Facile Preparation of Vinyl S-Trifluoromethyl NH Aryl Sulfoximines

Article abstract of DOI:10.1002/ejoc.201800324

We report herein the preparation of ortho-vinylaryl S-trifluoromethylated sulfoximines through cross-coupling reactions. Two efficient palladium-catalyzed procedures (Stille and Suzuki) were developed, with use of ortho-iodo aryl sulfoximines as substrate

Full text of DOI:10.1002/ejoc.201800324

DOI: 10.1002/ejoc.201800324
Full Paper
Sulfoximines Functionalization | Very Important Paper |
Facile Preparation of Vinyl S-Trifluoromethyl NH Aryl
Sulfoximines
Anne-Laure Barthelemy,[a][‡] Alexis Prieto,[a,b][‡] Patrick Diter,[a] Jérôme Hannedouche,[b]
Martial Toffano,[b] Elsa Anselmi,*[a] and Emmanuel Magnier*[a]
Abstract: We report herein the preparation of ortho-vinylaryl compared to nonfluorinated counterparts, allowed the use of
S-trifluoromethylated sulfoximines through cross-coupling reac- free NH sulfoximines in the coupling processes, where they
tions. Two efficient palladium-catalyzed procedures (Stille and proved to be inert to cyclization. Finally, further transformations
Suzuki) were developed, with use of ortho-iodo aryl sulfox- have been explored, such as metathesis coupling reactions,
imines as substrates, to give various vinyl derivatives in good after post-functionalization of the nitrogen atom by another
yields. The difference in reactivity of the fluorinated derivatives, vinyl group.
Introduction
recently demonstrated (Scheme 1).[9] By this simple methodol-
ogy, various electrophiles (halogen, oxygen, sulfur, boron,
stannyl) were attached to the aromatic ring. Amongst them, the
iodide derivative was the most important, as it represents an
entry for the easy introduction of various other functional
groups; this is the topic summarized in this article. The straight-
forward introduction of a π system at the ortho position of a
free NH S-perfluoroalkyl sulfoximine is discussed as well as post-
functionalization of the nitrogen atom. Metathesis–cyclization
reactions were then performed, to give the hitherto unknown
sulfoximines.
Since its seminal preparation in 1949 by Bentley and White-
head, the sulfoximine group has continuously grown in popu-
larity in modern organic chemistry.[1] More and more chemists
have used this intriguing and promising moiety with a remark-
able acceleration in recent years. The numerous and major re-
cent improvements in their synthesis enabled the use of sulfox-
imines in various fields (catalysis, chiral auxiliaries, directing
groups), in which they proved to be valuable entities.[2] They
are also promising for life science applications.[3] Sulfoximines
are considered “neglected opportunities” in this area, which
may now be exploited.[4] The S-perfluoroalkyl sulfoximines are
unique members of this peculiar family. They differ both in their
preparation, which is often much more complex than that of
the nonfluorinated series, and in their use.[5] Owing to their
structural modularity, S-perfluoroalkyl sulfoximines can be es-
pecially employed as a source of electrophilic,[6] nucleophilic,[7]
or radical[8] perfluorinated groups with widespread examples.
Recent works clearly highlight the need for the development of
new protocols for the preparation of sophisticated molecules
bearing an S-perfluoroalkyl sulfoximine group.
During our ongoing research program dedicated to these
halogenated sulfur(VI) compounds, the first use of a free NH
S-trifluoromethyl sulfoximine as an ortho-directing group was
Scheme 1. ortho-Functionalization of S-aryl S-trifluoromethyl sulfoximines.
We turned our attention to the ethylenic system for two
main reasons: the potential offered by this unsaturated group
and the synthetic challenge. In the non-fluorinated NH-sulfox-
imines series, attempts to prepare such targets by CH activation
lead most of the time to subsequent cyclization between the
nitrogen atom and the sp2 carbon.[10] To the best of our knowl-
edge, only two examples were published by Bolm et al. leading
to vinyl derivatives of the noncyclized sulfoximines: both of
them using an adaptation of the reaction conditions (substrate
and catalysis).[11] We assumed that, in our case, the behavior of
S-perfluoroalkyl sulfoximines might be different because of the
reduced nucleophilicity of the nitrogen which would prevent
[a] Lavoisier de Versailles, UMR CNRS 8180,
Université de Versailles St-Quentin-Yvelines,
45 Avenue des Etats-Unis, 78035 Versailles Cedex, France
E-mail: emmanuel.magnier@uvsq.fr
http://www.ilv.uvsq.fr/m-magnier-emmanuel-356331.kjsp?RH=
1429180098391
[b] Laboratoire de Catalyse Moléculaire, Institut de Chimie Moléculaire et des
Matériaux d′Orsay (ICMMO), UMR CNRS 8182,
Université Paris-Sud, 91405 Orsay Cedex, France
[‡] These authors contributed equally to this work
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.201800324.
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cyclization and could account for the expected stabilization of hand, the NH product 4a was regenerated from the mixture by
the isolated vinyl derivative.
silica gel treatment followed by classical purification in 63 %
yield.
Other vinylstannanes were then engaged in the Stille reac-
tion. The transformation proved efficient with double bonds
substituted at the 2-position by a silyl 4b–c, a methyl 4d, and
even a furyl 4e group. Interestingly, when a mixture of Z,E-
tributylstannylpropenyl was used, the reaction proceeded with
complete retention of the configuration of the starting material
[E(20)/Z(80) ratio].
