Iron(III) Chloride-Mediated Regio- and Stereoselective Chlorosulfonylation of Alkynes and Alkenes with Sodium Sulfinates

Article abstract of DOI:10.1002/adsc.201601211

The atom-economic and one-pot regio- and stereoselective addition of sodium arenesulfinates to either alkynes or alkenes can be achieved with an iron(III) chloride hexahydrate [FeCl₃?6 H₂O] catalytic system to afford β-haloalkenyl and β-chloroalkyl sulfones in moderate to good yields. (Figure presented.).

Full text of DOI:10.1002/adsc.201601211

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DOI: 10.1002/adsc.201601211
Iron(III) Chloride-Mediated Regio- and Stereoselective Chloro-
sulfonylation of Alkynes and Alkenes with Sodium Sulfinates
Kui Zeng,a Lang Chen,a,* Yi Chen,b Yongping Liu,b Yongbo Zhou,a
Chak-Tong Au,c and Shuang-Feng Yina,*
a
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan
University, Changsha 410082, Peopleꢀs Republic of China
Fax : (+86)-731-8882-1171; phone: (+86)-731-8882-1171; e-mail: huagong042cl@163.com or sf_yin@hnu.edu.cn
Medical College, Hunan University of Chinese Medicine, Changsha 410208, Peopleꢀs Republic of China
College of Chemistry and Chemical Engineering, Hunan Institute of Engineering, Xiangtan 411104, Hunan, Peopleꢀs
b
c
Republic of China
Received: November 1, 2016; Revised: December 23, 2016; Published online: && &&, 0000
Supporting information for this article can be found under: http://dx.doi.org/10.1002/adsc.201601211.
Abstract: The atom-economic and one-pot regio- catalytic system to afford b-haloalkenyl and b-
and stereoselective addition of sodium arenesulfi- chloro
nates to either alkynes or alkenes can be achieved
ACHTUNGTRENUNaNG lkyl sulfones in moderate to good yields.
with an iron(III) chloride hexahydrate [FeCl3·6H2O] Keywords: alkenes; alkynes; b-chloroalkyl sulfones;
b-haloalkenyl sulfones; sodium arenesulfinates
Introduction
sitive transition metal catalysts as well as poor toler-
ance towards functional groups. In recent years,
As basic starting materials, halide-functionalized al- sodium sulfinates have attracted significant attention,
kenyl compounds are versatile substrates in organic more than that of sulfonyl chlorides or sulfonyl hydra-
transformations.[1,2] Nonetheless, they are costly to zides, because sodium sulfinates are more air- and
buy due to their rare availability. On the other hand, moisture-stable. In 2014, Taniguchi et al. reported the
vinyl sulfone derivatives are valuable organic inter-
mediates in the fields of organic,[3] medicinal[4] and
materials chemistry.[5] For example, they are efficient
Michael acceptors[3b] as well as being good 2p part-
ners in cycloaddition reactions.[3g] Also, vinyl sulfone
derivatives can be readily exchanged by entities such
as hydrogen, alkyl, hydroxy, and carbonyl groups, and
are versatile reactive synthons in organic synthe-
ACHTUNGTRENNUNG
sis.[3a,c,e] Given the importance of vinyl sulfones and
the utility of halides, it is of great interest to make use
of the two moieties in organic synthesis.
Difunctionalization of alkynes is the most efficient
and direct method for the synthesis of b-haloalkenyl
sulfones (Scheme 1).[6] Transition metal-catalyzed di-
functionalization of alkynes with sulfonyl chlorides
has achieved various degrees of success in the control
of selectivity. In 2013, Xu et al. disclosed a method
for the synthesis of b-haloalkenyl sulfones using al-
kynes and sulfonyl hydrazides as starting materials,
where an iron halide was employed as the halide
source.[6b] However, the two methods have drawbacks
Scheme 1. Methods for the synthesis of b-haloalkenyl sul-
such as the need for special ligands and moisture-sen- fones.
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Table 1. Optimization of the reaction conditions.[a]
direct activation of alkynes with organic sodium sulfi-
nates for the preparation of b-haloalkenyl sulfones,
but there was the requirement for a special ligand. It
is well known that FeCl3 releases Cl ions in some radi-
cal reactions.[7] In the light of this information, we en-
visaged that the combination of sodium sulfinates
with FeCl3 may result in the chlorosulfonylation of al-
kynes.
