Oxidative coupling of dichalcogenides with sodium sulfinates via copper-catalyzed cleavage of s-s and se-se bonds

Article abstract of DOI:10.1021/jo5026805

A copper-catalyzed sulfonylation of disulfides was achieved using sodium sulfinates in air. The reaction formed various sulfur-sulfone bonds efficiently and afforded thiosulfonates in good yields. Selenosulfonates could also be prepared with this procedure. Furthermore, both chalcogenide groups on the dichalcogenides were available in these reactions.

Full text of DOI:10.1021/jo5026805

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Article
Oxidative Coupling of Dichalcogenides with Sodium Sulfinates
via Copper-Catalyzed Cleavage of S-S and Se-Se Bonds
Nobukazu Taniguchi
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/jo5026805 • Publication Date (Web): 06 Jan 2015
Downloaded from http://pubs.acs.org on January 12, 2015
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Oxidative Coupling of Dichalcogenides with
Sodium Sulfinates via Copper-Catalyzed
Cleavage of S−S and Se−Se Bonds
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Nobukazu Taniguchi*
Department of Chemistry, Fukushima Medical University, Fukushima 960-1295, Japan
taniguti@fmu.ac.jp
R1
O2
S
CuI-Phen•H2O
1
3
(
2x
R
Y)2
+
R
SO2Na
2x
Y
R2
DMA, H2O,
air, 30 ºC
R2
Y = S or Se
R3
Abstract. A copper-catalyzed sulfonylation of disulfides was achieved using sodium sulfinates in
air. The reaction formed various sulfur−sulfone bonds efficiently and afforded thiosulfonates in
good yields. Selenosulfonates could also be prepared with this procedure. Furthermore, both
chalcogenide groups on the dichalcogenides were available in these reactions.
Introduction
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The development of transition metal-catalyzed organosulfur syntheses is of much importance in
organic chemistry.1 In particular, the formation of sulfur−carbon bonds has already been
investigated. The products of these reactions have found widespread use as reagents or
intermediates.2,3
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However, exploration of the construction of a sulfur-hetero atom bond has been slow.1,4 The
synthetic method remains unchanged. Similarly, the formation of thiosulfonates having
sulfur−sulfone bonds, which are still generally prepared by traditional procedures, is difficult.
It is known that the oxidation of symmetrical disulfides5 or the coupling of a disulfide with
6
sodium thiosulfinate occurs in the presence of excess AgNO3 or oxidants such as iodine7c-d or
NBS7e (Figure 1). These oxidants work via the production of a radical or cation species.7
Unfortunately, the catalytic procedure using disulfides has not been explored. A similar reaction
using thioimide has recently been performed using a Sc(OTf)2 catalyst.8
Notably, the reaction of a thiol with sulfonyl chloride cannot be used to prepare the
corresponding thiosulfonates, unlike the analogous synthesis of sulfonamide. The procedure
usually affords disulfide as a major product owing to the rapid reaction of thiols with
thiosulfonates.9 Therefore, the development of such a convenient catalytic method using
disulfides or thiols is desirable.
Figure 1. Sulfonylation of disulfides
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(1) Oxidation of disulfides5
RCO3H
R1S-SO2R1
(R1S)2
(a)
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8
9
(2) Coupling of disulfides with sodium sulfinates using excess reagents6,7
AgNO3
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R1S-SO2R2
(R1S)2
R2SO2Na
R1S-Ag
+
(b)
(c) (R1S)2 + R2SO2Na
(3) Coupling of thiols with sulfonyl chlorides9
R1SH R2SO2Cl
+
I2 or NBS
R1S-SO2R2
(R1S)2
R1SH
(d)
+
R1S-SO2R2
(rapid reaction)
Thiols and disulfides are well known to be poisons for transition metals. The employment of
these compounds often gives transition metal-thiolate complexes that are stable and inactive.10
Consequently, the combination of transition metals with thiols stops reactions. To activate the
metal-thiolates, the conversion of oxidation states is required.
For example, the reactions of copper-thiolates with aryl halides give aryl sulfides in good
yields.11 This indicates that the oxidation of metal-thiolates can promote the reaction and that
oxidative reaction conditions are necessary for the transition metal-catalyzed sulfonylation using
disulfides or thiols. However, sulfonylation using disulfides has yet to be developed.
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Figure 2. Strategy for a copper-catalyzed sulfonylation of disulfides
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6
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8
CuI
R2SO2Na
(R1S)2
R1S-SO2R2
+
R1S CuI
+
9
Inactive
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Reductive elimnation
& Oxidation
Oxidation
CuI
SO2R2
R1S CuII
R1S CuII
R2SO2Na
X
NaX
As a general rule, disulfides are more stable than thiols, which are air sensitive and have rank
odors. Accordingly, the exploitation of reactions using disulfides is justified.
Recently, it was found that a copper-catalyzed synthesis of thiosulfonates from thiols with
sodium sulfinates could perform under an oxygen atmosphere.12 This method can suppress the
formation of disulfides as byproducts. In addition, copper salts are able to cleave disulfide
bonds.13 These facts show that the sulfonylation of disulfides is enabled by the presence of a
copper catalyst (Figure 2). It would seem that the oxidation of R1SCu(I) as an intermediate would
produce active R1SCu(II); however, a catalytic method has not been established to date.
One approach to solve this problem may be to perform this reaction under mild oxidative
conditions. With this, the copper-catalyzed sulfonylation of disulfides was achieved under air.
Furthermore, diselenides were also reactive under these conditions. The procedure consumed
both chalcogenide-groups on the dichalcogenides completely. In this article, this methodology
will be described.
