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@ARTICLE{Ermert:863799,
author = {Ermert, Johannes and Meleán, Johnny Castillo and Humpert,
Swen and Modemann, Daniel and Krupp, Dominik and Kern,
Isabel and Kreft, Sabrina and Coenen, Heinrich Hubert},
title = {{B}aeyer-{V}illiger oxidation tuned to chemoselective
conversion of non-activated [18{F}]fluorobenzaldehydes to
[18{F}]fluorophenols},
journal = {Journal of labelled compounds and radiopharmaceuticals},
volume = {62},
number = {8},
issn = {0362-4803},
address = {New York, NY [u.a.]},
publisher = {Wiley},
reportid = {FZJ-2019-03786},
pages = {380 - 392},
year = {2019},
abstract = {A reaction pathway via oxidation of
[18F]fluorobenzaldehydes offers a very useful tool for the
no‐carrier‐added radiosynthesis of [18F]fluorophenols, a
structural motive of several potential radiopharmaceuticals.
A considerably improved chemoselectivity of the
Baeyer‐Villiger oxidation (BVO) towards phenols was
achieved, employing 2,2,2‐trifluoroethanol as reaction
solvent in combination with Oxone or m‐CPBA as oxidation
agent. The studies showed the necessity of H2SO4 addition,
which appears to have a dual effect, acting as catalyst and
desiccant. For example, 2‐[18F]fluorophenol was obtained
with a RCY of $97\%$ under optimised conditions of 80°C and
30‐minute reaction time. The changed performance of the
BVO, which is in agreement with known reaction mechanisms
via Criegee intermediates, provided the best results with
regard to radiochemical yield (RCY) and chemoselectivity,
i.e. formation of [18F]fluorophenols rather than
[18F]fluorobenzoic acids. Thus, after a long history of the
BVO, the new modification now allows an almost specific
formation of phenols, even from electron‐deficient
benzaldehydes. Further, the applicability of the tuned,
chemoselective BVO to the n.c.a. level and to more complex
compounds was demonstrated for the products n.c.a.
4‐[18F]fluorophenol (RCY $95\%;$ relating to
4‐[18F]fluorobenzaldehyde) and
4‐[18F]fluoro‐m‐tyramine (RCY $32\%;$ relating to
[18F]fluoride), respectively.},
cin = {INM-5},
ddc = {610},
cid = {I:(DE-Juel1)INM-5-20090406},
pnm = {573 - Neuroimaging (POF3-573)},
pid = {G:(DE-HGF)POF3-573},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:31026351},
UT = {WOS:000475397300004},
doi = {10.1002/jlcr.3740},
url = {https://juser.fz-juelich.de/record/863799},
}