Results and Discussion
Our study began with the challenging Heck reaction.[12] Many
attempts at coupling between sulfoximine 1a and various dou-
ble bonds (styrenic and acrylic compounds) failed, whatever the
conditions tried. The Stille reaction was thus considered as an
alternative. We started with the coupling of tributyl(vinyl)tin
(2a) using the conditions previously defined by Englert under
microwave activation as a slight adaptation.[13] The reaction was
carried out with an excess of substrate 2a. We observed com-
plete conversion of the starting material and formation of a
mixture of the desired coupling product 4a with the N-tributyl-
tin compound 3a in a 23:77 ratio determined by 19F NMR spec-
troscopic data. The latter was isolated in pure form by chroma-
tography on alumina gel in 75 % yield (Scheme 2). On the other
The Suzuki–Miyaura cross-coupling reaction, which gives
more opportunities because there are more organoboronated
reagents available than stannyl ones, was then considered. Dif-
ferent catalysts and conditions were tested in this transforma-
tion. The first attempt was performed with potassium vinyltri-
fluoroborate (5a) (Table 1, entry 1).[14] A rather low conversion
was observed with formation of only the de-iodo product 1′
accompanied by an insignificant quantity of the desired sulfox-
imine 4a. The reaction conditions described by Bolm et al. for
nonfluorinated sulfoximines were also considered and gave rise
to a small amount of derivative 4a with a mixture of unidenti-
fied fluorinated products (Table 1, entry 2).[15] The conditions
of Grela et al. allowed the formation of target 4a in acceptable
yield (45 %) in a mixture with the S-phenyl sulfoximine 1′
(Table 1, entry 3).[16] Finally, an adaptation of the previous con-
ditions allowed complete conversion and provided 4a in 78 %
yield, with a reduced portion of de-iodinated sulfoximine 1′
(Table 1, entry 4). The same transformation was also performed
under classical thermal activation resulting in a slight decrease
of the overall yield (Table 1, entry 5).
The scope of the Suzuki reaction was further investigated
with various alkenyl vinyltrifluoroborates, pinacol boronic es-
ters, and boronic acids that were commercially available or pre-
pared by classical methods (Scheme 3).[17] These conditions al-
lowed the cross-coupling reaction with different boronated spe-
cies. We observed only a slight increase in yield of the S-phenyl
sulfoximine 1′ with use of the alkenyl boronic acid instead of
the trifluoroborate species. Consequently, pinacol boronic ester
and boronic acid species showed a tendency to give moderate
yields, while vinyl trifluoroborates were particularly suitable to
the applied conditions giving the best yields (4a,d,j,k,o). Mole-
cules 4a and 4d, prepared also by the Stille coupling, were
Scheme 2. Stille coupling reactions. Reaction conditions: 1 (0.3 mmol), 2
(0.9 mmol), LiCl (30 mol-%), PdCl2(PPh3)2 (7 mol-%), CuI (7 mol-%) in DMF
(3 mL). Isolated yields are given.
Table 1. Conditions for Suzuki–Miyaura coupling reactions.
Entry
RBF3K
(equiv.)
Catalyst[a]
Solvent
+ H2O
Base
T°, Time
Yield [%][b]
1a/4a/1′
1
2
3
4
5
1.2
2
1.2
4
A
B
C
C
C
toluene
CH3CN
THF
dioxane
dioxane
Cs2CO3
K2CO3
Cs2CO3
Cs2CO3
Cs2CO3
70 °C, 12 h
120 °C, 24 h
90 °C, 48 h
120 °C, 45 min (Mw)
120 °C, 18 h
80:2:11
2:10:21
0:45:26
0:78:10
0:58:7
4
[a] A = PdCl2dppf; B = Pd(PPh3)4; C=PdCl2(PPh3)2. [b] Determined by 19F NMR spectroscopy of the crude mixture with trifluoromethoxybenzene as an internal
standard.
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synthesized with improved yields. A small library of ortho-func-
To our satisfaction, whatever the conditions employed for
tionalized sulfoximines were isolated, including double bonds the coupling reaction (Stille or Suzuki) and the substrates, no
conjugated with a wide range of aromatic rings. Methyl substi- cyclization product was observed. The compounds were per-
tution on the aromatic starting sulfoximine did not significantly fectly stable, even if kept for a long time on the bench. This
influence the yield (4o).
behavior opened the way for further transformations.
Our recently published procedures for N-alkenyl- and N-
alkynylation of NH sulfoximines proved efficient on product
4a.[18] Compounds 6 and 7a–b were prepared in good yields
(Scheme 5). These latter would be good candidates for metath-
esis transformation, giving access to new and challenging cyclic
sulfoximine derivatives 8 and 9a–b. Pleasingly, the metathesis
succeeded with the N-alkenyl derivative 6 providing the ex-
pected and unknown product 8 in excellent yield (Scheme 5).
Two different types of catalysts were able to form sulfoximine
8, the Hoveyda–Grubbs[19] as well as the M73-SIPr developed
by Mauduit and co-workers.[20] The first attempts were run on
a mixture of Z/E isomers of the double bond attached to the
nitrogen. As the E isomer was much slower to react, we then
worked only with the pure Z compound 6. Substrates 7a and
7b remained, unfortunately, inert to the metathesis process
whatever the conditions employed (solvent, catalyst, and tem-
perature). An increase of the reaction time and of the tempera-
ture led only to degradation of the substrate.
To the best of our knowledge, this synthesis of the original
compound 8 is the first example of a ring-closure metathesis
involving a sulfoximine. This last result paves the way for the
construction of new compounds.
Scheme 3. Suzuki–Miyaura coupling reactions. Reaction conditions:
(0.3 mmol), 5 (1.2 mmol), Cs2CO3 (0.9 mmol), PdCl2(PPh3)2 (6 mol-%) in diox-
ane (3 mL) and water (1 mL). Isolated yields are given.
1
Finally, gram-scale experiments were conducted by using the
established microwave and thermal procedures as described in
Table 1. The two protocols allowed the isolation of 4a with
comparable yields, illustrating the robustness of our protocol
(Scheme 4).
Conclusions
We have described the efficient preparation of ortho-vinyl
S-trifluoromethyl S-arylsulfoximines through Stille and Suzuki–
Miyaura cross-coupling reactions, under microwave activation.