In this work, b-haloalkenyl sulfones are synthesized
with good to excellent yield in the iron halide-mediat-
ed regio- and stereoselective halosulfonylation of al-
kynes with sodium sulfinates. It is noted that the reac-
tion also works well for alkenes with excellent toler-
ance toward functional groups, affording the corre-
sponding difunctionalization derivatives in good
yields.[8] The starting materials are simple and com-
mercially available, and the system shows excellent
selectivity and yields. The approach is superior to the
methods reported so far in the literature, in which li-
gands and air-sensitive reagents were used.
Entry Cl source
[2 equiv.]
Solvent
[2 mL]
T
Yield
[%][b]
[oC]
1[d]
2
CuCl2
CuCl2·2H2O
FeCl3
FeCl3
FeCl3
FeCl3
FeCl3
FeCl2
FeCl3·6H2O
FeCl3·6H2O
FeCl3·6H2O
FeCl3·6H2O
FeCl3·6H2O
FeCl3·6H2O
FeCl3·6H2O
FeCl3·6H2O
FeCl3·6H2O
FeCl3·6H2O
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
DMF
80
80
80
80
80
80
80
80
80
80
80
80
80
80
25
60
100
120
80
80
80
80
80
80
80
trace
23
3
N.D.[c]
24
4[e]
5[f]
6[d]
7[g]
8[d]
9
62
90
88
N.D.
94
26
39
63
78
89
18
78
91
93
40
82
10
11
12
13
14
15
16
17
18
DMSO
toluene
CH3CN
C2H5OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
Results and Discussion
19[h] FeCl3·6H2O
We initiated our study by using phenylacetylene (1a)
and 4-MeC6H4SO2Na (2a) as substrates to optimize
the reaction. As shown in Table 1, when FeCl3
(2.0 equiv.) is adopted, the reaction gives no forma-
tion of the target product, i.e., (E)-1-[(2-chloro-2-phe-
nylvinyl)sulfonyl]-4-methylbenzene (3a) (Table 1,
entry 3). To our delight, when 2.0 equiv. of
FeCl3·6H2O is used under the optimized conditions,
3a is generated in 94% yield (Table 1, entry 9), and
2.0 equiv. of FeCl3·6H2O proved to be the most suita-
ble for the reaction (Table 1, entries 9 and 21). The
application of FeCl3 (2.0 equiv.), CuCl2 (2.0 equiv.) or
FeCl2 (2.0 equiv.) in combination with 12 equiv. H2O
was tested under the same conditions, (Table 1, en-
tries 1, 6 and 8), and only 90% yield of 3a is formed
when 2.0 equiv. FeCl3 are employed. Then we opti-
mized the amount of H2O, and found that 12 equiv.
H2O are the best (Table 1, entries 4–7). We also used
CuCl2·2H2O instead of FeCl3·6H2O under the opti-
mized conditions (Table 1, entries 2 and 9), and the
product was generated in 23% yield. All the results
indicate that H2O and Fe(III) play an essential role in
the reaction. A selection of solvents, i.e., CF3CH2OH,
DMF, DMSO, toluene, CH3CN and C2H5OH was
screened, and the results indicate that 2.0 mL of
20[i]
21[j]
FeCl3·6H2O
FeCl3·6H2O
74
92
93
89
22[k] FeCl3·6H2O
23[l]
FeCl3·6H2O
24[m] FeCl3·6H2O
25[n] FeCl3·6H2O
92
[a]
Reactions were carried out at 808C with phenylacetylene
(0.5 mmol), 4-MeC6H4SO2Na (0.75 mmol), Cl source in
a selected solvent (2 mL) under dry nitrogen with stir-
ring for 3 h.
Yield was determined by GC analysis, and dodecane was
used as the internal standard.
N.D. =not detected.
H2O (12 equiv.).
H2O (4 equiv.).
H2O (8 equiv.).
H2O (16 equiv.).
[b]
[c]
[d]
[e]
[f]
[g]
[h]
[i]
Under an air atmosphere.
4-MeC6H4SO2Na (1.2 equiv.).[j] FeCl3·6H2O (1.5 equiv.).
For 6 h.
[k]
[l]
For 9 h.
CF3CH2OH (1.0 mL).
CF3CH2OH (3.0 mL).
[m]
[n]
CF3CH2OH are the best (Table 1, entries 9–14, 24 and temperature (Table 1, entries 15–18). When the reac-
25). The result may be ascribed to the fact that tion is conducted in air rather than in nitrogen, there
CF3CH2OH is miscible with water in any proportions is a decline of product yield from 94% to 40%, plausi-
and is also a strongly protic solvent. Furthermore, bly due to the influence of oxygen on the generation
with the decrease of reaction temperature, there is de- of sulfonyl radicals (Table 1, entry 19). In the study of
cline in product yield. Since the increase of tempera- the effects of 4-MeC6H4SO2Na (2a) loading and reac-
ture from 808C to 1208C does not result in any in- tion time, we found that the maximum 3a yield is ach-
crease of product yield, we take 808C as the optimal ieved at a phenylacetylene/4-MeC6H4SO2Na molar
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ratio of 1/1.5 and in a reaction time of 3 h (Table 1,
entries 9, 20, 22 and 23).
