Generation of β-Halo Vinylsulfones through a Multicomponent Reaction with Insertion of Sulfur Dioxide

Article abstract of DOI:10.1002/chem.201701465

A four-component reaction of terminal alkynes, aryldiazonium tetrafluoroborates, sulfur dioxide surrogate of DABCO?(SO₂)₂, and potassium halide in the presence of copper(I) chloride (10 mol %) gives rise to β-halo vinylsulfones with good stereoselectivity. The vicinal difunctionalization of alkynes through sulfonylation and halogenation with the insertion of sulfur dioxide works efficiently. A plausible mechanism is proposed, which includes a radical process.

Full text of DOI:10.1002/chem.201701465

DOI: 10.1002/chem.201701465
Communication
&
Multicomponent Reactions
Generation of b-Halo Vinylsulfones through a Multicomponent
Reaction with Insertion of Sulfur Dioxide
Yuanchao Xiang,[a] Yunyan Kuang,*[a] and Jie Wu*[a, b]
worth–Emmons reactions.[10] Recent efforts have focused on
Abstract: A four-component reaction of terminal alkynes,
the sulfonylation of alkynes with sulfonyl compounds or cross-
aryldiazonium tetrafluoroborates, sulfur dioxide surrogate
coupling reactions of sulfonyl compounds with alkenes.[11,12]
of DABCO·(SO2)2, and potassium halide in the presence of
For example, (Z)-b-halo vinylsulfones could be obtained
copper(I) chloride (10 mol%) gives rise to b-halo vinylsul-
through the reaction of alkynes with arylsulfonyl chlorides or
fones with good stereoselectivity. The vicinal difunctionali-
arylsulfonohydrazides.[12] As mentioned above, the insertion of
zation of alkynes through sulfonylation and halogenation
sulfur dioxide would be promising and attractive for the incor-
with the insertion of sulfur dioxide works efficiently. A
poration of a sulfonyl group. Therefore, we initiated a program
plausible mechanism is proposed, which includes a radical
for the generation of b-halo vinylsulfones by using sulfur diox-
process.
ide as the source.
In the past few years, methods for the synthesis of sulfonyl
compounds through the insertion of sulfur dioxide have devel-
oped rapidly,[13,14] especially after the sulfur dioxide surrogate
Due to the importance of sulfones in organic synthesis and
medicinal chemistry,[1,2] the introduction of a sulfonyl unit into
[13a]
of DABCO·(SO2)2
was used as the source of sulfur dioxide.
small molecules has attracted much attention. Among the
methods for the incorporation of a sulfonyl group, recent ef-
forts have been aimed towards radical reactions from the
point of view of reactivity and selectivity. Usually, sulfonyl hal-
ides/selenides/azides/cyanides/hydrazides, sulfinates, and sul-
finic acids were utilized in the sulfonylative process through re-
ductive or oxidative approaches.[3,4] Recently, using sulfur diox-
ide as the source for the introduction of the sulfonyl unit into
small molecules has been employed as a replacement.[5] For
example, compared to the conventional approaches by using
sulfonyl compounds for the synthesis of 3-sulfonated coumar-
ins,[6] the strategy through insertion of sulfur dioxide in a radical
process for introducing the sulfonyl group was successfully es-
tablished under more mild condition.[7]
We have also been involved in this field, with the expectation
to provide efficient approaches for the access to sulfonyl-con-
taining pharmaceuticals. Recently, we described an efficient
process for the generation of arylsulfonyl radicals using a reac-
tion of aryldiazonium salts with DABCO·(SO2)2 under mild con-
ditions.[7] During the reaction process, the presence of DABCO
was also crucial for the successful transformation. The DABCO+
C
radical cation generated in situ would act as a carrier for
a single electron transfer (SET). Prompted by this result and
the importance of b-halo vinylsulfones, we conceived that b-
halo vinylsulfones would be formed through a four-component
reaction of terminal alkynes, aryldiazonium tetrafluoroborates,
sulfur dioxide surrogate of DABCO·(SO2)2, and metal hailde. The
proposed synthetic route is presented in Scheme 1. We envi-
sioned that a radical process would be involved with the inser-
tion of sulfur dioxide. A tandem radical addition of aryl radical
to sulfur dioxide and alkyne would provide an alkenyl radical.
