CuSO4?·5H2O-H-phosphonate-catalyzed intermolecular C-S bond formation: Synthesis of (E)-vinyl alkylsulfones from alkynes and DMSO

Article abstract of DOI:10.1002/ejoc.201403278

A CuSO₄?·5H₂O-H-phosphonate-catalyzed synthesis of (E)-vinyl alkylsulfones from alkynes and widely available DMSO was developed. The present protocol provides an alternative approach to various vinyl sulfones, with the advantages of cheap catalysts, readily available starting materials, operational simplicity and high stereo- and regioselectivity.

Full text of DOI:10.1002/ejoc.201403278

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SHORT COMMUNICATION
DOI: 10.1002/ejoc.201403278
1
CuSO4·5H2O-H-Phosphonate-Catalyzed Intermolecular C–S Bond Formation:
Synthesis of (E)-Vinyl Alkylsulfones from Alkynes and DMSO
Jian-Yu Chen,[a] Xiao-Lan Chen,*[a] Xu Li,[a] Ling-Bo Qu,*[b] Qing Zhang,[a]
Li-Kun Duan,[a] Ying-Ya Xia,[a] Xin Chen,[a] Kai Sun,[a] Zhi-Dong Liu,[a] and
Yu-Fen Zhao[a,c]
6
Keywords: Copper / Phosphonates / C–S Bond Formation / Synthetic methods / Vinyl sulfones
A CuSO4·5H2O-H-phosphonate-catalyzed synthesis of (E)-
vinyl alkylsulfones from alkynes and widely available DMSO
was developed. The present protocol provides an alternative
approach to various vinyl sulfones, with the advantages of
cheap catalysts, readily available starting materials, opera-
tional simplicity and high stereo- and regioselectivity.
11
dergo highly stereoselective nucleophilic conjugate ad-
ditions[1] and cycloadditions,[2] epoxidation,[3] and re-
Introduction
Vinyl sulfones are widely used as building blocks in syn- duction reactions.[4] Vinyl sulfones have been used for the
thetic organic chemistry. For example, the chemical versatil- total synthesis of natural products.[5] Furthermore, the sulf-
ity of the sulfone moiety enables these compounds to un- one group can be removed at the end of a synthetic se-
16
21
Scheme 1. Methods for the synthesis of vinyl sulfones.
[a] College of Chemistry and Molecular Engineering, Zhengzhou quence by a variety of reductive, alkylative, or oxidative
methods.[6] Moreover, in medicinal chemistry, vinyl sulfones
University
Henan Province, Zhengzhou, 450052, P. R. China
represent a new class of inhibitors of enzymes, such as cys-
teine proteases,[7] dipeptidyl peptidase I (DPPI), and trans-
peptidase.[8] Because of their wide applications, various
methodologies for the synthesis of vinyl sulfones have been
developed. The traditionally available methodologies for the
synthesis of vinyl sulfones mainly include the following:
1) Knoevenagel condensations of aldehydes with sulfon-
E-mail: chenxl@zzu.edu.cn
http://www.zzu.edu.cn/
[b] Chemistry and Chemical Engineering School, Henan
University of Technology
26
Henan Province, Zhengzhou, 450052, P. R. China
[c] Department of Chemistry, Xiamen University,
Xiamen, 361005, P. R.China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201403278.
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X.-L. Chen, L.-B. Qu, et al.
SHORT COMMUNICATION
31
36
41
46
51
ylacetic acids (Scheme 1-a),[9] 2) Wittig reactions of carb- inic acids by gold-catalyzed intermolecular C–S bond for-
onyl compounds and sulfonylphosphones (Scheme 1-b),[10] mation was carried out by Shi and co-workers.[17] Herein,
3) β-elimination of selenosulfones,[11] and 4) oxidation of we report an efficient method for the synthesis of vinyl sulf-
the corresponding vinyl sulfides.[12] A number of alternative ones from alkynes and DMSO, by using a cheap, easily
methods towards vinyl sulfone synthesis have also been de- available CuSO4·5H2O-H-phosphonate catalytic system
veloped, such as the cross-coupling of sulfinate salts with (Scheme 1-d). To the best of our knowledge, it is the first
vinyl triflates, vinyl bromides, or alkenylboronic acids cata- example of using widely available DMSO together with rel-
lyzed by Cu or Pd catalysts (Scheme 1-c).[13] However, most atively benign and inexpensive CuSO4·5H2O to prepare
of these methods suffer from some limitations, such as inac- vinyl sulfones.