Shown in Table 2 are the results of reacting a variety
of substituted alkynes with 4-MeC6H4SO2Na.
Table 2. Scope of the alkynes.[a]
Figure 1. ORTEP drawing of compound 3d. Hydrogen
atoms are omitted for clarity; ellipsoids are drawn at 50%
probability. Selected bond lengths [ꢂ] and angles [8]: S1–O1
1.426(3), S1–O2 1.435(3), S1–C4 1.756(4), S1–C7 1.757(3),
Cl1–C8 1.750(3), C8–C7 1.326(5), C8–C9 1.463(5), C8–C7–
S1 127.3(3), C7–C8–Cl1 115.7(3), C9–C8–Cl1 113.6(3), C4–
S1–C7 102.53(17).
hexylvinyl)sulfonyl]-4-methylbenzene (3q) and (E)-1-
[(2-chlorooct-1-en-1-yl)sulfonyl]-4-methylbenzene (3r)
are generated in 80% and 87% yields. To our surprise,
chains of aliphatic alkynes with a wide range of func-
tional groups such as carboxyl and ester are well tol-
erated, giving the target products in 80–82% yields
(3s and 3t). With internal alkynes the chlorosulfonyla-
tion products 3u and 3v are obtained in 83% and
86% yields, but 1,2-diphenylethyne only gives 3w in
trace amounts, this phenomenon may be ascribed to
the effect of steric hindrance.
[a]
The results of reacting phenylacetylene compounds
Reactions were carried out with alkynes (0.5 mmol), p-
TolSO2Na (0.75 mmol), and FeCl3·6H2O (1.0 mmol) in with a number of sodium sulfinates under the opti-
CF3CH2OH (2.0 mL) under stirring in dry nitrogen at
808C for 3 h.
mized condition are depicted in Table 3. Gratifyingly,
the introduction of CH3, H, CF3, NO2 and halogen
groups to the phenyl ring of sodium sulfinates is well
tolerated, and the sulfonylation products are isolated
It is obvious that electron-withdrawing groups, in good to excellent yields (4a–4f). Moreover, aliphat-
slightly electron-donating groups and steric groups at ic and naphthalene-substituted sodium sulfinates also
the phenyl ring are well tolerated (3a, 3b and 3d–3k). react efficiently with phenylacetylene, affording the
The X-ray structure of 3d is shown in Figure 1. How- corresponding b-haloalkenyl sulfones (4g and 4h).
ever, strong electron-donating groups are not compat- Unfortunately, sodium trifluoromethanesulfinate is
ible in this system, implying a Friedel–Crafts-type oxi- not suitable for this reaction (4i).
dation process (3c).[9] Functional groups at the meta
To our delight, there is no need to change any of
or ortho positions do not affect the reaction (3l–3n). the reaction conditions to pave the way for using al-
To our delight, C–X groups (X=Cl, Br, CN, NO2, kenes as reaction partners (Table 4). Substitution at
COCH3, COOC2H5) are well tolerated in the reac- the para position affords the desired products 5a–5d
tion, signifying that these compounds have great po- in excellent yields. Strong electron-donating groups
tential for further functionalization (3e–3l). In addi- are again not compatible (5e). Substitution at the
tion, p-F- and p-CF3-substituted phenylacetylenes are meta position does not affect the reaction (5f). Chains
compatible under the adopted conditions, which is of aliphatic alkene are well tolerated (5g and 5h).
a favorable factor for pharmaceutical and materials However, the internal alkene 1,2-diphenylethene fails
chemistry (3d, 3g). Moreover, a pyridine- or naphtha- in the reaction to give the desired product (5i) due to
lene-substituted alkyne is suitable for this transforma- steric hindrance.
tion, affording the desired 3o and 3p products in 78%
Control experiments were conducted to gain in-
and 84% yields, respectively. When chains or rings of sights into the reaction mechanism (Scheme 2). In the
aliphatic alkynes are applied, (E)-1-[(2-chloro-2-cyclo- case of Scheme 2 Eq. (1), there is no formation of the
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Table 3. Scope of the sodium sulfonates.[a]
[a]
Reactions were carried out with phenylacetylene
(0.5 mmol), sodium sulfinates (0.75 mmol), and
FeCl3·6H2O (1.0 mmol), in CF3CH2OH (2.0 mL) under
stirring in dry nitrogen at 808C for 3 h.