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Results and Discussion
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Preparation of Thiosulfonates from Disulfides and Sodium Sulfinates. Initially, to establish a
suitable condition, a mixture of bis(4-methylphenyl)disulfide 1a with sodium benzenesulfinate
2a was surveyed in air. As shown in table 1, in the absence of CuI catalyst, the reaction did not
occur, and disulfide was recovered (entry 1). Similarly, CuI itself gave the same result (entry 2).
Fortunately, the addition of amine ligands such as 1,10-phenanthroline•H2O (Phen•H2O) or
N,N,N’,N’-tetramethyl ethylenediamine (TMEDA) increased the yield of thiosulfonate 3aa to
72% or 67%, respectively (entries 3 and 4). Then, to improve the reactivity of copper catalyst,
NH4BF4 was added, which led to an 80% yield of 3aa without recovery of disulfide (entry 5).14
The reaction afforded the best result at 30 °C (entry 6). Although other additives such as NH4PF6
or Cs2CO3 were tested, these salts could not promote the reactivity satisfactorily (entries 7−8). In
the evaluation of other solvents or copper catalysts, desired results were not obtained (entries
9−15).
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Table 1. Investigation of suitable conditionsa
[Cu]-L
(1:1, 10 mol%)
additive
(4-MeC6H4S)2
2x
PhSO2Na
4-MeC6H4S-SO2Ph
+
air, 18 h
3aa
2a
1a
3aa/1ab 3aa
Entry [Cu] (mol %)
Solvent
Add.
Temp.
(ºC)
(%)
1
2
3
None
CuI
DMA/H2O(3/1)
DMA/H2O(3/1)
None
None
None
30
0/100
0/100
95/5
0
30
0
CuI-Phen.H2O DMA/H2O(3/1)
30
72
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CuI-TMEDA
DMA/H2O(3/1)
None
30
30
100
30
30
30
30
30
90/10
100/0
80/20
70/30
100/0
77/23
100/0
91/9
67
80
49
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36
65
58
64
CuI-Phen•H2O DMA/H2O(3/1)
DMA/H2O(3/1)
NH4BF4
NH4BF4
NH4PF4
Cs2CO3
NH4BF4
NH4BF4
NH4BF4
6
7
DMA/H2O(3/1)
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8
DMA/H2O(3/1)
9
DMF/H2O(3/1)
10
11
DMSO/H2O(3/1)
CuCl-
DMA/H2O(3/1)
DMA/H2O(3/1)
DMA/H2O(3/1)
DMA/H2O(3/1)
DMA/H2O(3/1)
Phen.H2O
12
13
14
15
CuBr-
NH4BF4
NH4BF4
NH4BF4
NH4BF4
30
30
30
30
83/17
91/9
61
77
52
53
Phen.H2O
CuCl2-
Phen.H2O
CuBr2-
79/21
83/17
Phen.H2O
Cu(OAc)2-
Phen.H2O
aA mixture of 1a (0.15 mmol), 2a (0.33 mmol) and additive (0.15 mmol) in DMA
(0.3 mL) and H2O (0.1 mL) was treated in air. The ratio was determined by H
NMR.
b
1
On the basis of the previously described method, the scope and limitations of the optimized
conditions were screened (Table 2). When the mixture of diaryl disulfides 1 with sodium
sulfinates 2 was treated by CuI-Phen•H2O in air, the expected thiosulfonates 3 were obtained in
excellent yields. The use of sodium sulfinates or disulfides having electron-withdrawing groups
slightly decreased the reactivity (entries 4, 5, 12−14). Unfortunately, the reaction using diaryl
disulfides with a non-protected group did not give the corresponding products, and a complex
mixture was detected (entry 10−11). On the contrary, dialkyl disulfides were successful reagents
under the reaction conditions (entries 18−20). However, the reaction of bis(t-butyl) disulfide was
not successful under an oxygen atmosphere (entry 21).
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Table 2. Copper-catalyzed coupling of disulfides with sodium sulfinatesa
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CuI-Phen•H2O
(1:1, 10 mol%)
NH4BF4
(R1S)2
+
R2SO2Na
R1S-SO2R2
DMA, H2O,
air, 30 ºC,18 h
1
2
3
Entry
R1
R2
Time
3
3 (%)
(h)
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18
18
36
36
18
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18
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48
18
1
(4-MeC6H4S)2
PhSO2Na
81
80
3aa
3ab
3ac
3ad
3ae
3af
2
4-MeC6H4SO2Na
4-MeOC6H4SO2Na
4-ClC6H4SO2Na
4-FC6H4SO2Na
3c
4c
5
77
66
72
6
4-AcHNC6H4SO2Na
MeSO2Na
65
7
71
3ag
3ba
3ca
3da
3ea
3fa
8
(PhS)2
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
94
9
(4-MeOC6H4S)2
(4-H2NC6H4S)2
(4-HOC6H4S)2
(4-ClC6H4S)2
(4-BrC6H4S)2
(4-O2NC6H4S)2
(2-MeC6H4S)2
(2-MeOC6H4S)2
(2-BrC6H4S)2
(MeS)2
74
10
11
12
13
14
15
16
17
18
19
20
21
trace
trace
65
61
69b
3ga
3ha
3ia
78
70
3ja
54
3ka
3la
79
(PhCH2S)2
60b
58b
traceb
3ma
3na
3oa
(n-BuS)2
(t-BuS)2
aCondition: A mixture of 1 (0.15 mmol), 2 (0.33 mmol) and NH4BF4
(0.15 mmol) in DMA (0.3 mL) and H2O (0.1 mL) was treated with CuI-
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Phen•H2O under air. The reaction was performed under an oxygen
atmosphere.
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Application to Preparation of Selenosulfonates using Diselenides. Attention was then
focused toward the coupling of diselenides (4) with sodium sulfinates (2). As shown in table 3,
numerous combinations of diselenides with sodium sulfinates gave good results. These reactions
required 20 mol % of CuI-Phen•H2O catalyst and are successful in DMA without the addition of
H2O (0.1 mL). However, some reactions required the addition of water to promote the reactivity
(entries 4, 11 and 13).
