Stereoselective Vicinal Difunctionalization of Alkynes through a Three-Component Reaction of Alkynes, Sodium Sulfinates, and Togni Reagent

Article abstract of DOI:10.1002/adsc.201700278

Stereoselective vicinal difunctionalization of alkynes through trifluoromethylation and sulfonylation via a three-component reaction of alkynes, sodium sulfinates, and Togni reagent under catalyst- and additive-free conditions has been realized. This reaction proceeds at room temperature in dimethyl sulfoxide (DMSO), providing (E)-β-trifluoromethylvinyl sulfones in moderate to good yields. The advantages of this tandem radical process include extremely mild conditions, excellent stereoselectivity, and easy experimental operation. (Figure presented.).

Full text of DOI:10.1002/adsc.201700278

Title: Stereoselective Vicinal Difunctionalization of Alkynes through A
Three-Component Reaction of Alkynes, Sodium Sulfinates, and
Togni Reagent
Authors: Yuanchao Xiang, Yuewen Li, and yunyan kuang
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700278
Link to VoR: http://dx.doi.org/10.1002/adsc.201700278

10.1002/adsc.201700278
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc. 201((will be filled in by the editorial staff))
Stereoselective Vicinal Difunctionalization of Alkynes through A Three-
Component Reaction of Alkynes, Sodium Sulfinates, and Togni Reagent
Yuanchao Xiang,[a] Yuewen Li,[a] Yunyan Kuang,[*,a] and Jie Wu[*,ab]
[a]
Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433, China
Fax: (+86)-21-6564-1740
E-mail: jie_wu@fudan.edu.cn; yykuang@fudan.edu.cn
[b]
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
345 Lingling Road, Shanghai 200032, China
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract: Stereoselective vicinal difunctionalization of Keywords: alkyne; sodium sulfinate; sulfonylation;
alkynes through trifluoromethylation and sulfonylation via a trifluoromethylation; (E)-β-trifluoromethyl vinylsulfone
three-component reaction of alkynes, sodium sulfinates, and
Togni reagent under catalyst- and additive-free conditions is
realized. This reaction proceeds at room temperature in
DMSO, providing (E)-β-trifluoromethyl vinylsulfones in
moderate to good yields. The advantages of this tandem
radical process include extremely mild conditions, excellent
stereoselectivity, and experimentally operational ease.
pharmaceuticals.[6] As part of a program for the
Introduction
generation of trifluoromethylated small molecules
with the subsequent biological evaluations,[7] we
therefore started to explore the direct route for the
preparation of β-trifluoromethyl vinylsulfones.
The importance of vinylsulfones is known, since
vinyl sulfones are widely used as valuable synthetic
intermediates in organic synthesis for their excellent
abilities as Michael acceptors to participate in many
chemical reactions.[1] Additionally, vinylsulfone as a
privileged unit can be found in many natural products
and pharmaceuticals with diverse biological
activities.[2] Therefore, efforts for the synthesis of
vinylsulfones are continuously appeared.[3,4] For
example, Lei and co-workers described a photoredox
process for the preparation of α-substituted
vinylsulfones.[3f] On the other hand, introduction of
fluorine-containing groups into small molecules has
attracted much attention, especially in the drug
discovery process. The medicinal properties of drugs
or leading compounds could often be improved if
fluorine atom or fluorine-containing group is installed
into the molecules.[5] For instance, the activity of (2-
Currently, growing interest has been focused on
the vicinal difunctionalization of alkynes, leading to
the formation of highly functionalized olefins.[8-10]
Usually, good stereoselectivity could be observed in
most cases. The concomitant incorporation of
functional moieties into alkynes is efficient through
vicinal difunctionalization. Trifluoromethylation of
alkynes was developed as well. So far,
carbotrifluoromethylation, oxytrifluoromethylation,
iodotrifluoromethylation, hydrotrifluoromethylation,
and aminosulfonyltrifluoromethylation of alkynes
have been demonstrated as an efficient way to
2
directly accomplish Csp –CF3 bond formation
(Scheme 1).[11] For example, reaction of alkynes with
CF3I in the presence of a photoredox catalysis under
visible light would afford trifluoromethylated alkenyl
iodides.[9a] Although progress has been made in the
above processes for the trifluoromethylation of
(vinylsulfonyl)ethyl)benzene
was
significantly
improved when trifluoromethyl group was
incorporated into the β-position of vinylsulfone.[2b]
Recently, we also interested in the synthesis of
alkynes,
transition
metal-free
or
precious
photocatalyst-free trifluoromethylative process is still
challenging. Recently, we developed some
sulfones
