Chemistry - A European Journal
10.1002/chem.201901607
COMMUNICATION
BT-SeCF
to prepare BT-SCF
trifluoromethylselenylated benzothiazole 9
3% yield from bis(2-benzothiazolyl)diselenide upon sequential
3
was synthesized via the same general strategy used
167, 16-29; f) A. Harsanyi, G. Sandford, Green Chem. 2015, 17, 2081-
2086.
3
.
In the first stage, the known
[
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5
reduction with NaBH
4
and UVA light-facilitated radical
22]
trifluoromethylation with CF
methylation with MeOTf (3 equiv) in CH
pure BT-SeCF in 92% yield upon precipitation with Et
filtration (Scheme 4). As for BT-SCF , the selenium derivative was
obtained as an off-white solid that is remarkably stable towards
hydrolysis in the absence of a base. With BT-SeCF in hand, its
potential as reagent for deoxytrifluoromethylselenylation
reactions was tested with a selection of aliphatic alcohols
3
I
and NaH.[9b,
Cl
Subsequent
2
2
at rt for 24 h provided
O and
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2
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3
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(
(
Scheme 5). Upon treating the benzylic alcohol 5b with BT-SeCF
1.25 equiv) under the same mild reaction conditions used with
, a clean deoxytrifluoromethylselenylation process was
observed leading to the SeCF -substituted product 10a in 88%
3
8
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BT-SCF
3
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3
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yield. Moreover, several other benzylic and propargylic alcohols
reacted with similarly high yields while, upon decreasing the
reaction temperature to −40 °C, the primary aliphatic alcohol 2a
and even the secondary alcohol 7b could be successfully
transformed into the corresponding selenoethers 10e and 10g in
[
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2
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55% and 44% yield, respectively.
2
In conclusion, we have introduced two new reagents for
installing valuable fluorine-containing functional groups onto
organic compounds. Based on the benzothiazolium motif, BT-
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SCF
that release SCF
activation in situ. Using only a slight excess of BT-SCF
3
and BT-SeCF
3
are bench stable and easy to handle solids
−
−
3
or SeCF
3
anions in a controlled fashion upon
, a wide-
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3
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while
BT-SeCF
3
enables
hitherto
unprecedented
deoxytrifluoromethylselenylation reactions. We believe that
benzothiazolium salts could open up new routes towards
important organofluorine compounds and further studies are
underway in our laboratory.
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Acknowledgements
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The authors thank Henry Simmons (University of Durham, UK) for
initial experiments and helpful discussions. Financial support from
the Deutsche Forschungsgemeinschaft (DFG, German Research
Foundation) through the Research Training Network “Fluorine as
a Key Element” (GRK 1582) and Project Number 387284271
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SFB 1349, “Fluorine-Specific Interactions”), and from the Fonds
der chemischen Industrie (FCI, Sachkostenzuschuss) is gratefully
acknowledged.
[
10] Higher yields of 1 were obtained upon reducing the reaction scale.
[11] See the supporting information for more details.
Keywords: fluorine • reagent development • trifluoromethylthio
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5
(
3 3
SCF ) group • trifluoromethylselenyl (SeCF ) group • alcohols
2
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1
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