As part of our interests in sulfones, we focused on the explo-
ration of b-halo vinylsulfones due to their versatile reactivity in
organic synthesis. It is well known that vinylsulfones have
been widely used in organic transformations as well as in phar-
maceuticals.[8,9] The elaboration of b-halo vinylsulfones through
coupling reactions would provide diverse vinylsulfones. The
typical methods for the generation of b-halo vinylsulfones in-
clude Knoevenagel-type condensation and Horner–Wads-
In the presence of DABCO+ radical cation (generated in situ),
C
an alkenyl cation would be formed, which would be subse-
quently trapped by halide to produce b-halo vinylsulfones. The
stereoselectivity of the final outcome would depend on the
steric hindrance during the transformation.
[a] Y. Xiang, Prof. Dr. Y. Kuang, Prof. Dr. J. Wu
Department of Chemistry, Fudan University
220 Handan Road, Shanghai 200433 (P. R. China)
Fax: (+86)21–6564-1740
E-mail: jie_wu@fudan.edu.cn
[b] Prof. Dr. J. Wu
State Key Laboratory of Organometallic Chemistry
Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences
345 Lingling Road, Shanghai 200032 (P. R. China)
Supporting information for this article can be found under:
https://doi.org/10.1002/chem.201701465.
Scheme 1. A proposed synthetic route to b-halo vinylsulfones through
a four-component reaction including the insertion of sulfur dioxide.
Chem. Eur. J. 2017, 23, 1 – 5
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We thus started to explore the practicability of the proposed
route in Scheme 1. Initially, a reaction of 1-ethynyl-4-methyl-
benzene 1a, 4-methylphenyldiazonium tetrafluoroborate 2a,
DABCO·(SO2)2, and sodium iodide in MeCN at room tempera-
ture was investigated (Table 1, entry 1). However, we did not
Table 2. Scope investigation for the reaction of alkynes 1, aryldiazonium
tetrafluoroborates 2, DABCO·(SO2)2, and potassium iodide.[a]
Table 1. Initial studies for the reaction of 1-ethynyl-4-methylbenzene 1a,
4-methylphenyldiazonium tetrafluoroborate 2a, DABCO·(SO2)2, and metal
iodide.[a]
Entry
“IÀ”
Additive
Solvent
T
[8C]
Yield
[%][b]
1
2
3
4
5
6
7
8
NaI
KI
KI
KI
KI
KI
KI
KI
KI
KI
KI
KI
KI
KI
–
–
CuI
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
DCE
25
25
25
25
25
45
60
80
90
80
80
80
80
80
0
17
20
24
5
40
47
62
59
CuCl
CuOAc
CuCl
CuCl
CuCl
CuCl
–
CuCl
CuCl
CuCl
CuCl
9
10
11
12
13
14
32
trace
trace
0
1,4-dioxane
DMSO
THF
trace
[a] Isolated yield based on alkyne 1.
[a] Reaction conditions: 1-ethynyl-4-methylbenzene 1a (0.2 mmol), DAB-
CO·(SO2)2 (0.16 mmol, 0.8 equiv), 4-methylphenyldiazonium tetrafluorobo-
rate 2a (0.4 mmol, 2.0 equiv), iodide (0.4 mmol, 2.0 equiv), solvent
(2.5 mL), under Ar protection. [b] Isolated yield based on 1-ethynyl-4-
methylbenzene 1a.
partners in the reaction of 1-ethynyl-4-methylbenzene 1a,
DABCO·(SO2)2, and potassium iodide. Different functional
groups including methyl, methoxy, chloro, bromo, fluoro, and
ester were all tolerated under the standard conditions. The
structure of product (E)-3b was illustrated after X-ray crystal-
lography analysis.[15] Various alkynes were examined subse-
quently, and the desired products were obtained as expected.
It is noteworthy that 2-ethynylthiophene is a good reactant as
well, affording the corresponding product 3k in 48% yield.