56
61
cessible starting materials, tedious procedures, relatively
harsh reaction conditions, or generation of large amounts
of unwanted byproducts. Recently, copper- or palladium-
Results and Discussion
catalyzed hydrosulfonylations of alkynes with sulfinic acids
or sodium sulfinates were developed.[14] Very recently, a
Initially, phenylacetylene (1a) and DMSO (2) were
copper-catalyzed aerobic decarboxylative sulfonylation of chosen as the substrates to optimize the reaction conditions.
alkenyl carboxylic acids with sodium sulfinates was devel- The screening results are shown in Table 1. The influences
oped by Guo and co-workers.[15] A synthesis of vinyl sulf- of four kinds of H-phosphonates on the model reaction
ones, by means of CuI-catalyzed aerobic oxidative N–S were first investigated (Table 1, Entries 1–4). The reaction
bond cleavage of sulfonyl hydrazides, followed by cross-cou- of 1a (1 equiv.) with 2 (1.0 mL) in the presence of
pling reactions with alkenes and aromatic compounds, was CuSO4·5H2O (25 mol-%), trifluoroacetic acid (TFA,
also described by Jiang and co-workers.[16] Moreover, the 0.2 equiv.) at 120 °C, and various H-phosphonates: diethyl
synthesis of α-substituted vinyl sulfones, rather than vinyl H-phosphonate (DEPH), diisopropyl H-phosphonate, di-
sulfones mentioned above, from terminal alkynes and sulf- propyl H-phosphonate, or diphenyl H-phosphonate
66
71
Table 1. Optimization of the reaction conditions.[a]
Entry
Cat
(mol-%)
H-phosphonate
HPO(OR)2
R (equiv.)
Acid
(equiv.)
Solvent
T
[°C]
Yield
[%]
(E)[b]
1
CuSO4·5H2O (25)
CuSO4·5H2O (25)
CuSO4·5H2O (25)
CuSO4·5H2O (25)
CuSO4·5H2O (25)
CuSO4·5H2O (25)
CuBr (25)
CH2CH3 (1.1)
CH(CH3)2 (1.1)
CH2CH2CH3 (1.1)
C6H5 (1.1)
TFA (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.2)
AcOH (0.2)
(CH3)3CO2H (0.2)
TsOH (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.2)
TFA (0.1)
–
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
120
120
120
120
120
120
120
120
120
120
120
120
120
80
100
140
120
120
120
120
120
120
120
120
120
89
2
86
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20[c]
21[c]
22[c]
23[c]
24
25
85
32
NR
38
trace
trace
50
NR
24
86
84
42
76
85
52
69
NR
trace
trace
trace
trace
45
–
CH2CH3(0.5)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CH2CH3 (1.1)
CuI (25)
Cu(OAc)·2H2O (25)
NiCl2·6H2O (25)
CuSO4·5H2O (10)
CuSO4·5H2O (40)
CuSO4·5H2O (60)
CuSO4·5H2O (25)
CuSO4·5H2O (25)
CuSO4·5H2O (25)
CuSO4·5H2O (25)
CuSO4·5H2O (25)
CuSO4·5H2O (25)
CuSO4·5H2O (25)
CuSO4·5H2O (25)
CuSO4·5H2O (25)
CuSO4·5H2O (25)
CuSO4·5H2O (25)
CuSO4·5H2O (25)
toluene
1,4-dioxane
(CH3CO)2O
DMSO
DMSO
30
[a] Reaction conditions: 1a (0.5 mmol), 2 (1.0 mL), dialkyl H-phosphonate (0–1.1 equiv.), catalyst (10–60 mol-%) and TFA (0–0.2 equiv.)
at 120 °C for 10 h. [b] Isolated yields. [c] DMSO (2.5 mmol) in solvent (1.0 mL).