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Thus, the copper-catalyzed sulfonylation of disulfides or diselenides using sodium sulfinates
could be used effectively to synthesize thiosulfonates or selenosulfonates and could efficiently
use the two chalcogenide groups on the dichalcogenide reagents.
Although the coupling of ditelluride with sodium sulfinate was attempted, the expected
reaction ultimately did not proceed, and the production of complex mixtures was observed
(Scheme 1).
Table 3. Copper-catalyzed sulfonylation of diselenidesa
CuI-Phen•H2O
(1:1, 20 mol%)
NH4BF4
(R1Se)2
+
R2SO2Na
2x R1Se-SO2R2
DMA, air, 30 ºC
4
2
5
Entry
R1
R2
(h)
5
5 (%)
71
51b
1
2
3
4
5
(PhSe)2
PhSO2Na
PhSO2Na
18
18
18
18
18
5aa
5aa
5ab
5ab
5ab
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
66
75b
65c
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7
4-MeOC6H4SO2Na
4-ClC6H4SO2Na
4-FC6H4SO2Na
36
18
18
18
36
36
36
18
68
65
5ac
5ad
5ae
5af
8
61
9
4-AcHNC6H4SO2Na
59
10
11
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13
(4-MeC6H4Se)2
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
4-MeC6H4SO2Na
63
70b
5bb
5cb
5db
5eb
(4-MeOC6H4Se)2
(1-NaphthylSe)2
(PhCH2Se)2
57
50b
aCondition: A mixture of 4 (0.15 mmol), 2 (0.33 mmol) and NH4BF4 (0.15 mmol) in
DMA (0.6 mL) was treated with CuI-Phen•H2O under air. The reaction was
performed in DMA (0.3 mL) and H2O (0.1 mL). Phen was used instead of
Phen•H2O.
b
c
Scheme 1. Reactivity of ditellureide
CuI-Phen•H2O
(1:1, 10 mol%)
2x PhTe-SO2C6H4Me-4
+
4-MeC6H4SO2Na
(PhTe)2
DMA,
7
2b
6
air, 30 ºC, 36 h
Not detected
Proposed Reaction Mechanism of The Copper-Catalyzed Coupling of Dichalcogenides
with Sodium Sulfinates. To elucidate the reaction mechanism, further experimentation was
attempted. In the absence of oxygen, where the reaction was investigated under a nitrogen
atmosphere, the corresponding products were produced at lower yields with the recovery of
dichalcogenides (Scheme 2).
The reactivity of PhYCu(I) (Y= S or Se) was also examined (Scheme 3).15 The reaction of
PhYCu(I) with sodium 4-tolylsulfinate gave the corresponding thiosulfonate and selenosulfonate
at yields of 35% and 37%, respectively.
These facts show that the procedure requires oxygen and that PhYCu(I) is formed as a reaction
intermediate.
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Scheme 2. Sulfonylation in the absence of oxygen
7
8
9
CuI-Phen•H2O
(1:1, 10 mol%),
NH4BF4
10
11
12
13
14
15
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60
(4-MeC6H4Y)2
+ 4-MeC6H4SO2Na
4-MeC6H4Y-SO2C6H4Me-4
DMA/H2O (3/1),
30 ºC, under N2
Y = S: 18% (18 h)
Se: 12% (36 h)
Scheme 3. Reactivity of PhYCu(I)
Phen•H2O,
NH4BF4
PhS-SO2C6H4Me-4
4-MeC6H4SO2Na
PhYCu
+
DMA/H2O (3/1),
air, 30 ºC, 18h
(0.3 mmol)
(0.36 mmol)
Y = S: 35%
Se: 37%
Given these results, a plausible mechanism was considered as shown (Figure 3).16 In cycle A,
after the formation of complex 8 from disulfide 1 with Cu(I)X13, the reaction of 8 with sodium
sulfinate 2 gives thiosulfinate 3 and copper thiolate 9 via reductive elimination. Subsequently,
the oxidation of 9 produces R1SCu(II)X 1011, and R1S(R2SO2)Cu(II) 11 is obtained by the
transmetallation. Finally, complex 11 gives thiosulfonate 3 and Cu(I)X after oxidation and then
reductive elimination.
However, in cycle B, after the generation of sulfonyl copper complex 14 from sodium sulfinate 2
with Cu(I)X, the reaction of 14 with disulfide 1 affords thiosulfonate 3 and thiolate copper
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complex 9. Consequently, the catalytic cycle is achieved and is able to consume both sulfide
5
6
groups on the disulfides. Similarly, the same process is able to accommodate diselenide reagents.
7
8
9
In addition, it is expected that the rates of these two processes are different according to the
distribution of substrates.
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Figure 3. A plausible mechanism
R2SO2Na
(R1S)2
2
1
(R1S)2CuXLn
R2SO2-CuILn
CuIXLn
3
8
1/4O2, X-
Cu0L
14
R1S
CuIIILn
1
12
2
n 13
R2SO2
1/4O2, X-
3
R1S-SO2R2
R1S
R2SO2
B
A
R1S-SO2R2
CuIILn
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3
3
R1S-CuILn
R1S-CuILn
R1S
X
2
CuIILn
9
9
10
1/4O2, X-
1/4O2, X-
This developed procedure can be scaled up as follows (Scheme 4). When the amount of
sulfonylation using bis(4-tolyl) disulfide was increased from 0.15 mmol to 1.5 mmol, the
corresponding thiosulfonate 3ab was produced in 75% yield. To promote the reaction, the use of
0.1 mL of water was most important. However, a large quantity of water decreased the formation
of 3ab.17 As a result, it was apparent that the presence of a small amount of water could promote
the reaction.
