, Michael S., Krska, Shane W., McQuade, Paul, Hooker, Jacob M., and Groves, John T. Site-selective 18 F fluorination of unactivated C–H bonds mediated by a manganese porphyrin. United Kingdom: N. p., 2018. Web. doi:10.1039/C7SC04545J.
Liu, Wei, Huang, Xiongyi, Placzek, Michael S., Krska, Shane W., McQuade, Paul, Hooker, Jacob M., & Groves, John T. Site-selective 18 F fluorination of unactivated C–H bonds mediated by a manganese porphyrin. United Kingdom. doi:10.1039/C7SC04545J.
Liu, Wei, Huang, Xiongyi, Placzek, Michael S., Krska, Shane W., McQuade, Paul, Hooker, Jacob M., and Groves, John T. Mon . "Site-selective 18 F fluorination of unactivated C–H bonds mediated by a manganese porphyrin". United Kingdom. doi:10.1039/C7SC04545J.
@article{osti_1413343,
title = {Site-selective 18 F fluorination of unactivated C–H bonds mediated by a manganese porphyrin},
author = {Liu, Wei and Huang, Xiongyi and Placzek, Michael S. and Krska, Shane W. and McQuade, Paul and Hooker, Jacob M. and Groves, John T.},
abstractNote = {The first direct C–H 18F fluorination reaction of unactivated aliphatic sites using no-carrier-added [18F]fluoride is reported. Under the influence of a manganese porphyrin/iodosylbenzene system, a variety of unactivated aliphatic C–H bonds can be selectively converted to C–18F bonds. The mild conditions, broad substrate scope and generally inaccessible regiochemistry make this radio-fluorination a powerful alternate to established nucleophilic substitution for the preparation of 18F labeled radio tracers.},
doi = {10.1039/C7SC04545J},
journal = {Chemical Science},
number = 5,
volume = 9,
place = {United Kingdom},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C7SC04545J

Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: (a) Traditional 18F labeling methods rely on nucleophilic substitution of pre-functionalized precursors with 18F fluorides. (b) Recent studies allow direct conversion of aliphatic C–H bonds to C–F with nucleophilic fluoride sources. (c) Current work enables 18F labeling of aliphatic sites by direct C–H activation.

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    Works referencing / citing this record:

    [Rh III (Cp*)]-catalyzed arylfluorination of α-diazoketoesters for facile synthesis of α-aryl-α-fluoroketoesters
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    • Ng, Fo-Ning; Chan, Chun-Ming; Li, Jianbin
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