However, alkyl-substituted alkynes were not effective during
the transformations. This could be rationalized by the lower
stability of the alkyl-substituted alkenyl radical intermediate
than the corresponding aryl-substituted alkenyl radical.
observe the formation of the desired product. To our delight,
the corresponding product 3a was obtained in 17% yield
when potassium iodide was used instead of sodium iodide
(Table 1, entry 2). We postulated that the presence of a copper
salt would facilitate the single electron transfer during the re-
action process. Thus, several copper salts were examined as
additives. Gratifyingly, the yield was increased to 24% in the
presence of copper(I) chloride (10 mol%) (Table 1, entry 4). Fur-
ther screening of the temperature revealed that the reaction
worked efficiently at 808C, leading to the desired b-iodo vinyl-
sulfone 3a in 62% yield (Table 1, entry 8), whereas compound
3a was afforded in 32% yield in the absence of copper(I) chlo-
ride (Table 1, entry 10). Reactions in other solvents were ex-
plored subsequently (Table 1, entries 11–14). However, the re-
sults were inferior. Interestingly, b-iodo vinylsulfone 3a was ob-
tained in the (E)-configuration exclusively.
We further evaluated the four-component reaction of termi-
nal alkynes using potassium bromide in an effort to obtain b-
bromo vinylsulfones. The results are shown in Table 3. Al-
though the preparation of b-bromo vinylsulfones 4 was ac-
complished under the copper(I) chloride-catalyzed conditions,
a mixture of stereoisomers was provided. As we mentioned
above, the stereoselectivity of the final outcome would
depend on the steric hindrance during the combination of an
alkenyl cation with halide. Thus, it is reasonable that (E)-b-iodo
vinylsulfones were produced exclusively, whereas b-bromo vi-
nylsulfones were formed as a mixture of stereoisomers. During
the transformations, (E)-b-bromo vinylsulfones were obtained
as the major products. The structure of compound (E)-4a was
confirmed by X-ray crystallography analysis as well.[15]
We next explored the scope of this four-component reaction
of terminal alkynes, aryldiazonium tetrafluoroborates, DABCO·(-
SO2)2, and potassium iodide catalyzed by copper(I) chloride
under the above optimized conditions (Table 2). From Table 2,
it seemed that all reactions worked smoothly to provide the
corresponding (E)-b-iodo vinylsulfones in moderate to good
yields. Various aryldiazonium tetrafluoroborates were good
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Communication
In summary, an efficient route for the synthesis of b-halo vi-
nylsulfones through a four-component reaction of terminal al-
kynes, aryldiazonium tetrafluoroborates, sulfur dioxide surro-
gate of DABCO·(SO2)2, and potassium halide in the presence of
copper(I) chloride (10 mol%) has been developed. The vicinal
difunctionalization of alkynes through sulfonylation and halo-
genation with the insertion of sulfur dioxide works efficiently.
The desired b-halo vinylsulfones are generated with good ste-
reoselectivity. (E)-b-iodo vinylsulfones are produced exclusively,
whereas (E)-b-bromo vinylsulfones are obtained as the major
products. A plausible mechanism is also proposed, which
would undergo a radical process.
Table 3. Scope investigation for the reaction of alkynes 1, aryldiazonium
tetrafluoroborates 2, DABCO·(SO2)2, and potassium bromide.[a]
Experimental Section
General experimental procedure for the four-component reac-
tion: Potassium halide (iodide or bromide; 2.0 equiv, 66.4 mg),
DABCO·(SO2)2 (0.8 equiv, 38.4 mg) and copper(I) chloride (10 mol%)
were mixed with aryldiazonium tetrafluoroborate 2 (2.0 equiv,
0.4 mmol) in a tube and dissolved by MeCN (2.5 mL) under Ar2 at-
mosphere (the flask was evacuated and backfilled with Ar2 three
times before MeCN was added). Then alkyne 1 (0.2 mmol) was
added to the mixture. The mixture was stirred at 808C (potassium
iodide) or 258C (potassium bromide). After completion of the reac-
tion as indicated by TLC, the mixture was purified directly by flash
column chromatography (EtOAc/n-hexane, 1:8) to provide the de-
sired product 3 or 4.
[a] Isolated yield based on alkyne 1.
Based on our previous report,[7] we envisioned that this four-
component reaction might proceed through a radical process.
As expected, the model reaction in Table 1 could not take
place when 2.0 equiv of 2, 2, 6, 6-tetramethyl-1-piperidinyloxy
(TEMPO) was added. Therefore, a plausible mechanism is pro-
posed as shown in Scheme 2. The combination of aryldiazoni-
Acknowledgements
Financial support from the National Natural Science Founda-
tion of China (Nos. 21372046, 21532001, 21202022) is gratefully
acknowledged.