Table 4. Scope of the alkenes.[a]
[a]
Scheme 2. Control reactions.
Reactions were carried out with alkene (0.5 mmol), p-
TolSO2Na (0.75 mmol), FeCl3·6H2O (1.0 mmol), in
CF3CH2OH (2.0 mL) stirred under nitrogen atmosphere
at 808C for 3 h.
could serve as a bridge to dissolve the two different
phases. Under the conditions of Scheme 2 Eq. (4), we
expected products, and the possibility of H2O promot- added extra 12 equiv. of H2O, and the product was
ing the conversion of sodium p-toluenesufinate to the generated in 95% yield [Scheme 2, Eq. (5)]. Combin-
corresponding nucleophile sulfinic acid can be dis- ing the results of Table 1 with Scheme 2 Eqs. (3)–(5),
carded.[10] Another possible mechanism for the gener- it is deduced that CF3CH2OH is soluble in the organic
ation of the desired product is via the formation of phase as well as miscible with H2O at any proportions.
a sulfonyl chloride, followed by the addition of the With the salt also soluble in H2O, there is promotion
sulfonyl chloride to alkynes.[6a] To examine such a pos- of the reaction in the inorganic phase as well as in the
sibility, we performed the reaction using p-TolSO2Cl organic phase. In an experiment of phenylacetylene
instead of p-TolSO2Na (0.75 mmol). As monitored by with 4-MeC6H4SO2Na under the optimized conditions
GC and GC-MS, there is no generation of the target with the extra addition of TEMPO (2,2,6,6-tetrameth-
product [Scheme 2, Eq. (2)], and the result shows that yl-1-piperidinyloxy) or BHT (butylated hydroxyto-
such a route is invalid. As discussed above, it is inter- luene), there is no generation of 3a or any formation
esting to find out that H2O plays an important role in of trapping reagent adduct [Scheme 2, Eqs (6) and
this reaction. Scheme 2 Eq. (4) implies that H2O (7)]. Surprisingly, when the reaction was conducted in
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the absence of phenylacetylene and with the addition
of BHT under the optimized conditions, there was
a 24% yield of BHT-sulfonyl [Scheme 2, Eq. (8)]. In
an XPS analysis of Fe after the reaction (Figure 2),
Scheme 3. A possible reaction mechanism.
synthetic purposes,[12] we performed a palladium-cata-
lyzed cross-coupling reaction of b-chloroalkenyl sul-
fones with p-tolylboronic acid according to the report-
ed procedure, and the arylation coupling product 6a
was obtained with 90% yield (Scheme 4).[12a]
Figure 2. XPS Fe 2p spectrum of Fe after reaction under the
optimized conditions.
there are signals at 710.9 and 724.4 eV binding energy
corresponding to Fe 2p3/2 and Fe 2p1/2, respectively.
These peaks could be deconvoluted into two sets of
peaks, i.e., 710.9 and 724.4 eV due to Fe in the +2
state, and 715.2 and 728.7 eV due to the satellite sig-
nals. The binding-energy difference between the main
and satellite peaks is 4.3 eV, which is in good agree-
Scheme 4. Transformation of b-haloalkenyl sulfones via
Suzuki coupling.
ment with the reported data.[11a,d] The XPS data sup- Conclusions
port the fact that FeCl3·6H2O acts as an oxidant in
this reaction.[11] In addition, GC and GC-MS informa- We have reported the preparation of b-haloalkenyl
tion for the reaction of 1-ethynyl-4- fluorobenzene sulfones and b-chloroalkyl sulfones with good to ex-
with 4-MeC6H4SO2Na confirms that the one-pot cellent yields through iron halide-mediated regio- and
regio- and stereoselective addition of sodium sulfi- stereoselective halosulfonylation of alkynes and al-
nates to alkynes can proceed efficiently with the kenes with sodium sulfinates. This protocol uses the
FeCl3·6H2O catalytic system (see Charts in the Sup- FeCl3·6H2O catalyst as Cl source as well as oxidant,
porting Information).
and avoids the use of air-sensitive reagents and spe-
On the basis of the obtained results and the infor- cial ligands. Furthermore, the reaction is easy to oper-
mation available in the literature,[6b] we propose a pos- ate and the starting materials are simple and commer-
sible mechanism for the reaction (Scheme 3). Initially, cially available. Considering the utility of the resulting
sulfonyl radicals (C) are generated via the assistance compounds, the protocol has potential for wide appli-
of the iron catalyst, where iron halide acts as a Lewis cation in the construction of biologically active mole-
acid to activate alkynes. Subsequently, the addition of cules, catalysis ligands, and functional materials.
sulfonyl radicals to the Fe-coordinated alkynes (D)
from the opposite side of the Fe moiety at the termi-
nal position leads to the regio- and stereoselective for-
Experimental Section
mation of the transition state (E). Eventually, reduc-
tive elimination of E occurs to afford the product E-
b-halovinyl sulfones (F) together with the regenera-
tion of the Fe(II) catalyst.