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Scheme 4. Large scale sulfonylation of disulfide
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CuI-Phen•H2O
(1:1, 10 mol%)
O2
S
(
S)2
+
2x
SO2Na
2x
S
DMA (4.5 mL),
H2O (0.1 mL),
air, 30 ºC, 40 h
1a
1.5 mmol
3ab
2b
3.6 mmol
628.2 mg (75%)
Conclusion
In conclusion, the sulfonylation of disulfides was achieved using sodium sulfinates under air. The
procedure afforded numerous thiosulfonates in good yields. Furthermore, selenosulfonates could
be readily synthesized. These reactions were able to use both chalcogenide-groups on the
dichalcogenide reagents. Although tested, ditellurides did not successfully yield the desired
products under these conditions
Experimental Section
1
13
General Procedure and Chemicals. All reactions were carried out in air. H and C NMR
spectra were recorded at 270 and 67.5 MHz, respectively. Chemical shifts are reported in δ ppm
1
referenced to an internal tetramethylsilane standard for H NMR and chloroform-d (δ 77.0) for
13C NMR. Compounds 3aa,7 3ab,7 3ac,5c 3ad,5c,7 3ae,7 3ag,7 3ba,7 3ca,5c,7 3fa,7 3ga,7 3ha,18
3la,5 3ma,6e 5aa,3c 5ab,3c and 5ad3c showed the identical spectra reported in the literature.
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Typical procedure for copper-catalyzed sulfonylation of disulfides: Synthesis of S-4-tolyl
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benzenethiosulfonate (3aa) (Table 2, entry 1)
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To a mixture of bis(4-tolyl) disulfide (37.0 mg, 0.15 mmol), sodium phenylsulfinate (54.2 mg,
0.33 mmol), and NH4BF4 (15.7 mg, 0.15 mmol), in DMA (0.3 mL) and H2O (0.1 mL) were
added CuI (2.9 mg, 0.015 mmol) and Phen•H2O (3.0 mg, 0.015 mmol), and the mixture was
stirred at 30 °C for 18 h in air using balloon. After the residue was dissolved in Et2O, the solution
was washed with H2O and saturated sodium chloride and dried over anhydrous magnesium
sulfate. Chromatography on silica gel (30% diethyl ether / hexane) gave 3aa (64.5 mg, 81%):
White solid. Mp: 48−51 °C; 1H NMR (270 MHz, CDCl3) δ 7.60–7.55 (m, 3H, Ar-H), 7.44 (d, J
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= 8.1 Hz, 2H, Ar-H), 7.24−7.21 (m, 2H, Ar-H), 7.13 (d, J = 8.1 Hz, 2H, Ar-H), 2.37 (s, 3H,
CH3); 13C{1H} NMR (67.5 MHz, CDCl3) δ 142.9, 142.1, 136.4, 133.5, 130.2, 128.7, 127.5,
124.3, 21.4; IR (CHCl3) 1595, 1490, 1325, 1145 cm-1; Anal. Calcd for C13H12O2S2: C, 59.06; H,
4.58. Found: C, 59.00; H, 4.51.
S-4-Tolyl 4-toluenethiosulfonate (3ab): The title compound was obtained as a white solid (67.1
mg, 80%). M: Colorless crystals. Mp: 73−75 °C; 1H NMR (270 MHz, CDCl3) δ 7.46 (d, J = 8.2
Hz, 2H, Ar-H), 7.26−7.19 (m, 4H, Ar-H), 7.14 (d, J = 8.2 Hz, 2H, Ar-H), 2.42 (s, 3H, CH3), 2.37
(s, 3H, CH3); 13C{1H} NMR (67.5 MHz, CDCl3) δ 144.6, 142.0, 140.4, 136.4, 130.1, 129.3,
127.5, 124.5, 21.6, 21.4; IR (CHCl3) 1595, 1491, 1327, 1143 cm-1; Anal. Calcd for C14H14O2S2:
C, 60.40; H, 5.07. Found: C, 60.31; H, 5.05.
S-4-Tolyl 4-methoxybenzenethiosulfonate (3ac): The title compound was obtained as a white
solid (68.0 mg, 77%). Mp: 54−55 °C; 1H NMR (270 MHz, CDCl3) δ 7.51 (d, J = 8.5 Hz, 2H, Ar-
H), 7.25 (d, J = 8.5 Hz, 2H, Ar-H), 7.15 (d, J = 8.5 Hz, 2H, Ar-H), 6.87 (d, J = 8.5 Hz, 2H, Ar-H),
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3.87 (s, 3H, CH3), 2.38 (s, 3H, CH3); C{1H} NMR (67.5 MHz, CDCl3) δ 163.5, 141.9, 136.5,
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135.0, 130.2, 129.9, 124.7, 113.8, 55.7, 21.5; IR (CHCl3) 1593, 1495, 1327, 1140 cm-1; Anal.
Calcd for C14H14O3S2: C, 57.12; H, 4.79. Found: C, 57.08; H, 4.76.
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S-4-Tolyl 4-chlorobenzenethiosulfonate (3ad): The title compound was obtained as a white solid
(59.6 mg, 66%). Mp: 127−128 °C; 1H NMR (270 MHz, CDCl3) δ 7.50 (d, J = 8.2 Hz, 2H, Ar-H),
7.40 (d, J = 8.8 Hz, 2H, Ar-H), 7.25 (d, J = 8.8 Hz, 2H, Ar-H), 7.17 (d, J = 8.2 Hz, 2H, Ar-H),
2.39 (s, 3H, CH3); 13C{1H} NMR (67.5 MHz, CDCl3) δ 142.4, 141.5, 140.1, 136.4, 130.4, 129.1,
128.9, 124.0, 21.5; IR (CHCl3) 1582, 1475, 1331, 1146 cm-1; Anal. Calcd for C13H11ClO2S2: C,
52.25; H, 3.71. Found: C, 55.21; H, 3.67.