Conflict of interest
The authors declare no conflict of interest.
Keywords: alkyne
·
aryldiazonium tetrafluoroborate
·
potassium halide · sulfur dioxide · b-halo vinylsulfone
[1] For selected examples, see: a) X. Yang, F. Cheng, Y-.D. Kou, S. Pang, Y.-C.
Shen, Y.-Y. Huang, N. Shibata, Angew. Chem. Int. Ed. 2017, 56, 1510;
Angew. Chem. 2017, 129, 1532; b) X. Sun, F. Yu, T. Ye, X. Liang, J. Ye,
Chem. Eur. J. 2011, 17, 430; c) Q. Zhu, Y. Lu, Org. Lett. 2009, 11, 1721;
d) Q. Zhu, L. Cheng, Y. Lu, Chem. Commun. 2008, 6315; e) R. A. Lꢁpez-
Pꢂrez, R. Machꢃn, J. Adrio, J. C. Carretero, Angew. Chem. 2007, 119, 9421.
[2] For selected examples, see: a) D. C. Meadows, J. Gervay-Hague, Med.
Res. Rev. 2006, 26, 793; b) B. A. Frankel, M. Bentley, R. G. Kruger, D. G.
McCafferty, J. Am. Chem. Soc. 2004, 126, 3404; c) R. van der Westhuyzen,
E. Straussa, J. Am. Chem. Soc. 2010, 132, 12853; d) P. Chauhan, C.
Hadad, A. H. Lꢁpez, S. Silvestrini, V. L. Parola, E. Frison, M. Maggini, M.
Prato, T. Carofiglio, Chem. Commun. 2014, 50, 9493; e) E. Dunny, W.
Doherty, P. Evans, J. P. G. Malthouse, D. Nolan, A. J. S. Knox, J. Med.
Chem. 2013, 56, 6638.
Scheme 2. Investigation of the mechanism.
um cation with DABCO·(SO2)2 would provide sulfur dioxide, ni-
trogen, aryl radical, and tertiary amine radical cation B through
a complex A.[7] Then, the addition of aryl radical to sulfur diox-
ide would occur to produce arylsulfonyl radical D, which
would attack alkyne 1 leading to the more stable (Z)-alkenyl
radical E.[16] Subsequently, copper (I) chloride would promote
the oxidation of alkenyl radical E to alkenyl cation F by
a single electron transfer. Nucleophilic attack of halide to al-
kenyl cation F preferably from the less-hindered side would
give rise to the corresponding b-halo vinylsulfone 3 or 4.
[3] For selected examples, see: a) N. Taniguchi, Synlett 2011, 1308; b) N. Ta-
niguchi, Tetrahedron 2014, 70, 1984; c) A. U. Meyer, S. Jꢄger, D. P. Hari, B.
Kçnig, Adv. Synth. Catal. 2015, 357, 2050; d) A. Kariya, T. Yamaguchi, T.
Nobuta, N. Tada, T. Miura, A. Itoh, RSC Adv. 2014, 4, 13191; e) Y. Xu, X.
Tang, W. Hu, W. Wu, H. Jiang, Green Chem. 2014, 16, 3720; f) H.-S. Li, G.
Chem. Eur. J. 2017, 23, 1 – 5
www.chemeurj.org
3
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
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Communication
Liu, J. Org. Chem. 2014, 79, 509; g) W. Wei, J. Wen, D. Yang, J. Du, J. You,
H. Wang, Green Chem. 2014, 16, 2988; h) D. Xia, T. Miao, P. Li, L. Wang,
Chem. Asian J. 2015, 10, 1919; i) Q. Lu, J. Zhang, F. Wei, Y. Qi, H. Wang,
Z. Liu, A. Lei, Angew. Chem. Int. Ed. 2013, 52, 7156; Angew. Chem. 2013,
125, 7297; j) Q. Lu, J. Zhang, P. Peng, G. Zhang, Z. Huang, H. Yi, J. T.
Miller, A. Lei, Chem. Sci. 2015, 6, 4851.