As we hypothesized, the decreased nucleophilicity of the nitro-
gen atom of the perfluorinated sulfoximines prevents hydro-
amination during the coupling reaction, allowing the isolation
of noncyclized ortho-functionalized sulfoximines in good yields.
Further transformations were thus possible, such as a successful
metathesis delivering the hitherto unknown cyclic sulfoximine.
Other transformations are currently under development in our
laboratory.
Scheme 4. Gram-scale experiments.
Scheme 5. Post-functionalization.
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the solvent removed under reduced pressure to yield pure com-
pounds 4.
Experimental Section
General Information: Chemicals were purchased from commercial
suppliers and used without further purification. Reactions were
monitored by 19F NMR spectroscopy. Yields refer to materials puri-
fied by preparative TLC chromatography. NMR spectra were re-
corded with a Bruker AC-200 or AC-300 spectrometer. Reported
coupling constants and chemicals shifts are based on a first order
analysis. Internal reference was the residual peak of CHCl3 (δ =
7.26 ppm) for 1H (200 or 300 MHz), central peak of CDCl3 (δ =
77.16 ppm) for 13C (75 or 50 MHz) NMR spectra, and CFCl3 (δ =
0.00 ppm) for 19F (188 MHz) NMR spectra. High-resolution mass
spectrometry (HRMS) was performed with a mass spectrometer
XEVO-QTOF in the Institute Lavoisier of Versailles-University of Ver-
sailles Saint Quentin. Microwave experiments were conducted with
an Anton Paar Monowave 300 instrument by using the following
method: P = 600 W, full air cooling ON, stirring ON. Imino(2-iodo-
phenyl)(trifluoromethyl)-λ6-sulfanone (1a) was prepared following a
literature procedure.[9]
General Procedure (GP B): Preparation of Sulfoximines 4
through Suzuki Coupling: o-Iodosulfoximine (0.3 mmol, 1 equiv.),
Cs2CO3 (293 mg, 0.9 mmol, 3 equiv.), and the PdCl2(PPh3)2 catalyst
(13 mg, 6 mol-%), were placed in a microwave vial and then diluted
with 1,4-dioxane (3 mL) and water (1 mL). The selected boron pre-
cursor (4 equiv.) was then added to the solution and the vial was
flushed with argon and sealed. The reaction mixture was then irradi-
ated under microwave conditions at 120 °C for 45 min. After cool-
ing, EtOAc was added to the resulting solution and the mixture was
successively washed with brine. The organic layer was dried with
magnesium sulfate and concentrated under reduced pressure. The
residue was finally purified by preparative TLC with use of the ap-
propriate eluent (pentane/diethyl ether or toluene).
[(Tributylstannyl)imino](trifluoromethyl)(2-vinylphenyl)-λ6-
sulfanone (3a): Colorless oil (according to GP A: 120 mg, 75 %
yield). 1H NMR (200 MHz, CD3CN): δ = 8.13 (d, J = 7.9 Hz, 1 H), 8.01–
7.87 (m, 1 H), 7.87–7.74 (m, 1 H), 7.66 (t, J = 7.3 Hz, 1 H), 7.50 (t, J =
7.6 Hz, 1 H), 5.74 (d, J = 17.4 Hz, 1 H), 5.38 (d, J = 11.1 Hz, 1 H), 1.39
(m, 15 H), 0.85 (t, J = 7.2 Hz, 9 H) ppm. 13C NMR (75 MHz, CD3CN):
Imino(2-iodo-4-methylphenyl)(trifluoromethyl)-λ6-sulfanone
(1b): nBuLi (2.5
M in hexane, 600 μL, 1.5 mmol) was added dropwise
to a solution of NH tolyltrifluoromethylsulfoximine (105 mg,
0.5 mmol) in freshly distilled THF (10 mL) at –50 °C. The reaction
temperature was then slowly increased to –30 °C under magnetic
stirring for 1 h. The reaction mixture was cooled again to –50 °C for
the dropwise addition of the electrophile (1–5 mmol, 2–10 equiv.)
and warmed to room temperature whilst stirring for 2 h prior to
quenching with a saturated NH4Cl (aq.) solution (10 mL). The aque-
ous layer was extracted with Et2O (3 × 7 mL), dried with anhydrous
MgSO4, filtered, and concentrated. The residue was purified by flash
column or by preparative TLC by using petroleum ether/diethyl
ether (9:1) as the eluent to afford the product as a brownish solid
in 98 % yield. M.p. 71 °C. 1H NMR (300 MHz, CDCl3): δ = 8.29 (d, J =
8.2 Hz, 1 H), 8.08 (s, 1 H), 7.39 (d, J = 7.6 Hz, 1 H), 3.76 (br. s, 1 H),
2.41 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 147.6, 145.3, 134.3,
131.3, 129.9, 120.9 (q, J = 332.4 Hz), 94.4, 21.1 ppm. 19F NMR
(282 MHz, CDCl3): δ = –76.4 (s) ppm. HRMS (ESI): calcd. for
C8H8F3NOS [M + H+, 100 %] 349.9326; found 349.9323.
δ = 140.5, 136.5, 135.5, 135.3, 133.2, 129.2, 129.1, 122.3 (q, JC,F
=
335 Hz), 118.2, 28.8 (JSn,C = 24 Hz, 3 × C), 27.6 (JSn,C = 63 Hz, 3 × C),
16.3 (JSn,C = 371.4 Hz, 3 × C), 13.9 ppm. 19F NMR (188 MHz, CD3CN):
δ = –79.4 (s) ppm. HRMS (ESI): calcd. for C21H35F3NOSSn [M + H]+
526.1413; found 526.1400.