S-4-Tolyl 4-fluorobenzenethiosulfonate (3ae): The title compound was obtained as a white solid
1
(61.5 mg, 72%). Mp: 103−105 °C; H NMR (270 MHz, CDCl3) δ 7.62−7.56 (m, 2H, Ar-H),
7.27−7.22 (m, 2H, Ar-H), 7.17−7.06 (m, 4H, Ar-H), 2.39 (s, 3H, CH3); 13C{1H} NMR (67.5
MHz, CDCl3) δ 165.4 (d, 1J(c-F) = 254 Hz), 142.3, 139.0 (d, 4J(c-F) = 3 Hz), 136.4, 130.4 (d, 3J(c-
F) = 9 Hz), 127.5, 124.2, 116.0 (d, 2J(c-F) = 23 Hz), 21.5; IR (CHCl3) 1588, 1491, 1331, 1142 cm-
1; Anal. Calcd for C13H11FO2S2: C, 55.44; H, 3.95. Found: C, 55.50; H, 3.91.
S-4-Tolyl 4-acetylaminobenzenethiosulfonate (3af): The title compound was obtained as a white
1
solid (62.7 mg, 65%). Mp: 175−176 °C; H NMR (270 MHz, CDCl3) δ 7.73 (br, 1H, NH), 7.59
(d, J = 8.8 Hz, 2H, Ar-H), 7.49 (d, J = 8.8 Hz, 2H, Ar-H), 7.24 (d, J = 8.1 Hz, 2H, Ar-H), 7.14 (d,
J = 8.1 Hz, 2H, Ar-H), 2.37 (s, 3H, CH3), 2.22 (s, 3H, CH3); 13C{1H} NMR (67.5 MHz, CDCl3)
δ 168.8, 142.8, 142.3, 137.6, 136.5, 130.3, 128.9, 124.3, 118.7, 24.8, 21.5; IR (CHCl3) 1703,
1513, 1326, 1142 cm-1; Anal. Calcd for C15H15NO3S2: C, 56.05; H, 4.70; N, 4.30. Found: C,
56.00; H, 4.69; N, 4.23.
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S-4-Tolyl 4-methanethiosulfonate (3ag): The title compound was obtained as a colorless oil (43.2
mg, 71%). 1H NMR (270 MHz, CDCl3) δ 7.59 (d, J = 8.1 Hz, 2H, Ar-H), 7.29 (d, J = 8.1 Hz, 2H,
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Ar-H), 3.16 (s, 3H, CH3), 2.42 (s, 3H, ArCH3); 13C{1H} NMR (67.5 MHz, CDCl3) δ 142.5,
136.1, 130.7, 124.4, 47.1, 21.4; IR (CHCl3) 1594, 1490, 1325, 1136 cm-1; Anal. Calcd for
C8H10O2S2: C, 47.50; H, 4.98. Found: C, 47.54; H, 4.94.
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S-4-Phenyl 4-toluenethiosulfonate (3ba): The title compound was obtained as a white solid (74.6
1
mg, 94%). Mp: 75−76 °C; H NMR (270 MHz, CDCl3) δ 7.47–7.42 (m, 3H, Ar-H), 7.38–7.33
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(m, 4H, Ar-H), 7.20 (d, J = 8.1 Hz, 2H, Ar-H), 2.41 (s, 3H, CH3); C{1H} NMR (67.5 MHz,
CDCl3) δ 144.7, 140.3, 136.5, 131.3, 129.4, 129.3, 128.0, 127.5, 21.6; IR (CHCl3) 1594, 1442,
1328, 1143 cm-1; Anal. Calcd for C13H12O2S2: C, 59.06; H, 4.58. Found: C, 58.94; H, 4.54.
S-4-Metoxyphenyl 4-toluenethiosulfonate (3ca): The title compound was obtained as a white
solid (65.3 mg, 74%). Mp: 67−68 °C; 1H NMR (270 MHz, CDCl3) δ 7.46 (d, J = 8.5 Hz, 2H, Ar-
H), 7.29−7.20 (m, 4H, Ar-H), 6.84 (d, J = 8.5 Hz, 2H, Ar-H), 3.83 (s, 3H, OCH3), 2.42 (s, 3H,
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ArCH3); C{1H} NMR (67.5 MHz, CDCl3) δ 162.2, 144.5, 140.3, 138.3, 129.3, 127.6, 118.7,
114.9, 55.4, 21.6; IR (CHCl3) 1590, 1493, 1325, 1141 cm-1; Anal. Calcd for C14H14O3S2: C,
57.12; H, 4.79. Found: C, 57.08; H, 4.75.
S-4-Chlorophenyl 4-toluenethiosulfonate (3fa): The title compound was obtained as a white solid
1
(58.3 mg, 65%). Mp: 89−90 °C; H NMR (270 MHz, CDCl3) δ 7.46 (d, J = 7.9 Hz, 2H, Ar-H),
7.34−7.36 (brs, 4H, Ar-H), 7.23 (d, J = 8.2 Hz, 2H, Ar-H), 2.43 (s, 3H, CH3); 13C{1H} NMR
(67.5 MHz, CDCl3) δ 144.9, 140.1, 138.1, 137.7, 129.7, 129.5, 127.6, 126.5, 21.7; IR (CHCl3)
1573, 1331, 1420, 1145 cm-1; Anal. Calcd for C13H11ClO2S2: C, 52.25; H, 3.71. Found: C, 52.20;
H, 3.69.
