10.1002/chem.201805055
Chemistry - A European Journal
COMMUNICATION
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NMR analysis. The nucleophilic attack of an acetate anion on this
short lived species (SN2 type reaction, Scheme 2, red arrows)
delivers the observed sulfanenitrile intermediate F. Subsequent
attack of TFE on the latter account for the formation of the NH-
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sulfoximine
as
proved
by
the
presence
of
the
trifluoroethanolacetate G[26] (observed in the crude mixture). Last,
the NH-sulfoximine can react either with the PIDA (formation of
H) or with the sulfanenitrile F according to the isolated mixture of
NH and NAc sulfoximines. Although not proved by our
experimental observations, a second pathway cannot be totally
ruled out. The formation of a thiazynium E should be possible via
a SN1 like mechanism from sulfilimine D (Scheme 2, purple
arrows), as proposed by Yoshimura.[27] Considering the poor
nucleophilicity of trifluoroethanol, the thiazynium E would evolve
into sulfanenitrile F instead of F’.
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X = AcO or CF3CH2O
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F3C
F3C
H
O
H
O
O
OAc
N
X
N
NH3
TFE
O
O
Ph
I
Ph
I
X
Ph
O
I
Ph
I
A
B
Nitrene
C Activated
nitrene
OAc
N
O
N
CF3
TFE
S
S
R RF
SN1 like
(disfavored)
R
RF
Ph
I
E
S
F' (not detected)
R
RF
N
CF3
O
AcO
S
F3C
R
RF
OAc
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TFE
(favored)
O
O
AcN
R
HN
R
F
D
H
O
S
S
SN2 like
O
H
RF
RF
O
AcO
CF3
N
PIDA
G
S
R
RF
I
O
N
Ph
F
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H
S
R
RF
AcO
Scheme 2. Proposed mechanism.
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In summary, we have reported the first direct synthesis of
fluorinated NH-sulfoximines from sulfides in both the alkyl and aryl
series. A diverse set of important functional groups were well
tolerated. Remarkable reactivity enhancement with TFE was
observed. In agrochemical and medicinal chemistry, the use of
fluorinated sulfoximines has been neglected for a long time[28] and
we expect this methodology will be used in order to increase
chemical diversity. Further investigations to expand the reactivity
of such species are also in progress in our laboratories.
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Acknowledgements
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S.C. thanks Labex Synorg and Labex Charmmmat for
a
postdoctoral fellowship. A.-L.B. thanks the French Ministry of
Research for a doctoral fellowship. We gratefully acknowledge Dr.
K. Wright for the improvement of the English manuscript, K.
Jarsalé for HRMS analysis, H. Elsiblani and R. Legay for 1H NMR
studies.
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Keywords: fluorinated NH-sulfoximines • PIDA • iodonitrene •
thiazynium • λ6–sulfanenitrile
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