(E)-[(Tributylstannyl)imino](trifluoromethyl){2-[2-(trimethyl-
silyl)vinyl]phenyl}-λ6-sulfanone (3b): Colorless oil (according to
GP A: 130 mg, 69 % yield). 1H NMR (200 MHz, CD3CN): δ = 8.23–
8.07 (m, 2 H), 7.79 (d, J = 7.8 Hz, 1 H), 7.64 (td, J = 7.7, 0.9 Hz, 1 H),
7.52–7.41 (m, 1 H), 6.53 (d, J = 19.1 Hz, 1 H), 1.68–1.08 (m, 18 H),
0.84 (t, J = 7.2 Hz, 9 H), 0.15 (s, 9 H) ppm. 13C NMR (75 MHz, CD3CN):
δ = 141.7, 141.3, 136.4, 135.4, 135.1, 132.8, 129.0, 128.9, 122.2 (q,
JC,F = 333 Hz), 28.8 (JSn,C = 22 Hz, 3 × C), 27.0 (JSn,C = 64 Hz, 3 × C),
16.3 (JSn,C = 369 Hz, 3 × C), 13.9, –1.2 ppm. 19F NMR (188 MHz,
CD3CN): δ = –79.1 (s) ppm. HRMS (ESI): calcd. for C24H43F3NOSSiSn
[M + H]+ 598.1902; found 598.2161.
Imino(trifluoromethyl)(2-vinylphenyl)-λ6-sulfanone (4a): White
solid (according to GP A: 44 mg, 63 % yield; according to GP B,
starting from the potassium vinyltrifluoroborate: 52 mg, 73 % yield);
Microwave gram-scale experiment. Performed according to GP B,
except for the dilution and the reaction time. For 1 (1 g, 3 mmol),
DMF (15 mL) and water (5 mL) were used, and the reaction time
was extended to 90 min. M.p. 47 °C. 1H NMR (200 MHz, CD3CN): δ =
8.22 (d, J = 7.9 Hz, 1 H), 7.92–7.69 (m, 3 H), 7.66–7.53 (m, 1 H), 5.80
(dd, J = 17.4, 0.8 Hz, 1 H), 5.47 (dd, J = 11.1, 0.7 Hz, 1 H), 4.84 (s, 1
H) ppm. 13C NMR (75 MHz, CDCl3): δ = 141.3, 135.6, 133.9, 132.8,
129.2, 128.5, 128.3, 119.2, 121.2 (q, J = 333 Hz) ppm. 19F NMR
(188 MHz, CD3CN): δ = –78.6 (s) ppm. HRMS (ESI): calcd. for
C9H9F3NOS [M + H]+ 236.0357; found 236.0358.
(E)-Imino(trifluoromethyl){2-[2-(trimethylsilyl)vinyl]phenyl}-λ6-
sulfanone (4b): Colorless oil (according to GP A: 77 mg, 83 % yield).
1H NMR (300 MHz, CDCl3): δ = 8.23 (d, J = 8.1 Hz, 1 H), 7.99 (d, J =
19.0 Hz, 1 H), 7.81–7.62 (m, 2 H), 7.47 (t, J = 7.7 Hz, 1 H), 6.48 (d,
J = 19.0 Hz, 1 H), 3.77 (s, 1 H), 0.17 (s, J = 14.1 Hz, 8 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 142.3, 140.2, 137.1, 135.4, 132.6, 129.1,
128.4, 128.1, 121.3 (q, J = 333 Hz), –1.4 ppm. 19F NMR (188 MHz,
CDCl3): δ = –77.5 (s) ppm. HRMS (ESI): calcd. for C12H17F3NOSSi [M
+ H]+ 308.0752; found 308.0744.
General Procedure (GP A): Preparation of Sulfoximines 4 and 3
through Stille Coupling: o-Iodosulfoximine (0.3 mmol, 1 equiv.),
LiCl (4 mg, 30 mol-%), CuI (4 mg, 7 mol-%), and the PdCl2(PPh3)2
catalyst (15 mg, 7 mol-%) were placed in a microwave vial and then
diluted with DMF (3 mL). The selected tributyltin precursor
(3 equiv.) was added to the solution and the vial was flushed with
argon and sealed. The reaction mixture was then irradiated under
microwave conditions at 100 °C for 20 min.
For the Isolation of Derivatives 3: After cooling, EtOAc was added
to the resulting solution and the mixture successively extracted sev-
eral times with H2O. The organic layer was dried with magnesium
sulfate and concentrated under reduced pressure. The residue was
finally purified by an alumina chromatography column with use of
the appropriate eluent (pentane/diethyl ether 95:5) to afford the
pure compound 3.
For the Isolation of Derivatives 4: After cooling, EtOAc was added
to the resulting solution and the mixture was successively extracted
several times with HCl (1 N). The organic layer was dried with mag-
nesium sulfate and concentrated under reduced pressure. The resi-
due was finally purified by preparative TLC with use of the appropri-
ate eluent (pentane/diethyl ether or toluene) to afford the pure
compound 4. If a mixture of products 3 and 4 was obtained, the
mixture was then added to a suspension of silica gel (200 mg) in
CH2Cl2 (5 mL) and stirred overnight. The silica was filtered off, and
(E)-Imino{4-methyl-2-[2-(trimethylsilyl)vinyl]phenyl}-
(trifluoromethyl)-λ6-sulfanone (4c): Yellow pale oil (according to
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GP A: 58 mg, 60 % yield). 1H NMR (200 MHz, CDCl3): δ = 8.10 (d, J =
8.2 Hz, 1 H), 7.94 (d, J = 18.9 Hz, 1 H), 7.56 (s, 1 H), 7.28 (d, J =
8.2 Hz, 1 H), 6.46 (d, J = 18.9 Hz, 1 H), 3.66 (s, 1 H), 2.46 (s, 3 H),
0.17 (s, 9 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 146.8, 142.1, 140.4,
7.40 (m, 2 H), 7.40–7.17 (m, 3 H), 6.83 (s, 1 H), 3.87 (s, 2 H), 3.61 (s,
1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 145.0, 144.5, 143.8, 142.2,
134.9, 133.1, 133.0, 132.0, 130.4, 128.6, 126.7, 125.2, 123.7, 121.3,
121.1 (q, J = 334 Hz), 45.3 ppm. 19F NMR (188 MHz, CDCl3): δ =
136.6, 132.8, 129.8, 129.0, 125.4, 121.4 (q, J = 333 Hz), 21.8, –1.3 –78.2 (s) ppm. HRMS (ESI): calcd. for C16H13F3NOS [M + H]+
ppm. 19F NMR (188 MHz, CDCl3): δ = –78.6 (s) ppm. HRMS (ESI):
324.0670; found 324.0670.