2
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CuSO4·5H2O-H-Phosphonate Catalyzed C–S Bond Formation
(1.1 equiv.) afforded the desired product (E)-[2-(methyl-sulf- amount was above 25 mol-% (Table 1, Entries 1, 11–13).
onyl)vinyl]benzene (3a), in 89, 86, 85, and 32% yields, The subsequent investigation of the influence of tempera-
respectively (Table 1, entries 1–4). The ideal amount of H- ture (Table 1, Entries 1 and 14–16) revealed that the reac-
phosphonate was then explored. When the reaction was tion proceeded most efficiently at 120 °C (Table 1, Entry 1).
carried out in the absence of diethyl H-phosphonate, the It can be seen that the yield increased over the temperature
product was not obtained (Table 1, Entry 5). Addition of range of 80 to 120 °C, from 42 to 89%, and then gradually
0.5 equiv. of diethyl H-phosphonate resulted in a yield of decreased to 85% after 140 °C was reached (Table 1, Entries
38% (Table 1, Entry 6). Increasing the amount of diethyl 1 and 14–16). The effects of the acid used were also investi-
H-phosphonate to 1.1 equiv. (Table 1, Entry 1) gave a yield gated (Table 1, Entries 1 and 17–19). A higher yield of 3a
of 89%. Subsequently, the influence of a variety of catalysts (89%) was obtained when TFA was used (Table 1, Entry 1). 101
on the model reaction was investigated (Table 1, Entries 1 Other acids resulted in relatively low yields of 3a: i.e.,
and 7–10). Among the catalysts employed (i.e., CuSO4· AcOH (52%), (CH3)3CCOOH (69%), TsOH (0%) (Table 1,
5H2O, CuBr, CuI, Cu(OAc)2·H2O and NiCl2·6H2O), Entries 17–19). The choice of solvent also highly affected
CuSO4·5H2O (Table 1, Entry 1) turned out to be the best, the reaction efficiency. Compared with DMSO, DMF, tolu-
giving a yield of 89%. The influence of the amount of ene, 1,4-dioxane, and (CH3CO)2O resulted in only trace 106
CuSO4·5H2O was investigated. It was found that the yield amounts of the product (Table 1, Entries 20–23). The opti-
increased from 24 to 89% with the increase of the catalyst mal amount of TFA was finally investigated (Table 1, En-
from 10 to 25 mol-%, but the yield decreased when the tries 1 and 24–25), which indicated that 0.2 equiv. of TFA
76
81
86
91
96
Table 2. Scope of the hydrosulfonylation.[a]
[a] Reaction conditions: 1 (1.0 mmol), 2 (2.0 mL), DEPH (1.1 mmol), CuSO4·5H2O (25 mol-%), TFA (20 mol-%) at 120 °C for 10 h. [b]
Isolated yields.
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X.-L. Chen, L.-B. Qu, et al.
SHORT COMMUNICATION
(Table 1, Entry 1) resulted in the most satisfactory yield.
111 Further screening of the reaction time showed that 10 h was
the best choice. Therefore, optimal reaction conditions in-
volved 1.1 equiv. diethyl H-phosphonate, 25 mol-%
CuSO4·5H2O and 20 mol-% TFA in DMSO at 120 °C for
10 h.
116
With the optimized conditions in hand, we next explored
the scope of this hydrosulfonylation of various alkynes. As
shown in Table 2, a large variety of aryl terminal alkynes,
with both electron-donating (OCH3, CH3, C2H5, n-C3H7,
n-C4H9, n-C5H11) and electron-withdrawing groups (F, Cl,
121 Br) on the aryl ring, reacted smoothly with 2, affording the
corresponding vinyl alkylsulfones 3a–3r in good to excellent
yields from 55 to 89%. The substituents on the benzene
ring had no obvious influence on the corresponding yields.
Functionalities such as halogen, methoxy, acetamide and
126 cyano groups were well tolerated in the reaction processes.