due
to
their
importance
in
1
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10.1002/adsc.201700278
Advanced Synthesis & Catalysis
transformations via radical process under metal- and
additive-free conditions.[6a,b] Encouraged by these
results and vicinal difunctionalization of alkynes, we
envisioned that β-trifluoromethyl vinylsulfones could
be generated through trifluoromethylation and
sulfonylation of alkynes under suitable conditions as
well. We postulated a tandem radical process
(Scheme 1), which would involve the formation of
trifluoromethyl radical, its subsequent addition of
alkyne, and combination of sulfonyl radical to
CF3
I
O
O
S
R2
O
Na
+
CF3
2
O
1
R1
O
O
A
S
R2
O
O
R1
F3C
R1
F3C
S
R2
B
3
provide
the
corresponding
β-trifluoromethyl
vinylsulfones. Herein, we report our recent efforts for
the design and synthesis of (E)-β-trifluoromethyl
vinylsulfones through a three-component reaction of
alkynes, Togni reagent, and sodium sulfinates. This
reaction proceeded through trifluoromethylation and
Scheme 2. A plausible mechanism for the generation of
(E)-β-trifluoromethyl vinylsulfones
Results and Discussion
sulfonylation
of
alkynes
with
excellent
stereoselectivity under extremely mild conditions.
During the transformation, no catalyst and additives
are needed.
Having this original reaction mechanism in mind,
we chose 1-ethynyl-4-methylbenzene 1a as the model
substrate and sodium benzenesulfinate as the sulfonyl
source to initiate our studies. At the beginning, the
reaction was performed at room tempertaure in
acetonitrile. To our delight, we observed the
formation of desired product 3a in 32% yield with
(E)-configuration (Table 1, entry 1). Lower yield was
obtained when the solvent was replaced by DMF
(Table 1, entry 2). Gratifyingly, the reaction worked
well in DMSO, leading to the corresponding product
3a in 45% yield (Table 1, entry 3). The yield was
increased to 61% when 1.1 equivalent of Togni’s
reagent was employed in the reaction (Table 1, entry
4). The result was inferior when the reaction
temperature was changed to 40 °C (Table 1, entry 5).
a) previous work
FG
metal or photocatalyst
R
+
" CF3 " +
" FG "
CF3
R
R= Ar, alkyl; "FG" = NR2, alkyl, allkenyl, aryl, OR, I
b) this work
CF3
I
O
trifluoromethylation/
O
O
O
R1
S
sulfonylation
R2
R1
+
+
S
R2 ONa
DMSO, rt
F3C
O
R1
R2
highly selective radical tandem process
catalyst- and additive-free reaction
extremely mild conditions
SO2
CF3
excellent stereoselectivity
Table 1. Initial studies for the reaction of 1-ethynyl-4-
methylbenzene 1a, Togni reagent, with sodium
benzenesulfinate 2a [a]
Scheme 1. A proposed route for the generation of (E)-β-
trifluoromethyl vinylsulfones
CF3
O
O
O
S
I
p-MeC6H4
S
Initially, Togni’s reagent was selected as the
source for trifluoromethylation and sodium sulfonates
would be used for sulfonylation. A plausible
mechanism is shown in Scheme 2. We reasoned that
the combination of Togni’s reagent with sodium
sulfonate 2 would provide trifluoromethyl radical and
sulfonyl radical A concomitantly via a single electron
transfer (SET), with the release of 2-iodobenzonic
acid.[12] The subsequent attack of trifluoromethyl
radical to alkyne 1 would preferentially afford a (Z)-
isomer of alkenyl radical B, which would then be
trapped by sulfonyl radical A to produce α-
substituted-β-trifluoromethyl vinylsulfones 3 with
(E)-configuration.[13] From the proposed mechanism,
it seemed that no catalyst and additives were needed
to afford the final outcome. An alternative route
could not be excluded, which would undergo addition
of sulfonyl radical A to alkyne 1 and subsequently
trapped by trifluoromethyl radical. A competitive
pathway for the combination of sulfonyl radical A
with trifluoromethyl radical was also possible.
Ph
+
+
O
Ph
ONa
solvent
F3C
1a
O
2a
3a
Entry
Solvent
Yield (%)[b]
T (C)
1
2
MeCN
DMF
DMSO
DMSO
DMSO
25
25
25
25
40
32
9
45
61
35
3
4[c]
5[c]
[a]
Reaction conditions: 1-ethynyl-4-methylbenzene 1a
(0.2 mmol), Togni reagent (0.3 mmol), sodium
benzenesulfinate 2a (0.4 mmol) and solvent (2.0 mL),
[b]
13 h.
Isolated yield based on 1-ethynyl-4-
methylbenzene 1a. [c] In the presence of 1.1 equivalent
of Togni reagent.
Table 2. Scope investigation for the three-component
reaction of alkynes, sodium sulfinates, and Togni reagent.
[a]
2
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10.1002/adsc.201700278
Advanced Synthesis & Catalysis
of terminal alkynes. Without exception, all reactions
provided exclusively the (E)-β-trifluoromethyl
vinylsulfones anticipated in the plausible mechanism,
which exhibited excellent stereoselectivity during the
reaction process.
To gain more insights into the mechanism of this
three-component reaction of alkynes, sodium
sulfinates, and Togni reagent under catalyst- and
additive-free conditions as shown in Scheme 2, we