[13] a) B. Nguyen, E. J. Emmett, M. C. Willis, J. Am. Chem. Soc. 2010, 132,
16372; b) E. J. Emmett, C. S. Richards-Taylor, B. Nguyen, A. Garcia-Rubia,
R. Hayter, M. C. Willis, Org. Biomol. Chem. 2012, 10, 4007; c) L. Martial,
Synlett 2013, 24, 1595; d) W. Li, H. Li, P. Langer, M. Beller, X.-F. Wu, Eur. J.
Org. Chem. 2014, 3101; e) W. Li, M. Beller, X.-F. Wu, Chem. Commun.
2014, 50, 9513; f) X. Wang, L. Xue, Z. Wang, Org. Lett. 2014, 16, 4056;
g) A. S. Deeming, C. J. Russell, M. C. Willis, Angew. Chem. Int. Ed. 2015,
54, 1168; Angew. Chem. 2015, 127, 1184; h) C. C. Chen, J. Waser, Org.
Lett. 2015, 17, 736; i) A. S. Deeming, C. J. Rusell, A. J. Hennessy, M. C.
Willis, Org. Lett. 2014, 16, 150; j) B. N. Rocke, K. B. Bahnck, M. Herr, S.
Lavergne, V. Mascitti, C. Perreault, J. Polivkova, A. Shavnya, Org. Lett.
2014, 16, 154; k) E. J. Emmett, B. R. Hayter, M. C. Willis, Angew. Chem.
Int. Ed. 2013, 52, 12679; Angew. Chem. 2013, 125, 12911; l) E. J. Emmett,
B. R. Hayter, M. C. Willis, Angew. Chem. Int. Ed. 2014, 53, 10204; Angew.
Chem. 2014, 126, 10368; m) A. Shavnya, S. B. Coffey, A. C. Smith, V. Mas-
citti, Org. Lett. 2013, 15, 6226; n) M. W. Johnson, S. W. Bagley, N. P.
Mankad, R. G. Bergman, V. Mascitti, F. D. Toste, Angew. Chem. Int. Ed.
2014, 53, 4404; Angew. Chem. 2014, 126, 4493; o) A. Shavnya, K. D.
Hesp, V. Mascitti, A. C. Smith, Angew. Chem. Int. Ed. 2015, 54, 13571;
Angew. Chem. 2015, 127, 13775; p) A. S. Deeming, C. J. Russell, M. C.
Willis, Angew. Chem. Int. Ed. 2016, 55, 747; Angew. Chem. 2016, 128,
757; q) A. S. Tsai, J. M. Curto, B. N. Rocke, A. R. Dechert-Schmitt, G. K.
Ingle, V. Mascitti, Org. Lett. 2016, 18, 508; r) W. Zhang, M. Luo, Chem.
Commun. 2016, 52, 2980; s) J. Sheng, Y. Li, G. Qiu, Org. Chem. Front.
2017, 4, 95; t) A. T. Davies, J. M. Curto, S. W. Bagley, M. C. Wiliis, Chem.
Sci. 2017, 8, 1233; u) B. Du, Y. Wang, W. Sha, P. Qian, H. Mei, J. Han, Y.
Pan, Asian J. Org. Chem. 2017, 6, 153; v) A. L. Tribby, I. Rodrꢃguez, S.
Shariffudin, N. D. Ball, J. Org. Chem. 2017, 82, 2294; w) N.-W. Liu, S.
Liang, G. Manolikakesa, Adv. Synth. Catal. 2017, 359, 1308.
[14] a) D. Zheng, Y. An, Z. Li, J. Wu, Angew. Chem. Int. Ed. 2014, 53, 2451;
Angew. Chem. 2014, 126, 2483; b) S. Ye, J. Wu, Chem. Commun. 2012,
48, 7753; c) S. Ye, J. Wu, Chem. Commun. 2012, 48, 10037; d) S. Ye, H.
Wang, Q. Xiao, Q. Ding, J. Wu, Adv. Synth. Catal. 2014, 356, 3225; e) Y.
An, D. Zheng, J. Wu, Chem. Commun. 2014, 50, 11746; f) Y. Luo, X. Pan,
C. Chen, L. Yao, J. Wu, Chem. Commun. 2015, 51, 180; g) D. Zheng, Y. Li,
Y. An, J. Wu, Chem. Commun. 2014, 50, 8886; h) D. Zheng, Y. Kuang, J.
Wu, Org. Biomol. Chem. 2015, 13, 10370; i) D. Zheng, R. Mao, Z. Li, J.