calcd. for C13H18F3NNaOSSi [M + Na]+ 344.0728; found 344.0730.
(E)-Imino(2-styrylphenyl)(trifluoromethyl)-λ6-sulfanone (4i): Yel-
low pale solid (according to GP B, starting from the trans-2-phenyl-
vinylboronic acid pinacol ester: 50 mg, 54 % yield). M.p. 77 °C. 1H
NMR (300 MHz, CDCl3): δ = 8.30 (dd, J = 12.4, 3.6 Hz, 2 H), 7.88 (d,
J = 7.8 Hz, 1 H), 7.72 (t, J = 7.4 Hz, 1 H), 7.60–7.45 (m, 3 H), 7.44–
7.28 (m, 3 H), 7.06 (d, J = 16.1 Hz, 1 H), 3.65 (br. s, 1 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 140.9, 136.8, 135.6, 133.9, 133.1, 128.9,
128.8, 128.7, 128.5, 127.9, 127.3, 125.2, 121.3 (q, J = 333 Hz) ppm.
19F NMR (188 MHz, CDCl3): δ = –78.5 (s) ppm. HRMS (ESI): calcd. for
C15H13F3NOS [M + H]+ 312.0670; found 312.0680.
Imino[2-(prop-1-en-1-yl)phenyl](trifluoromethyl)-λ6-sulfanone
(4d): Colorless oil [according to GP A, starting from a mixture of
E,Z-tributyl(prop-1-en-1-yl)stannane in a 20:80 ratio: 69 mg of a mix-
ture E/Z stereoisomers in a 20:80 ratio was obtained with 89 %
yield]. For the mixture E/Z, 20:80: 1H NMR (300 MHz, CDCl3): δ =
8.27 (d, J = 8.0 Hz, 1 H), 8.22 (d, J = 8.1 Hz, 0.2 H), 7.73–7.59 (m, 0.4
H), 7.53–7.35 (m, 3 H), 7.05 (d, J = 11.6 Hz, 1 H), 6.21 (dq, J = 15.4,
7.1 Hz, 0.2 H), 5.95 (dq, J = 11.6, 7.1 Hz, 1 H), 3.52 (s, 1 H), 1.93 (dd,
J = 6.7, 1.6 Hz, 0.7 H), 1.71 (dd, J = 7.1, 1.8 Hz, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 141.5, 141.4, 135.4, 134.9, 133.9, 133.0, 132.7,
131.9, 129.6, 129.2, 129.0, 127.8, 127.4, 127.3, 121.2 and 121.1 (2 × q,
J = 333 Hz) ppm. 19F NMR (188 MHz, CDCl3): δ = –78.5 (s), –78.6 (s)
ppm. HRMS (ESI): calcd. for C10H11F3NOS [M + H]+ 250.0513; found
250.0506.
(E)-Imino[2-(4-methylstyryl)phenyl](trifluoromethyl)-λ6-sulfan-
one (4j): White solid [according to GP B, starting from the potas-
sium (E)-trifluoro(4-methylstyryl)borate: 94 mg, 96 % yield]. M.p.
1
103 °C. H NMR (300 MHz, CDCl3): δ = 8.29 (dd, J = 11.7, 8.9 Hz, 2
H), 7.87 (d, J = 7.8 Hz, 1 H), 7.70 (t, J = 7.4 Hz, 1 H), 7.48 (dd, J =
7.5, 4.3 Hz, 3 H), 7.21 (d, J = 8.0 Hz, 2 H), 7.05 (d, J = 16.1 Hz, 1 H),
3.77 (s, 1 H), 2.38 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 141.0,
138.7, 135.5, 134.1, 133.8, 133.0, 129.6, 128.6, 128.3, 127.7, 127.2,
124.1, 121.3 (q, J = 333 Hz), 21.4 ppm. 19F NMR (188 MHz, CDCl3):
δ = –78.5 (s) ppm. HRMS (ESI): calcd. for C16H15F3NOS [M + H]+
326.0826; found 326.0821.
According to GP B, starting from the potassium trans-1-propenyltri-
fluoroborate: 71 mg, 95 % yield. 1H NMR (200 MHz, CDCl3): δ = 8.19
(t, J = 11.0 Hz, 1 H), 7.75–7.58 (m, 2 H), 7.55–7.32 (m, 2 H), 6.21 (dq,
J = 13.4, 6.7 Hz, 1 H), 3.71 (d, J = 6.8 Hz, 1 H), 1.93 (dd, J = 6.6,
1.4 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 141.5, 135.4, 132.7,
131.9, 129.2, 127.9, 127.8, 127.4, 121.3 (q, J = 333.0 Hz), 19.0 ppm.
19F NMR (188 MHz, CDCl3): δ = –78.5 (s) ppm.