In addition, the reaction of 1-ethynylcyclohexene with
DMSO efficiently afforded the conjugated sulfone 3s in
82% yield. Most importantly, heteroaromatic alkynes also
gave the corresponding products 3t–3w in good to excellent
131 yields from 60 to 75%. To our delight, the reaction of 1-
phenylpropyne, an internal alkyne, with 2 afforded the vinyl
sulfone 3x in a satisfactory yield (68%). All products ob-
tained (3a–3x) had an E configuration, which indicated a
high stereoselectivity of this hydrosulfonylation reaction
136 (spectra and characterization data can be found in the Sup-
porting Information).
A plausible mechanism for the hydrosulfonylation reac-
tion is depicted in Scheme 2. It is worth mentioning here
that the dialkyl H-phosphonates occupy a major position
141 in organophosphorus chemistry, since they are frequent
intermediates in the synthesis of a variety of bioactive
phosphorus-containing products.[18] A property that is most
important from the point of view of the synthetic applica-
tions is the tautomeric equilibrium between their phosphite
146 and phosphonate forms: the tricoordinate phosphorus form
Scheme 2. Plausible mechanism.
and the tetracoordinate phosphorus form.[19] Here, the ion 11 was protonated to give diethyl H-phosphonate 4.
cheap, easily prepared and preserved diethyl H-phos- Here, the selective addition of radical 12 to the β position
phonate 4 (tetracoordinate form) existed with its tautomer rather than α position of terminal alkyne 1, afterwards, led
diethyl phosphite 5 (tricoordinate form). Initially, diethyl to the formation of the more stable α-carbon-centered vinyl 171
151 phosphite 5 and DMSO 2 coordinated with Cu2+ to form radical 13 rather than less stable β-carbon-centered vinyl
the copper complex 6 with concomitant formation of an radical 14. The selective addition of 12 to 1 well explains
intramolecular hydrogen bond (O–H···O=S) to give a six- the high regioselectivity of the hydrosulfonylation reaction.
membered ring. Subsequently proton transfer from the OH Then vinyl radical 13 interacted with water to yield the final
group to the oxygen atom of the S=O group occurred, lead- vinyl sulfone 3 and hydroxy radical.[20] Meanwhile the vinyl 176
156 ing to the formation of complex 7. It is worth emphasizing radical 13 could react with another molecule of 4 to pro-
here that complex 7 could be in resonance with 8. The two duce the final product 3 together with phosphite radical 15.
positive charges at the sulfur atom of resonance structure 8 Then dialkyl phosphate 16 might possibly be formed by a
implied a great sensitivity of the protonated sulfinyl group termination reaction of phosphite radical 15 and hydroxy
to nucleophilic attack. A molecule of water can sub- radical in the related reaction process.
181
161 sequently attack the protonated sulfinyl group of 7, to give
More synthetic experiments were subsequently carried
pentavalent intermediate 9. Then intermediate 9 immedi- out to give support to the reaction mechanism mentioned
ately loses a molecule of methane as well as a proton, to above (Scheme 3). Isotopic labeling experiments with H218O
give copper complex 10.
and D2O were then performed. The reaction of phenyl-
Copper complex 10 then homolytically cleaved to a phos- acetylene with DMSO in the presence of 10 equiv. H218O 186
166 phonate anion 11, Cu+ and sulfonyl radical 12. Cu+ was afforded 18O-labeled 3a (Scheme 3-a), demonstrating clearly
oxidized back to Cu2+ by oxygen in air, and phosphonate that the additional oxygen atom of 3a originated from H2O
4
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CuSO4·5H2O-H-Phosphonate Catalyzed C–S Bond Formation
Scheme 3. Proposed reaction of alkynes and DMSO with different reaction conditions. Reaction conditions: (a) 1a (1.0 mmol), 2 (2.0 mL),
DEPH (1.1 mmol), CuSO4 (25 mol-%), TFA (20 mol-%), H218O (10 equiv.) at 120 °C for 10 h; (b) 1a (1.0 mmol), 2 (2.0 mL), DEPH
(1.1 mmol), CuSO4 (25 mol-%), TFA (20 mol-%), D2O (10 equiv.) at 120 °C for 10 h; (c) 1a (1.0 mmol), 2 (2.0 mL), DEPH (1.1 mmol),
CuSO4·5H2O (25 mol-%), TFA (20 mol-%) at 120 °C under nitrogen atmosphere for 10 h; (d) 1a (1.0 mmol), 2 (2.0 mL), DEPH
(1.1 mmol), CuSO4·5H2O (25 mol-%), TFA (20 mol-%), TEMPO (3 equiv.) at 120 °C for 10 h.