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S-4-Bromophenyl 4-toluenethiosulfonate (3ga): The title compound was obtained as a white
solid (63.1 mg, 61%). Mp: 99−100 °C; 1H NMR (270 MHz, CDCl3) δ 7.50−7.45 (m, 4H, Ar-H),
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7.26−7.20 (m, 4H, Ar-H), 2.43 (s, 3H, CH3); 13C{1H} NMR (67.5 MHz, CDCl3) δ 145.0, 140.1,
137.8, 132.6, 129.5, 127.5, 127.1, 126.6, 21.7; IR (CHCl3) 1521, 1423, 1332, 1145 cm-1; Anal.
Calcd for C13H11BrO2S2: C, 45.49; H, 3.23. Found: C, 45.50; H, 3.20.
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S-4-Nitrophenyl 4-toluenethiosulfonate (3ha): The title compound was obtained as a yellow solid
(79.1 mg, 69%). Mp: 129−131 °C; 1H NMR (270 MHz, CDCl3) δ 8.18 (d, J = 8.8 Hz, 2H, Ar-H),
7.59 (d, J = 8.8 Hz, 2H, Ar-H), 7.49 (d, J = 8.3 Hz, 2H, Ar-H), 7.25 (d, J = 8.3 Hz, 2H, Ar-H),
2.44 (s, 3H, CH3); 13C{1H} NMR (67.5 MHz, CDCl3) δ 145.6, 140.1, 137.0, 135.7, 129.7, 127.5,
126.4, 124.4, 21.7; IR (CHCl3) 1599, 1344, 1214, 1146 cm-1; Anal. Calcd for C13H11NO4S2: C,
50.47; H, 3.58; N, 4.53. Found: C, 50.23; H, 3.46; N, 4.35.
S-2-Tolyl 4-toluenethiosulfonate (3ia): The title compound was obtained as a white solid (65.2
1
mg, 78%). Mp: 98−99 °C; H NMR (270 MHz, CDCl3) δ 7.43 (d, J = 8.2 Hz, 2H, Ar-H),
7.39−7.15 (m, 6H, Ar-H), 2.42 (s, 3H, CH3), 2.15 (s, 3H, CH3); 13C{1H} NMR (67.5 MHz,
CDCl3) δ 144.7, 144.2, 140.7, 138.3, 131.8, 130.9, 129.4, 127.5, 127.2, 126.8, 21.6, 20.6; IR
(CHCl3) 1592, 1471, 1327, 1143 cm-1; Anal. Calcd for C14H14O2S2: C, 60.40; H, 5.07. Found: C,
60.36; H, 5.03.
S-2-Methoxyphenyl 4-toluenethiosulfonate (3ja): The title compound was obtained as a white
1
solid (61.7 mg, 70%). Mp: 98−99 °C; H NMR (270 MHz, CDCl3) δ 7.51−7.41 (m, 4H, Ar-H),
7.20 (d, J = 7.9 Hz, 2H, Ar-H), 6.96 (t, J = 8.6 Hz, 1H, Ar-H), 6.79 (d, J = 8.6 Hz, 1H, Ar-H),
3.47 (s, 3H, OCH3), 2.41 (s, 3H, CH3); 13C{1H} NMR (67.5 MHz, CDCl3) δ 160.2, 144.2, 141.5,
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139.5, 133.8, 129.1, 127.6, 121.2, 115.6, 111.3, 55.4, 21.6; IR (CHCl3) 1585, 1478, 1326, 1142
cm-1; Anal. Calcd for C14H14O3S2: C, 57.12; H, 4.79. Found: C, 57.20; H, 4.74.
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S-2-Bromophenyl 4-toluenethiosulfonate (3ka): The title compound was obtained as a white
solid (55.4 mg, 54%). Mp: 119−120 °C; 1H NMR (270 MHz, CDCl3) δ 7.71 (d, J = 7.6 Hz, 1H,
Ar-H), 7.57 (d, J = 7.3 Hz, 1H, Ar-H), 7.46 (t, J = 8.2 Hz, 2H, Ar-H), 7.40−7.27 (m, 4H, Ar-H),
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2.43 (s, 3H, CH3); 13C{1H} NMR (67.5 MHz, CDCl3) δ 145.1, 140.7, 139.4, 133.6, 132.7, 131.1,
129.6, 129.4, 128.3, 127.5, 21.7; IR (CHCl3) 1594, 1447, 1330, 1144 cm-1; Anal. Calcd for
C13H11BrO2S2: C, 45.49; H, 3.23. Found: C, 45.43; H, 3.22.
S-Methyl 4-toluenethiosulfonate (3la): The title compound was obtained as a white solid (23.8
mg, 79%). Mp: 57−58 °C; 1H NMR (270 MHz, CDCl3) δ 7.81 (d, J = 8.6 Hz, 2H, Ar-H), 7.35 (d,
J = 8.6 Hz, 2H, Ar-H), 2.50 (s, 3H, CH3), 2.46 (s, 3H, CH3); 13C{1H} NMR (67.5 MHz, CDCl3)
δ 144.8, 140.8, 129.8, 127.1, 21.6, 18.0; IR (CHCl3) 1596, 1333, 1215, 1143 cm-1; Anal. Calcd
for C8H10O2S2: C, 47.50; H, 4.98. Found: C, 47.66; H, 4.89.
S-Benzyl 4-toluenethiosulfonate (3ma): The title compound was obtained as a white solid (50.2
1
mg, 60%). Mp: 31−33 °C; H NMR (270 MHz, CDCl3) δ 7.72 (d, J = 8.2 Hz, 2H, Ar-H),
7.28−7.19 (m, 7H, Ar-H), 4.24 (s, 2H, CH2), 2.43 (s, 3H, CH3); 13C{1H} NMR (67.5 MHz,
CDCl3) δ 144.6, 142.0, 133.7, 129.7, 129.1, 128.7, 127.9, 127.0, 40.3, 21.6; IR (CHCl3) 1594,
1494, 1454, 1326, 1140 cm-1; Anal. Calcd for C14H14O2S2: C, 60.40; H, 5.06. Found: C, 60.53;
H, 4.99.