(E)-Imino[2-(4-methoxystyryl)phenyl](trifluoromethyl)-λ6-
sulfanone (4k): Yellow pale oil [according to GP B, starting from
the potassium (E)-trifluoro(4-methoxystyryl)borate: 77 mg, 75 %
[2-(Furan-2-yl)phenyl](imino)(trifluoromethyl)-λ6-sulfanone
1
(4e): Colorless oil (according to GP A: 49 mg, 59 % yield). H NMR
1
yield]. H NMR (300 MHz, CDCl3): δ = 8.27 (d, J = 8.1 Hz, 1 H), 8.17
(200 MHz, CD3CN): δ = 8.33 (d, J = 7.7 Hz, 1 H), 7.91–7.79 (m, 1 H),
7.78–7.61 (m, 3 H), 6.70 (d, J = 3.3 Hz, 1 H), 6.55 (dd, J = 3.3, 1.8 Hz,
1 H), 4.62 (s, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 149.4, 143.4,
135.0, 133.5, 133.3, 133.2, 131.1, 129.3, 121.1 (q, J = 333.6 Hz), 111.7,
111.6 ppm. 19F NMR (188 MHz, CD3CN): δ = –77.0 (s) ppm. HRMS
(ESI): calcd. for C11H9F3NOS [M + H]+ 276.0306; found 276.0305.
(E)-Imino[2-(pent-1-en-1-yl)phenyl](trifluoromethyl)-λ6-sulfan-
one (4f): Yellow pale solid [according to GP B, starting from the (E)-
1-pentenylboronic acid pinacol ester: 47 mg, 56 % yield]. 1H NMR
(300 MHz, CD3CN): δ = 8.18 (d, J = 8.1 Hz, 1 H), 7.77 (dt, J = 15.6,
7.0 Hz, 2 H), 7.61–7.38 (m, 2 H), 6.31 (dt, J = 15.6, 7.0 Hz, 1 H), 4.76
(s, 1 H), 2.23 (td, J = 7.9, 1.3 Hz, 2 H), 1.51 (dq, J = 14.7, 7.3 Hz, 2
H), 0.96 (t, J = 7.3 Hz, 3 H) ppm. 13C NMR (75 MHz, CD3CN): δ =
142.0, 137.8, 136.6, 133.4, 130.0, 129.2, 128.6, 127.3, 122.3 (q, J =
333.1 Hz), 35.9, 22.8, 13.9 ppm. 19F NMR (188 MHz, CD3CN): δ =
–77.6 (s) ppm. HRMS (ESI): calcd. for C12H15F3NOS [M + H]+
278.0826; found 278.0825.
(d, J = 16.1 Hz, 1 H), 7.84 (d, J = 7.9 Hz, 1 H), 7.67 (t, J = 7.5 Hz, 1
H), 7.57–7.38 (m, 3 H), 7.02 (d, J = 16.1 Hz, 1 H), 6.91 (d, J = 8.7 Hz,
2 H), 3.81 (s, J = 8.4 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
160.1, 135.4, 133.4, 133.0, 129.6, 128.6, 128.4, 128.1, 127.4, 121.3 (q,
J = 333.0 Hz), 114.3, 55.3 ppm. 19F NMR (188 MHz, CDCl3): δ = –78.5
(s) ppm. HRMS (ESI): calcd. for C17H15F3NO2S [M + H]+ 342.0776;
found 342.0776.
(E)-Imino(trifluoromethyl){2-[4-(trifluoromethyl)styryl]phenyl}-
λ6-sulfanone (4l): White solid {according to GP B, starting from the
trans-2-[4-(trifluoromethyl)phenyl]vinylboronic acid: 51 mg, 45 %
yield}. M.p. 141 °C. 1H NMR (200 MHz, CDCl3): δ = 8.34 (t, J = 11.2 Hz,
2 H), 8.00–7.70 (m, 2 H), 7.60–7.49 (m, 5 H), 7.05 (d, J = 16.2 Hz, 1
H), 3.79 (s, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 140.3 (d, J =
1.0 Hz), 140.2, 135.7, 133.3, 132.1, 130.3 (q, J = 32.5 Hz), 129.0, 128.9,
128.6, 127.9, 127.4, 125.9 (q, J = 3.8 Hz), 124.3 (q, J = 271.3 Hz),
121.3 (q, J = 333 Hz) ppm. 19F NMR (188 MHz, CDCl3): δ = –63.1 (s),
–78.6 (s) ppm. HRMS (ESI): calcd. for C16H12F6NOS [M + H]+
380.0544; found 380.0553.
(E)-[2-(4-Fluorostyryl)phenyl](imino)(trifluoromethyl)-λ6-sulfan-
one (4m): Colorless oil [according to GP B, starting from the trans-
2-(4-fluorophenyl)vinylboronic acid: 67 mg, 68 % yield]. 1H NMR
(200 MHz, CDCl3): δ = 8.25 (dd, J = 8.1, 1.1 Hz, 1 H), 8.15 (d, J =
16.1 Hz, 1 H), 7.81 (dd, J = 8.1, 1.1 Hz, 1 H), 7.68 (td, J = 7.7, 1.0 Hz,
1 H), 7.54–7.41 (m, 3 H), 7.12–6.88 (m, 3 H), 3.74 (s, 1 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 163.0 (d, J = 248.6 Hz), 140.8, 135.6, 133.2,
133.1 (d, J = 3.4 Hz), 132.6, 128.9, 128.8 (d, J = 6.6 Hz), 128.5, 128.0,
125.0, 121.3 (q, J = 333 Hz), 115.9 (d, J = 21.8 Hz) ppm. 19F NMR
(188 MHz, CDCl3): δ = –78.6 (s), –111.4 to –116.1 (m) ppm. HRMS
(ESI): calcd. for C15H12F4NOS [M + H]+ 330.0576; found 330.0581.
(E)-Imino[2-(3-phenylprop-1-en-1-yl)phenyl](trifluoromethyl)-
λ6-sulfanone (4g): Yellow pale oil (according to GP B, starting from
the trans-3-phenyl-1-propen-1-ylboronic acid: 79 mg, 80 % yield).