instead of O2 in the air. The reaction was also carried out
Experimental Section
in the presence of 10 equiv. D2O, and D-labeled 3a was ob-
Experimental Procedures for the Synthesis of Vinyl Alkylsulfones
191 tained in this case (Scheme 3-b). As illustrated in the
(3a–3x): A 25-mL round-bottom flask containing a stirrer bar was
mechanism, it is O2 from the air that oxidizes Cu+ back to
charged with a terminal alkyne (1.0 mmol), DMSO (2.0 mL),
DEPH (1.1 mmol), CuSO4·5H2O (25 mol-%), and TFA (20 mol- 221
Cu2+. The reaction in the absence of oxygen was therefore
carried out. When the reaction was carried out under a ni-
trogen atmosphere, the corresponding vinyl sulfone 3a was
196 not obtained (Scheme 3-c). This result showed that the cop-
per-catalyzed hydrosulfonylation of alkynes required the
presence of oxygen. A radical pathway was also thought to
be involved in this reaction. The following radical-trapping
experiments might support this assumption. When TEMPO
201 (2,2,6,6-tetramethyl-1-piperidinyloxy), a well-known radi-
cal-capturing species, was added to the reaction system, the
reaction was completely suppressed (Scheme 3-c) (for de-
tails see the Supporting information).
%). The reaction was stirred at 120 °C for 10 h (monitored by
TLC). Upon completion of the reaction, the mixture was diluted
with brine (3.0 mL) and extracted with dichloromethane (10 mL
ϫ3). The organic layers were combined, washed with brine, dried
with anhydrous Na2SO4, and filtered. The solvents were removed
by rotary evaporator under reduced pressure and the residue was
purified by flash chromatography (silica gel, gradient eluent of pe-
troleum ether/ethyl acetate = 2:1) to yield the desired product.
226
Acknowledgments
Financial support from The National Natural Science Foundation
of China (No. 21072178), Innovation Specialist Projects of Henan
Province (No. 114200510023), Technology and Science talent Culti-
vation Project in Zhengzhou City (No. 112PLJRC359), The Special
Fund for the Doctoral Program of Higher Education (No.
20124101110003), Foundational and Frontier Technology Research
Foundation of Henan Province for their financial support (No.
132300410027).
231
236
Conclusions
206
A novel and practical CuSO4·5H2O-H-phosphonate-cat-
alyzed synthesis of (E)-vinyl alkylsulfones from alkynes and
widely available DMSO was developed. The cleavage of the
C–S bond of DMSO catalyzed by CuSO4·5H2O-H-phos-
phonate was the key step for this transformation. The
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Received: September 30, 2014 321
Published Online: ᭿
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Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O43278
/KAP1
Date: 03-12-14 18:22:25
Pages: 7
CuSO4·5H2O-H-Phosphonate Catalyzed C–S Bond Formation
Vinyl Sulfones
J.-Y. Chen, X.-L. Chen,* X. Li, L.-B. Qu,*
Q. Zhang, L.-K. Duan, Y.-Y. Xia,
X. Chen, K. Sun, Z.-D. Liu,
326
331
Y.-F. Zhao ......................................... 1–7
CuSO4·5H2O-H-Phosphonate-Catalyzed
Intermolecular C–S Bond Formation: Syn-
thesis of (E)-Vinyl Alkylsulfones from
Alkynes and DMSO
A
novel and efficient CuSO4·5H2O-H-
vinyl alkylsulfones from alkynes and widely
available DMSO was developed.
phosphonate-catalyzed synthesis of (E)-
Keywords: Copper / Phosphonates / C–S
Bond Formation / Synthetic methods /
Vinyl sulfones
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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