Wu, Org. Chem. Front. 2016, 3, 359; j) Y. Li, D. Zheng, H. Xia, J. Wu, Org.
Chem. Front. 2016, 3, 574; k) R. Mao, D. Zheng, H. Xia, J. Wu, Org. Chem.
Front. 2016, 3, 693; l) K. Zhou, H. Xia, J. Wu, Org. Chem. Front. 2016, 3,
865; m) D. Zheng, M. Chen, L. Yao, J. Wu, Org. Chem. Front. 2016, 3,
985; n) Y. Li, Y. Xiang, Z. Li, J. Wu, Org. Chem. Front. 2016, 3, 1493; o) R.
Mao, Z. Yuan, R. Zhang, Y. Ding, X. Fan, J. Wu, Org. Chem. Front. 2016, 3,
1498; p) T. Liu, D. Zheng, Y. Ding, X. Fan, J. Wu, Chem. Asian J. 2017, 12,
465; q) Y. Xiang, Y. Li, Y. Kuang, J. Wu, Chem. Eur. J. 2017, 23, 1032.
[15] CCDC 1534886 [(E)-3b] and 1540861 [(E)-4a] contain the supplementary
crystallographic data for this paper. These data are provided free of
charge by The Cambridge Crystallographic Data Centre.
[4] For selected examples, see: a) T. Taniguchi, A. Idota, H. Ishibashi, Org.
Biomol. Chem. 2011, 9, 3151; b) X. Li, Y. Xu, W. Wu, C. Jiang, C. Qi, H.
Jiang, Chem. Eur. J. 2014, 20, 7911; c) S. Tang, Y. Wu, W. Liao, R. Bai, C.
Liu, A. Lei, Chem. Commun. 2014, 50, 4496; d) K. Sun, Y. Lv, Z. Zhu, Y.
Jiang, J. Qi, H. Wu, Z. Zhang, G. Zhang, X. Wang, RSC Adv. 2015, 5,
50701; e) X. Li, X. Xu, X. Shi, Tetrahedron Lett. 2013, 54, 3071; f) G. Rong,
J. Mao, H. Yan, Y. Zheng, G. Zhang, J. Org. Chem. 2015, 80, 4697; g) W.
Wei, C. Liu, D. Yang, J. Wen, J. You, Y. Suo, H. Wang, Chem. Commun.
2013, 49, 10239; h) X. Li, X. Xu, C. Zhou, Chem. Commun. 2012, 48,
12240.
[5] For reviews: a) G. Liu, C. Fan, J. Wu, Org. Biomol. Chem. 2015, 13, 1592;
b) P. Bisseret, N. Blanchard, Org. Biomol. Chem. 2013, 11, 5393; c) A. S.
Deeming, E. J. Emmett, C. S. Richards-Taylor, M. C. Willis, Synthesis 2014,
46, 2701.
[6] W. Yang, S. Yang, P. Li, L. Wang, Chem. Commun. 2015, 51, 7520.
[7] D. Zheng, J. Yu, J. Wu, Angew. Chem. Int. Ed. 2016, 55, 11925; Angew.
Chem. 2016, 128, 12104.
[8] For selected examples, see: a) M. N. Noshi, A. El-awa, E. Totrres, P. L.
Fuchs, J. Am. Chem. Soc. 2007, 129, 11242; b) O. Arjona, R. Menchaca, J.
Plumet, Org. Lett. 2001, 3, 107; c) S. Sulzer-Mossꢂ, A. Alexakis, J. Mareda,
G. Bollot, G. Bernardinelli, Y. Filinchuk, Chem. Eur. J. 2009, 15, 3204; d) H.
Kumamoto, K. Deguchi, T. Wagata, Y. Furuya, Y. Odanaka, Y. Kitade, H.
Tanaka, Tetrahedron 2009, 65, 8007; e) Y. Fang, Z. Luo, X. Xu, RSC Adv.
2016, 6, 59661; f) S. Cai, Y. Xu, D. Chen, L. Li, Q. Chen, M. Huang, W.
Weng, Org. Lett. 2016, 18, 2990; g) R. Singh, B. K. Allam, N. Singh, K.