1H NMR (300 MHz, CDCl3): δ = 8.24 (d, J = 7.8 Hz, 1 H), 7.65 (m, 3
H), 7.50–7.38 (m, 1 H), 7.39–7.15 (m, 5 H), 6.31 (dt, J = 15.5, 7.0 Hz,
1 H), 3.61 (d, J = 6.8 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
141.2, 139.5, 135.5, 135.2, 132.9, 129.4, 128.9, 128.7, 128.2, 127.9,
127.7, 126.5, 121.3 (q, J = 333 Hz), 39.8 ppm. 19F NMR (188 MHz,
CDCl3): δ = –78.5 (s) ppm. HRMS (ESI): calcd. for C16H15F3NOS [M +
H]+ 326.0826; found 326.0822.
[2-(1H-Inden-2-yl)phenyl](imino)(trifluoromethyl)-λ6-sulfanone
(4h): Orange oil (according to GP B, starting from the 1H-indene-2-
boronic acid: 57 mg, 60 % yield). 1H NMR (200 MHz, CDCl3): δ =
8.34 (d, J = 8.1 Hz, 1 H), 7.67 (dtd, J = 15.4, 7.5, 3.8 Hz, 2 H), 7.54–
(E)-[2-(4-Chlorostyryl)phenyl](imino)(trifluoromethyl)-λ6-sulfan-
one (4n): Yellow pale oil [according to GP B, starting from the trans-
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2-(4-Chlorophenyl)vinylboronic acid: 80 mg, 77 % yield]. 1H NMR
(200 MHz, CDCl3): δ = 8.34–8.18 (m, 2 H), 7.89–7.65 (m, 2 H), 7.59–
7.42 (m, 3 H), 7.40–7.30 (m, 2 H), 6.98 (d, J = 16.2 Hz, 1 H), 3.83 (s,
1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 140.5, 135.6, 135.4, 134.3,
133.2, 132.5, 129.1, 128.8, 128.6, 128.4, 128.2, 125.8, 121.3 (q, J =
333 Hz) ppm. 19F NMR (188 MHz, CDCl3): δ = –78.6 (s) ppm. HRMS
(ESI): Calcd for C15H12F3NOSCl [M + H]+ 346.0280; found 346.0280.
NMR (300 MHz, CDCl3): δ = 8.20 (d, J = 8.1 Hz, 1 H), 7.75 (d, J =
4.0 Hz, 2 H), 7.63 (dd, J = 8.5, 4.3 Hz, 1 H), 7.56–7.50 (m, 1 H), 5.73
(d, J = 17.2 Hz, 1 H), 5.52 (d, J = 11.2 Hz, 1 H), 2.24 (t, J = 6.7 Hz, 2
H), 1.54–1.30 (m, 4 H), 0.89 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 141.7, 136.4, 133.2, 132.8, 129.6, 128.6, 126.1,
122.2 (q, J = 338.7 Hz), 120.3, 72.3, 60.9 (d, J = 1.6 Hz), 31.6, 22.0,
18.4, 13.8 ppm. 19F NMR (188 MHz, CDCl3): δ = –71.8 (s) ppm. HRMS
(ESI): calcd. for C15H17F3NOS [M + H]+ 316.0994; found 316.0983.
1-(Trifluoromethyl)-1λ4-benzo[e][1,2]thiazine 1-Oxide (8): Sulf-
oximine 6 (100 mg, 0.36 mmol, 1 equiv.) was added to a solution
of the Hoveyda–Grubbs 2nd generation catalyst (11 mg, 5 mol-%)
in CH2Cl2 (20 mL). The reaction was stirred for 6 h at 40 °C. The
solvent was removed under vacuum, and the crude residue was
purified by preparative silica gel column chromatography to afford
the cyclic sulfoximine 8 (82 mg, 98 %) as a colorless oil. 1H NMR
(200 MHz, CDCl3): δ = 7.90 (d, J = 8.1 Hz, 1 H), 7.76 (t, J = 7.4 Hz, 1
H), 7.63–7.34 (m, 2 H), 7.14 (d, J = 6.8 Hz, 1 H), 6.20 (d, J = 6.8 Hz,
1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 140.1, 138.3, 135.9, 128.2,
127.2, 126.7, 120.6 (q, J = 333.1 Hz), 112.3, 104.2 ppm. 19F NMR
(188 MHz, CDCl3): δ = –80.4 (s) ppm. HRMS (ESI): calcd. for
C9H6F3NOSNa [M + Na]+ 256.0020; found 256.0020.
(E)-Imino[4-methyl-2-(4-methylstyryl)phenyl](trifluoromethyl)-
λ6-sulfanone (4o): Yellow pale solid [according to GP B, starting
from the potassium (E)-trifluoro(4-methylstyryl)borate: 78 mg, 81 %
yield]. M.p. 104 °C. 1H NMR (200 MHz, CDCl3): δ = 8.26–8.08 (m, 2
H), 7.64 (s, 1 H), 7.43 (d, J = 8.1 Hz, 2 H), 7.25 (d, J = 8.5 Hz, 1 H),
7.16 (d, J = 8.0 Hz, 2 H), 7.00 (d, J = 16.1 Hz, 1 H), 3.71 (s, 1 H), 2.46
(s, 3 H), 2.35 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 146.8,
140.9, 138.6, 134.2, 133.5, 133.2, 129.6, 129.2, 128.6, 127.2, 125.4,
124.2, 121.4 (q, J = 333 Hz), 21.8, 21.4 ppm. 19F NMR (188 MHz,
CDCl3): δ = –78.7 (s) ppm. HRMS (ESI): calcd. for C17H17F3NOS [M +
H]+ 340.0983; found 340.0981.