S-n-Butyl 4-toluenethiosulfonate (3na): The title compound was obtained as a colorless oil (42.5
1
mg, 58%). H NMR (270 MHz, CDCl3) δ 7.82 (d, J = 8.2 Hz, 2H, Ar-H), 7.35 (d, J = 8.2 Hz,
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1.40−1.26 (m, 2H, CH2), 0.85 (d, J = 6.8 Hz, 3H, CH3); C{1H} NMR (67.5 MHz, CDCl3) δ
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144.6, 141.9, 129.7, 126.9, 35.6, 30.5, 21.7, 21.6, 13.3; IR (neat) 2960, 1594, 1455, 1326, 1142
cm-1; Anal. Calcd for C11H16O2S2: C, 54.06; H, 6.60. Found: C, 53.92; H, 6.52.
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Typical procedure for copper-catalyzed sulfonylation of diselenides: Synthesis of Se-phenyl
benzeneselenosulfonate (5aa) (Table 3, entry 1)
To a mixture of diphenyl diselenide (46.8 mg, 0.15 mmol), sodium phenylsulfinate (54.2 mg,
0.33 mmol), and NH4BF4 (15.7 mg, 0.15 mmol), in DMA (0.6 mL) were added CuI (5.7 mg, 0.03
mmol) and Phen･H2O (5.9 mg, 0.03 mmol), and the mixture was stirred at 30 °C for 18 h in air
using balloon. After the residue was dissolved in Et2O, the solution was washed with H2O and
saturated sodium chloride and dried over anhydrous magnesium sulfate. Chromatography on
silica gel (20% diethyl ether / hexane) gave 5aa (63.1 mg, 71%): White solid. Mp: 53−54 °C; 1H
NMR (270 MHz, CDCl3) δ 7.55−7.26 (m, 10H, Ar-H); 13C{1H} NMR (67.5 MHz, CDCl3) δ
145.2, 137.2, 133.5, 130.9, 129.6, 128.7, 127.9, 127.0; IR (CHCl3) 1447, 1307, 1215, 1135 cm-1;
Anal. Calcd for C12H10O2SSe: C, 48.49; H, 3.39. Found: C, 48.16; H, 3.50.
Se-4-Phenyl 4-tolueneselenosulfonate (5ab): The title compound was obtained as a white solid
1
(61.5 mg, 66%). Mp: 79−80 °C; H NMR (270 MHz, CDCl3) δ 7.52−7.31 (m, 7H, Ar-H), 7.18
(d, J = 8.2 Hz, 2H, Ar-H), 2.41 (s, 3H, CH3); 13C{1H} NMR (67.5 MHz, CDCl3) δ 144.5, 142.6,
137.2, 130.8, 129.5, 129.2, 128.0, 127.0, 21.6; IR (CHCl3) 1594, 1440, 1318, 1215, 1134 cm-1;
Anal. Calcd for C13H12O2SSe: C, 50.16; H, 3.89. Found: C, 50.09; H, 3.85.
Se-Phenyl 4-methoxybenzeneselenosulfonate (5ac): The title compound was obtained as a white
1
solid (66.8 mg, 68%). Mp: 58−60 °C; H NMR (270 MHz, CDCl3) δ 7.52−7.31 (m, 7H, Ar-H),
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6.83 (d, J = 9.2 Hz, 2H, Ar-H), 3.85 (s, 3H, CH3); C{1H} NMR (67.5 MHz, CDCl3) δ 163.4,
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137.4, 137.2, 130.8, 129.5, 129.3, 128.1, 113.7, 55.7; IR (CHCl3) 1586, 1490, 1292, 1212, 1174
cm-1; Anal. Calcd for C13H12O3SSe: C, 47.71; H, 3.70. Found: C, 47.59; H, 3.69.
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Se-4-Phenyl 4-chlorobenzeneselenosulfonate (5ad): The title compound was obtained as a white
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solid (64.8 mg, 65%). Mp: 95−97 °C; H NMR (270 MHz, CDCl3) δ 7.52−7.34 (m, 9H, Ar-H);
13C{1H} NMR (67.5 MHz, CDCl3) δ 143.5, 140.0, 137.2, 131.1, 129.7, 128.9, 128.3, 127.6; IR
(CHCl3) 1578, 1474, 1213, 1136 cm-1; Anal. Calcd for C12H9ClO2SSe: C, 43.45; H, 2.74. Found:
C, 43.28; H, 2.71.
Se-Phenyl 4-fluorobenzeneselenosulfonate (5ae): The title compound was obtained as a white
1
solid (60.1 mg, 61%). Mp: 105−106 °C; H NMR (270 MHz, CDCl3) δ 7.54−7.46 (m, 5H, Ar-
H), 7.38−7.33 (m, 2H, Ar-H), 7.09−7.03 (m, 2H, Ar-H); 13C{1H} NMR (67.5 MHz, CDCl3) δ
165.3 (d, J = 256 Hz), 141.1 (d, J = 3 Hz), 137.2, 131.1, 129.8 (d J = 10 Hz), 129.7, 127.7, 115.9
(d, J = 23 Hz); IR (CHCl3) 1590, 1490, 1323, 1216, 1134 cm-1; Anal. Calcd for C12H9FO2SSe: C,
45.72; H, 2.88. Found: C, 45.69; H, 2.89.
Se-Phenyl 4-acetylaminobenzeneselenosulfonate (5af): The title compound was obtained as a
white solid (62.6 mg, 59%). Mp: 112−113 °C; 1H NMR (270 MHz, CDCl3) δ 7.65 (br, 1H, NH),
7.57−7.31 (m, 9H, Ar-H), 2.21 (s, 3H, CH3); 13C {1H} NMR (67.5 MHz, CDCl3) δ 168.7, 142.7,
139.9, 137.2, 131.0, 129.6, 128.4, 127.8, 118.6, 24.8; IR (CHCl3) 3430, 1701, 1589, 1513, 1319,
1215, 1133 cm-1; Anal. Calcd for C14H13NO3SSe: C, 47.46; H, 3.70; N, 3.95. Found: C, 47.56;
H, 3.42; N, 3.56.
