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L. Kang et al.
Letter
Synlett
erates six-membered ring anion C. After defluorination, ad-
duct 2 is generated and the released HF acid can be trapped
by the 3Å MS to assist with base-catalyst regeneration.12
References and Notes
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A: Effect of MS 3Å and fluorine
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O
O
O
O
O
S
F
S
F
TMG (5 mol%)
R1
yield: 27%
DMF, Pyridine (1.0 equiv)
80 °C, 10 h
O
R1
F
1a
2a
without MS 3Å
O
O
O
O
O
S
F
S
X
TMG (5 mol%)
R1
yield: trace (5)
yield: trace (6)
DMF, MS 3Å, 80 °C, 10 h
O
R1
F
X = Cl, 5
Br, 6
2a
B: Proposed mechanism
O
O
R1
O
O
O
O
O
O
S
F
S
F
S
R1
R1
O
TMG
F
F
F
F
1
A
B
3Å
TMG-H+
Activator
F
O
R1
F
O
O
R1
MS
3Å
MS
3Å
H
F
F
+
S
S
Deacid reagent
F
O
O
O
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C
2
Scheme 4 Mechanistic hypothesis
In summary, we have developed a novel base-catalyzed
defluorination/O-arylation that streamlines the synthesis
of 3-fluoro-1,4-oxathiine 4,4-dioxide derivatives from read-
ily accessible substituted -fluoro--one-sulfones,13 which
might be valuable for the exploitation of fluorine-contain-
ing pharmaceutical molecules and materials. Unlike tradi-
tional defluorination reactions with transition-metal catal-
ysis or with stoichiometric base as the deacid reagent, our
process is triggered by a catalytic amount of base and mo-
lecular sieves act as the deacid reagent and activator. This
method, is complementary and contradistinctive to the
classical transformations of defluorination reactions and
represents a valuable method for organofluorine chemistry.
Funding Information
Financial support from the National Natural Science Foundation of
China (21602231), the Natural Science Foundation of Jiangsu Province
(BK20160396 and BK20191197), and the Chinese Academy of Scienc-
es (‘Light of West China’ Program) is gratefully acknowledged.
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Supporting Information
Supporting information for this article is available online at
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Chem. 2014, 57, 2832. (d) Hamamoto, I.; Aoyama, H.; Sakamshi,
© 2021. Thieme. All rights reserved. Synlett 2021, 32, 785–789