Preparation of (Z)-(Prop-1-en-1-ylimino)(trifluoromethyl)(2-cin-
ylphenyl)-λ6-sulfanone (6): Under argon, sulfoximine 4a (200 mg,
0.85 mmol, 1 equiv.), K2CO3 (235 mg, 1.7 mmol, 2 equiv.), and CuI
(24 mg, 0.12 mmol, 0.15 equiv.) were placed in a dry Schlenk tube.
Toluene (5 mL) and DMEDA (190 μL, 1.7 mmol, 2 equiv.) were
added, and the reaction mixture was stirred at room temperature.
After 10 min, a mixture of (Z)-bromopropene (180 μL, 2.1 mmol,
2.5 equiv.) was added. The mixture was heated at 110 °C for 4 h;
then it was cooled to room temperature, diluted with diethyl ether,
and filtered through a thin pad of Celite. The solvents were re-
moved under vacuum, and the crude residue was purified by pre-
parative TLC (SiO2, dichloromethane/petroleum ether 2:8) to give 6
(202 mg, 86 %) as a colorless oil. 1H NMR (300 MHz, CD3CN): δ =
8.24 (d, J = 8.2 Hz, 1 H), 7.89–7.69 (m, 3 H), 7.67–7.57 (m, 1 H), 6.39
(ddd, J = 5.7, 3.1, 1.5 Hz, 1 H), 5.81 (d, J = 17.3 Hz, 1 H), 5.49 (d, J =
11.1 Hz, 1 H), 5.12 (p, J = 6.9 Hz, 1 H), 1.75 (dd, J = 6.7, 1.1 Hz, 3 H)
ppm. 13C NMR (75 MHz, CD3CN): δ = 141.5, 137.1, 134.7, 133.1,
130.4, 129.8, 124.5, 122.4 (q, J = 340.2 Hz), 120.0, 118.2, 117.4 (d,
J = 1.0 Hz), 11.6 ppm. 19F NMR (188 MHz, CDCl3): δ = –72.9 (s)
ppm. HRMS (ESI): calcd. for C12H13F3NOS [M + Na]+ 276.0670; found
276.0672.
Acknowledgments
A. L. B. thanks the French Ministry of Research for a PhD grant.
A. P. thanks Labex Charmmmat for a postdoctoral fellowship.
We gratefully thank Centre National de la Recherche Scientif-
ique (CNRS) and the French Fluorine Network (GIS fluor). Dr.
Mauduit is acknowledged for the gift of catalyst M73-SIPr. We
acknowledge Pr. Jérôme Thibonnet from the University of Tours
as well as Dr. François Metz (Solvay-Rhodia Lyon) for the gift of
chemicals, Aurélie Damond for mass spectra analysis, Flavien
Bourdreux for NMR assistance, and Dr. Karen Wright for the
careful reading and improvement of the English.
Keywords: Fluorinated compounds · Palladium · Cross-
coupling · Sulfur · Sulfoximines
Preparation of N-Alkynyl Sulfoximines 7: Sulfoximine 4a (60 mg,
0.26 mmol, 1 equiv.), Na2CO3 (28 mg, 0.52 mmol, 2 equiv.), and
CuCl2 (6 mg, 0.026 mmol, 0.10 equiv.) were placed in a dry Schlenk
tube under oxygen. Dioxane (2 mL) and pyridine (25 μL, 0.31 mmol,
1.2 equiv.) were added, and the reaction mixture was heated to
70 °C. A solution of the selected alkyne (1.5 equiv.) in dioxane (1 mL)
was then added, and the mixture was stirred at 70 °C for 4 h. The
reaction mixture was cooled to room temperature, diluted with di-
chloromethane, and filtered through a thin pad of Celite. The sol-
vents were removed under vacuum, and the crude residue was puri-
fied by preparative silica gel column chromatography (dichloro-
methane/petroleum ether 1:9) neutralized with Et3N (5 %).
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[(Phenylethynyl)imino](trifluoromethyl)(2-vinylphenyl)-λ6-
1
sulfanone (7a): Yellow oil (with phenylacetylene, 60 mg, 72 %) H
NMR (200 MHz, CD3CN): δ = 8.25 (d, J = 8.2 Hz, 1 H), 7.91 (d, J =
4.0 Hz, 2 H), 7.71–7.49 (m, 2 H), 7.40–7.22 (m, 5 H), 5.87 (d, J =
17.2 Hz, 1 H), 5.59 (d, J = 11.1 Hz, 1 H) ppm. 13C NMR (75 MHz,
CD3CN): δ = 142.4, 138.5, 133.7, 133.5, 132.2, 131.1, 130.3, 129.4,
128.3, 125.5, 124.9, 122.2 (q, J = 336.5 Hz), 121.6, 83.4, 62.0 (d, J =
1.6 Hz) ppm. 19F NMR (188 MHz, CD3CN): δ = –71.3 (s) ppm. HRMS
(ESI): calcd. for C17H13F3NOS [M + H]+ 336.0670; found 336.0677.
[(n-Butylethynyl)imino](trifluoromethyl)(2-vinylphenyl)-λ6-
sulfanone (7b): Yellow pale oil (with 1-hexyne, 47 mg, 58 %) 1H
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Received: February 23, 2018
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
Sulfoximines Functionalization
A.-L. Barthelemy, A. Prieto, P. Diter,
J. Hannedouche, M. Toffano,
E. Anselmi,* E. Magnier* .................. 1–8
Facile Preparation of Vinyl S-Tri-
fluoromethyl NH Aryl Sulfoximines
o-Iodo S-perfluoroalkylated sulfoxim- a metathesis–cyclization reaction de-
ines were functionalized by palladium livered a cyclic sulfoximine.
catalysis with various alkenes. Further,
VIP Manuscript by Anselmi and Magnier: Trifluoromethyl Sulfoximines by Pd-catalyzed #CrossCoupling Reactions
#OutstandingOrganics @EmmanuelMagnier
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DOI: 10.1002/ejoc.201800324
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