Kumari, S. K. Singh, K. N. Singh, Org. Lett. 2015, 17, 2656.
[9] For selected examples, see: a) S. Liu, R. P. Hanzlik, J. Med. Chem. 1992,
35, 1067; b) W. R. Roush, S. L. Gwaltney II, J. Cheng, K. A. Scheidt, J. H.
McKerrow, E. Hansell, J. Am. Chem. Soc. 1998, 120, 10994; c) G. Wang, U.
Mahesh, G. Y. J. Chen, S. Q. Yao, Org. Lett. 2003, 5, 737; d) S. Liu, B.
Zhou, H. Yang, Y. He, Z.-X. Jiang, S. Kumar, L. Wu, Z.-Y. Zhang, J. Am.
Chem. Soc. 2008, 130, 8251; e) R. Ettari, E. Nizi, M. E. D. Francesco, M.-A.
Dude, G. Pradel, R. Vick, T. Schirmeister, N. Micale, S. Grasso, M. Zappa-
la, J. Med. Chem. 2008, 51, 988; f) I. D. Kerr, J. H. Lee, C. J. Farady, R.
Marion, M. Rickert, M. Sajid, K. C. Pandey, C. R. Caffrey, J. Legac, H. Eliza-
beth, J. H. McKerrow, C. S. Craik, P. J. Rosenthal, L. S. Brinen, J. Biol.
Chem. 2009, 284, 25697.
[10] a) D. A. R. Happer, B. E. Steenson, Synthesis 1980, 10, 806; b) S. Chodroff,
W. F. Whitmore, J. Am. Chem. Soc. 1950, 72, 1073; c) M. Balasubramani-
an, V. Baliah, J. Chem. Soc. 1954, 1844; d) D. Dana, A. R. Dava-los, G.
Subramaniam, N. Afzal, W. H. Hersh, S. Kumar, Tetrahedron Lett. 2013,
54, 2717; e) P. R. Sacasa, J. Zayas, S. F. Wnuk, Tetrahedron Lett. 2009, 50,
5424; f) ref. [9c]; g) P. L. Fuchs, T. F. Braish, Chem. Rev. 1986, 86, 903; h) I.
Forristal, J. Sulfur Chem. 2005, 26, 163.
[16] a) U. Wille, Chem. Rev. 2013, 113, 813; b) K. Gilmore, B. Gold, R. J. Clark,
I. V. Alabugin, Aust. J. Chem. 2013, 66, 336.
[11] a) X. Zeng, L. Ilies, E. Nakamura, Org. Lett. 2012, 14, 954; b) X. Li, X. Shi,
M. Fang, X. Xu, J. Org. Chem. 2013, 78, 9499; c) Y. Gao, W. Wu, Y. Huang,
K. Huang, H. Jiang, Org. Chem. Front. 2014, 1, 361; d) W. Wei, J. Wen, D.
Yang, H. Jing, J. You, H. Wang, RSC Adv. 2015, 5, 4416.
[12] a) X. Liu, X. Duan, Z. Pan, Y. Han, Y. Liang, Synlett 2005, 1752; b) J.-P.
Wan, D. Hu, F. Bai, L. Wei, Y. Liu, RSC Adv. 2016, 6, 73132.
Manuscript received: April 2, 2017
Accepted Article published: April 4, 2017
Final Article published: && &&, 0000
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Chem. Eur. J. 2017, 23, 1 – 5
www.chemeurj.org
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ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Communication
COMMUNICATION
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Multicomponent Reactions
Y. Xiang, Y. Kuang,* J. Wu*
&& – &&
Generation of b-Halo Vinylsulfones
through a Multicomponent Reaction
with Insertion of Sulfur Dioxide
A four-component reaction of terminal
alkynes, aryldiazonium tetrafluorobo-
rates, sulfur dioxide surrogate of DAB-
CO·(SO2)2, and potassium halide in the
presence of copper(I) chloride (10
with good stereoselectivity. The vicinal
difunctionalization of alkynes through
sulfonylation and halogenation with the
insertion of sulfur dioxide works effi-
ciently.
mol%) gives rise to b-halo vinylsulfones
Chem. Eur. J. 2017, 23, 1 – 5
www.chemeurj.org
5
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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These are not the final page numbers! ÞÞ