Se-4-Tolyl 4-tolueneselenosulfonate (5bb): The title compound was obtained as a white solid
(61.9 mg, 63%). Mp: 107−108 °C; 1H NMR (270 MHz, CDCl3) δ 7.41 (d, J = 8.5 Hz, 2H, Ar-H),
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7.38 (d, J = 8.3 Hz, 2H, Ar-H), 7.20 (d, J = 8.5 Hz, 2H, Ar-H), 7.15 ( d, J = 8.3 Hz, 2H, Ar-H),
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2.41 (s, 3H, CH3), 2.39 (s, 3H, CH3); C{1H} NMR (67.5 MHz, CDCl3) δ 144.4, 142.8, 141.5,
137.2, 130.3, 129.2, 127.0, 124.7, 21.6, 21.5; IR (CHCl3) 1594, 1318, 1214, 1133 cm-1; Anal.
Calcd for C14H14O2SSe: C, 51.69; H, 4.34. Found: C, 51.51; H, 4.24.
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Se-4-Methoxyphenyl 4-tolueneselenosulfonate (5cb): The title compound was obtained as a
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white solid (68.7 mg, 70%). Mp: 77−79 °C; H NMR (270 MHz, CDCl3) δ 7.40 (d, J = 7.9 Hz,
2H, Ar-H), 7.40 (d, J = 8.8 Hz, 2H, Ar-H), 7.20 (d, J = 7.9 Hz, 2H, Ar-H), 6.84 (d, J = 8.8 Hz,
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2H, Ar-H), 3.84 (s, 3H, CH3), 2.41 (s, 3H, CH3); C{1H} NMR (67.5 MHz, CDCl3) δ 161.9,
144.4, 142.7, 139.0, 129.3, 127.0, 118.9, 115.1, 55.4, 21.6; IR (CHCl3) 1592, 1494, 1211, 1130
cm-1; Anal. Calcd for C14H14O3SSe: C, 49.27; H, 4.13. Found: C, 49.49; H, 4.07.
Se-1-Naphtyl 4-tolueneselenosulfonate (5db): The title compound was obtained as a yellow solid
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(61.9 mg, 57%). Mp: 119−121 °C; H NMR (270 MHz, CDCl3) δ 8.03−7.95 (m, 2H, Ar-H),
7.85−7.80 (m, 2H, Ar-H), 7.46−7.35 (m, 3H, Ar-H), 7.24 (d, J = 8.1 Hz, 2H, Ar-H), 6.99 (d, J =
8.1 Hz, 2H, Ar-H), 2.30 (s, 3H, CH3); 13C{1H} NMR (67.5 MHz, CDCl3) δ 144.4, 142.3, 138.7,
134.6, 134.0, 132.4, 129.1, 128.4, 127.9, 127.7, 127.3, 127.0, 126.5, 125.8, 21.5; IR (CHCl3)
1595, 1445, 1214, 1134 cm-1; Anal. Calcd for C17H14O2SSe: C, 56.51; H, 3.91. Found: C, 56.58;
H, 3.96.
Se-Benzyl 4-tolueneselenosulfonate (5eb): The title compound was obtained as a pale yellow oil
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(48.9 mg, 50%). H NMR (270 MHz, CDCl3) δ 7.70 (d, J = 8.2 Hz, 2H, Ar-H), 7.29−7.23 (m,
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7H, Ar-H), 4.49 (s, 2H, CH2), 2.44 (s, 3H, CH3); C{1H} NMR (67.5 MHz, CDCl3) δ 144.5,
144.5, 135.0, 129.7, 129.3, 128.8, 127.8, 126.4, 36.9, 21.6; IR (neat) 3061, 1594, 1493, 1454,
1301, 1133 cm-1; Anal. Calcd for C14H14O2SSe: C, 51.69; H, 4.34. Found: C, 51.29; H, 4.32.
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Large scale of sulfonylation of disulfide (Scheme 5)
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To a mixture of bis(4-tolyl) disulfide (369.6 mg, 1.5 mmol), sodium phenylsulfinate (641.5 mg,
3.6 mmol), and NH4BF4 (157.2 mg, 1.5 mmol), in DMA (0.3 mL) and H2O (0.1 mL) were added
CuI (28.6 mg, 0.15 mmol) and Phen･H2O (29.7 mg, 0.15 mmol), and the mixture was stirred at
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30 °C for 40 h in air using balloon. After the residue was dissolved in Et2O, the solution was
washed with H2O and saturated sodium chloride and dried over anhydrous magnesium sulfate.
Chromatography on silica gel (30% diethyl ether / hexane) gave S-4-tolyl 4-toluenethiosulfonate
(3ab) (628.2 mg, 75%).
1
Supporting Information. Supporting Information. Copies of the H NMR and 13C NMR
Spectra are provided. This material is available free of charge via the Internet at
http://pubs.acs.org.
REFERENCES
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13 A disulfide bond can be cleaved by Cu(I)X: (a) Kadooka, M. M.; Warner, L. G.; Seff, K. J.
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14 Many examples are described: Metal-Catalyzed Cross-Coupling Reactions; Meijere, A. de;
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16 Kochi, J. K.; Organometallic Mechanisms And Catalysis; Academic Press: San Diego, 1978.
17 When the reaction was in DMA (4.5 mL) and H2O (0.5 mL) was performed, the yield of 3ab
was 50%.
18 Weider, J. P.; Block, S. S. J. Med. Chem. 1967, 10, 1167−1170.
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