added 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)
into the reaction of 1-ethynyl-4-methylbenzene 1a,
sodium benzenesulfinate, and Togni reagent. It was
found that the reaction was terminated when 2.0
equivalent of TEMPO was employed. Additionally, a
control experiment under the standard conditions
without the addition of 1-ethynyl-4-methylbenzene
1a delivered ((trifluoromethyl)sulfonyl)benzene 4,
which was detected by 19F NMR (Scheme 3).
Moreover, reaction of 1-ethynyl-4-methylbenzene 1a
with trifluoromethylsulfonylbenzene 4 did not take
place under the standard conditions. These results
would provide evidence for the mechanism proposed
in Scheme 2.
CF3
I
O
O
S
O
O
+
S
4
Ph
ONa
Ph
CF3
DMSO, rt
2a
detected by 19F NMR
O
d -79.4
O
O
S
+
n.r.
[a] Isolated yield based on alkyne 1.
Ph
CF3
DMSO, rt
4
1a
With the above results in hand, we set out to
Scheme 3 Reaction of sodium benzenesulfinate with
explore the scope of this three-component reaction of
alkynes, sodium sulfinates, and Togni reagent under
catalyst- and additive-free conditions. The results are
summarized in Table 2. For various alkynes utilized,
it was found that different funactional groups could
be tolerated. Alkynes with electron-donating and
electron-withdrawing groups attached on the aromatic
ring all worked well to provide the desired products
in moderate to good yields. For example, the acetyl-
substituted product 3l was generated in 80% yield.
The cyano-substituted product 3n was obtained in
76% yield. 3-Ethynylpyridine was a good partner as
well, furnishing the corresponding product 3p in 55%
yield. Interestingly, The desilyl product 3q was
obtained when trimethylsilyl acetylene was employed
as the substrate. Moreover, sodium sulfinates were
further examined in the reactions of 1-chloro-4-
ethynylbenzene with Togni reagent. As expected, all
reactions proceeded well to produce the desired
products. Not only sodium benzenesulfinates but also
sodium heteroaromatic sulfonate or sodium alkyl
sulfonate could act as reactants in the transformations.
The X-ray structure of compound 3s was obtained in
the meantime.[14] However, compound 3v was
isolated in 15% yield when internal alkyne of
phenylpropyne was employed under the standard
condition. It might be caused by the larger steric
hindrance in disubstituted alkyne compared to those
Togni reagent
Conclusion
In summary, we have realized a directional
vicinal difunctionalization of alkynes through
trifluoromethylation and sulfonylation via a three-
component reaction of alkynes, sodium sulfinates,
and Togni reagent under catalyst- and additive-free
conditions. This reaction proceeds at room
temperature
in
DMSO,
providing
(E)-β-
trifluoromethyl vinylsulfones in moderate to good
yields. A broad reaction scope is demonstrated. A
possible mechanism is proposed, which indicates that
the formation of trifluoromethyl radical and sulfonyl
radical via combination of Togni reagent with sodium
sulfonate through a single electron transfer would be
the key. The advantages of this tandem radical
process include extremely mild conditions, excellent
stereoselectivity, and experimentally operational ease.
Experimental Section
General experimental procedure for the synthesis of
(E)-β-trifluoromethyl vinylsulfones under catalyst-
3
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10.1002/adsc.201700278
Advanced Synthesis & Catalysis
and additive-free conditions: Alkyne 1 (0.2 mmol)
was combined with Togni reagent (0.22 mmol, 69.52
mg) in a tube. After that, the tube was evacuated and
backfilled with N2 three times before DMSO (1.0
mL) was added. The solution was stirred for several
minutes, and sodium benzenesulfinate 2 (0.4 mmol)
in DMSO (2.0 mL) was added to the solution. The
mixture was then stirred for 13h. After completion of
reaction as indicated by TLC, water (10 mL) was
added and the mixture was extracted by EtOAc (3 x
10 mL). The solvent was evaporated and the residue
was purified by flash column chromatography
(EtOAc/n-hexane, 1:8) to give the desired product 3.
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Acknowledgements
Financial support from the National Natural
Science Foundation of China (Nos. 21372046,
21532001) is gratefully acknowledged.
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10.1002/adsc.201700278
Advanced Synthesis & Catalysis
FULL PAPER
Stereoselective Vicinal
Difunctionalization of Alkynes
through A Three-Component
Reaction of Alkynes, Sodium
Sulfinates, and Togni Reagent
CF3
no catalyst
no additive
O
O
O
R1
S
I
R2
R1
+
+
S
O
R2 ONa
DMSO, rt
F3C
highly selective radical tandem process
O
Adv. Synth. Catal. 2017, Volume, Page – Page
Yuanchao Xiang, Yuewen Li, Yunyan
Kuang*, and Jie Wu*
6
This article is protected by copyright. All rights reserved.