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@INPROCEEDINGS{Keuthen:911349,
author = {Keuthen, Yannick and Zlatopolskiy, Boris and Neumaier,
Bernd},
title = {{A}pplication of quaternary 1,4-diazabicyclo[2.2.2]octan
({DABCO}) salts for {SN}2 “minimalist”
radiofluorination},
issn = {0969-8051},
reportid = {FZJ-2022-04641},
year = {2022},
abstract = {Objectives: The piperazine scaffold is a privileged
structuralmotif contained in numerous pharmaceuticals,
including severalPET-tracers. The aim of this work was to
evaluate quaternary DABCOsalts as precursors for the
preparation of probes containing a
N-(2-[18F]Fluoroethyl)piperazyl fragment by the
“minimalist” approach.[1]The latter allows for the
preparation of 18F-labeled compounds usingonly [18F]F– and
onium salt precursors, obviating the need for externalbase,
other additives and azeotropic drying.Methods: Quaternary
DABCO salts were prepared by direct
alkylation,(het)arylation, benzoylation or tosylation of
DABCO. If necessary,anion metathesis was carried out.
[18F]F– was eluted from ananion exchange resin with a
solution of the corresponding DABCO saltin MeOH. MeOH was
evaporated at 60°C for 8 min, the residue wastaken up into
a suitable solvent and heated in a Monowave 50 (AntonPaar,
Ostfildern-Scharnhausen, Germany) synthesis reactor. The
radiolabelingprocedure was optimized with respect to
reaction time,temperature, solvent and DABCO salt counter
ion. Radiolabeled compoundsprepared from alkyl-substituted
DABCO salts were isolatedby solid phase extraction (SPE).
Additionally,
N-(2-[18F]Fluoroethyl)-N’-pentynyl-piperazine ([18F]1)
isolated by SPE was clicked withbenzyl azide (2) to afford a
18F-fluorinated model triazole ([18F]3).Results: Reaction of
DABCO with alkyl halogenides or sulfonatesled to quaternary
alkyl DABCO salts, radiofluorination of which
under“minimalist” conditions furnished the corresponding
ring openingproducts, N-alkyl-N’-(2-[18F]Fluoroethyl)
piperazines, in $48–93\%RCYs$ (determined by HPLC) and,
after isolation by simple SPE, activityyields of up to
$31\%.$ Reaction of [18F]1 with 2 delivered [18F]3 in
aquantitative RCY (determined by HPLC). (Het)arylation,
benzoylationand tosylation of DABCO afforded the respective
N’-substituted piperazyl-N-ethyl DABCO salts (addition
products of two DABCO molecules)in up to $90\%$ yields as
single isolable products. 18F-Fluorinationof such substrates
mainly occurred via substitution of the DABCOgroup, leading
to formation of the corresponding
radiofluorinatedN-substituted
N’-(2-[18F]Fluoroethyl)piperazines in RCYs of
$28–46\%(determined$ by HPLC).Conclusions: Quaternary
DABCO salts are efficient precursors forrapid preparation of
probes containing an N-(2-[18F]Fluoroethyl)piperazinemotif
using the simple and convenient “minimalist”
protocol.Acknowledgement: This work was supported by the DFG
grantZL 65/4-1.Reference:[1] B. D. Zlatopolskiy, et al.;
Org. Biomol. Chem., 2014, 12, 8094.},
month = {May},
date = {2022-05-29},
organization = {24th International Symposium on
Radiopharmaceutical Sciences, Nantes
(France), 29 May 2022 - 3 Jun 2022},
subtyp = {After Call},
cin = {INM-5},
ddc = {570},
cid = {I:(DE-Juel1)INM-5-20090406},
pnm = {5253 - Neuroimaging (POF4-525)},
pid = {G:(DE-HGF)POF4-5253},
typ = {PUB:(DE-HGF)6},
doi = {10.1016/S0969-8051(22)00134-2},
url = {https://juser.fz-juelich.de/record/911349},
}