General
All solvents used in the reactions were freshly distilled. The
reagents were recrystallized or distilled as necessary. All re-
In order to explore the potential applications of the
obtained functionalized tetrasubstituted alkenes for actions were performed under an atmosphere of dry nitro-
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1
gen unless specified otherwise. H (400 MHz) and 13C NMR
Crystallographic Information
(100 MHz) spectra were recorded on a 400 MHz spectrome-
ter with the sample dissolved in CDCl3. H NMR chemical
shifts are reported using TMS as internal standard while
13C NMR chemical shifts are reported relative to CDCl3.
The electron ionization method was used for HR-MS meas-
urements, and the mass analyzer type was double-focusing.
1
CCDC 1510491 (3d) contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free
of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
General Procedure for the Preparation of Sodium
Sulfinates
Acknowledgements
The authors thank the Natural Science Foundation of China
(Nos. 21273067, 21476065 and 21571060) and the Fundamen-
tal Research Funds for the Central Universities (Hunan Uni-
versity). CTA thanks the Hunan University for an adjunct
professorship.
Sulfinic acid sodium salts C6H4SO2Na, sodium 4-chloroben-
zenesulfinate, sodium 3-chloro-4-methylbenzenesulfinate,
sodium methanesulfinate and sodium trifluoromethanesulfi-
nate were purchased from Alfa-Aesar with purity equal to
or greater than 98.0%. They were used as received without
further purification. Sodium 4-bromobenzenesulfinate was
prepared by heating 5.0 g of sodium sulfite, 4.12 g of 4-bro-
mobenzenesulfonyl chloride, and 3.36 g of sodium bicarbon-
ate in 20 mL of water at 808C for 8 h. After cooling to room
temperature, water was removed under vacuum. Recrystalli-
zation of the residue in ethanol afforded the product as
a white solid; yield: 2.76 g (70%). Similarly, other sodium
arenesulfinates (sodium 4-nitrobenzenesulfinate, sodium 4-
(trifluoromethyl) benzenesulfinate, sodium naphthalene-2-
sulfinate) were prepared from the corresponding sulfonyl
chlorides.
References
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Procedure for the Suzuki Coupling Reaction of 3u
with p-Tolylboronic Acid
Under an argon atmosphere, 0.5 mmol (E)-1-[(1-chloro-1-
phenylprop-1-en-2-yl)sulfonyl]-4-methylbenzene 3u was
added to
a mixture of 0.6 mmol p-tolylboronic acid,
0.05 mmol Pd(PPh3)2Cl2 and 0.6 mmol K2CO3 in 3 mL
CH3CN. After stirring at 1108C for 30 min, the reaction mix-
ture was quenched with saturated NaCl, extracted with ethyl
acetate (3ꢃ10 mL) and dried over anhydrous Na2SO4. After
filtration and concentration under vacuum, the crude prod-
uct was purified with flash chromatography on silica gel
(ethyl acetate/petroleum ether=1/20) to give 6a.
General Procedure for the Preparation of b-
Haloalkenyl Sulfones and b-Chloroalkyl Sulfones
FeCl3·6H2O was purchased from Sinophsrm Chemical Re-
agent Co., Ltd with a purity equal or greater than 99.0%.
CF3CH2OH was purchased from Aladdin with purity equal
or greater than 99.8%. For the reaction of alkynes com-
pounds with sodium sulfinates: a mixture of alkyne com-
pound
(0.5 mmol),
sodium
sulfinate
(0.75 mmol),
FeCl3·6H2O (1 mmol) in CF3CH2OH (2 mL) was stirred at
808C under a nitrogen atmosphere for 3 h. The reactions
were conducted in a sealed Schlenk tube and heated by an
IKA magnetic heating agitator with aluminum heating
sleeve. The reaction temperature was directly read from the
screen of the IKA apparatus and was not calibrated. Re-
moval of the solvent under reduced pressure gave the crude
product; and the pure product was obtained by passing the
crude product through a short silica gel column using
hexane/EtOAc as eluent.
[4] a) A. F. Kisselev, A. L. Goldberg, Chem. Biol. 2001, 8,
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Chlorosulfonylation of Alkynes and Alkenes with Sodium
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