Copper-catalyzed 1,2-hydroxysulfenylation of alkene using disulfide via cleavage of the S-S bond

Article abstract of DOI:10.1021/jo060834l

(Chemical Equation Presented) Copper-catalyzed 1,2-hydroxysulfenylation of alkenes can be carried out by the use of disulfides and acetic acid in air. This reaction regio- and anti-selectively gave the corresponding 1,2-acetoxysulfides. Furthermore, the p

Full text of DOI:10.1021/jo060834l

Copper-Catalyzed 1,2-Hydroxysulfenylation of
Alkene Using Disulfide via Cleavage of the S-S
Bond
SCHEME 1. Strategy of 1,2-Hydroxysulfenylation of
Alkene with Disulfide
Nobukazu Taniguchi
Department of Chemistry, Fukushima Medical UniVersity,
Fukushima 960-1295, Japan
taniguti@fmu.ac.jp
As a rule, to synthesize hydroxysulfide with disulfide from
ReceiVed April 20, 2006
+
alkene, employment of RS is necessary. To date, a reaction
6,7
using a stoichiometric oxidant such as Pb(OAc)4 or an addition
8
of RSX has been explored. However, methods for a transition-
metal-catalyzed preparation of 1,2-hydroxysulfide using alkene
and disulfide are very limited. For instance, a procedure by
copper(II) acetate catalyst requires long reaction time and cannot
9
use both sulfide groups in disulfide. This is attributable to the
1
0
lower reactivity of the generated RSCu(I) as an intermediate.
As an approach to solve the problem, we researched a
Copper-catalyzed 1,2-hydroxysulfenylation of alkenes can
be carried out by the use of disulfides and acetic acid in air.
This reaction regio- and anti-selectively gave the correspond-
ing 1,2-acetoxysulfides. Furthermore, the present method
enables the use of both organosulfide groups of disulfide.
1
1 +
condition whereby (R S) or R S was formed by the oxidation
2
1
of R SCu(I) (Scheme 1) and found that a copper-catalyzed
reaction can be carried out in the presence of acetic acid. In
this paper, we wish to describe the methodology of a copper-
catalyzed 1,2-hydroxysulfenylation of alkene using disulfide in
DMF-AcOH.
Initially, the addition of various ROH was investigated in
order to optimize the reaction condition. In a combination of
DMF with alcohol or H2O using CuI-bpy (10 mol %), no
product was detected (Table 1, entries 1-3). Surprisingly, the
use of ethylene glycol afforded the corresponding hydroxysulfide
Transition-metal-catalyzed introduction of a sulfide-group to
an unsaturated carbon-carbon bond is an important procedure
in organic synthesis.1 In particular, hydrosulfenylation or
disulfenylation of alkene or alkyne using thiol or disulfide has
2,3
been developed by many researchers. Although hydroxysulfe-
nylation of alkene is a convenient procedure for the purpose of
direct introduction both organothio- and hydroxy-groups, a
catalytic process is developed rarely. These compounds obtained
herein can be synthesized by ring-opening of epoxides by
3
4
in 74% yield without the other regio-isomer (Table 1, entry
). It is noteworthy that in the case with CuI-bpy (5 mol %)
in acetic acid and DMF, 1,2-acetoxysulfide 3 could be obtained
in 92% yield (Table 1, entry 5). Two phenylsulfide groups in
4
,5
thiol.
(
5) (a) Metzner, P.; Thuillier, A. Sulfur Reagents in Organic Synthesis;
(
1) (a) Baird, C. P.; Rayner, C. M. J. Chem. Soc., Perkin Trans. 1 1998,
973-2003. (b) Payner, C. M. Contemp. Org. Synth. 1996, 3, 499-533.
c) Kondo, T.; Mitsudo, T.-a. Chem. ReV. 2000, 100, 3205-3220.
2) Hydrosulfenylation of alkene: (a) Kanemasa, S.; Oderaotoshi, Y.;
Katritzky, A. R., Meth-Cohn O., Rees, C. W., Eds.; Academic Press: San
Diego, 1994. (b) Swiss, K. A.; Liotta, D. C. ComprehensiVe Organic
Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press Ltd.: New York,
1991; Vol. 7, pp 515-526.
1
(
(
Wada, E. J. Am. Chem. Soc. 1999, 121, 8675-8676. (b) Munro-Leighton,
C.; Blue, E. D.; Gunnoe, T. B. J. Am. Chem. Soc. 2006, 128, 1446-1447.
Hydrosulfenylation of alkyne: (c) Kuniyasu, H.; Ogawa, A.; Sato, K.-I.;
Ryu, I.; Kambe, N.; Sonoda, N. J. Am. Chem. Soc. 1992, 114, 5902-5903.
(6) (a) Trost, B. M.; Ochiai, M.; McDougal, P. G. J. Am. Chem. Soc.
1978, 100, 7103-7106. (b) Toshimitsu, A.; Aoai, T.; Owada, H.; Uemura,
S.; Okano, M. J. Chem. Soc., Chem. Commun. 1980, 412-413. (c) Bewick
A.; Mellor, J. M.; Owton, W. M. J. Chem. Soc., Perkin Trans. 1 1985,
1039-1044. (d) Samii, Z. K. M. A. E.; Ashmawy, M. I. A.; Mello, J. M.
Tetrahedron Lett. 1986, 27, 5289-5292.
(7) (a) Wirth, T., Ed. Organoselenium Chemistry; Topics in Current
Chemistry, Vol. 208; Springer-Verlag: Heidelberg, Germany, 2000. (b)
Toshimitsu, A.; Terao, K.; Uemura, S. J. Org. Chem. 1986, 51, 1724-
1729. (c) Back, T. G.; Moussa, Z. Org. Lett. 2000, 2, 3007-3009. (d)
Bosman, C.; D’Annibale, A.; Resta, S.; Trogolo, C. Tetrahedron Lett. 1994,
35, 6525-6528. (e) Uneyama, K.; Kanai, M. Tetrahedron Lett. 1990, 31,
3583-3586.
(8) (a) Benati, L.; Mantevecci, P. C.; Spagnolo, P. Tetrahedron Lett.
1984, 25, 2039-2042. (b) Brownbridge, P. Tetrahedron Lett. 1984, 25,
3759-3762. (c) Hopkins, P. B.; Fuchs, P. L. J. Org. Chem. 1978, 43, 1208-
1217. (d) Tuladhar, S. M.; Fallis, A. G. Tetrahedron Lett. 1987, 28, 523-
526. (e) Reich, H. J. J. Org. Chem. 1973, 38, 428-429. (f) Sharpless, K.
B.; Lauer, R. F. J. Org. Chem. 1974, 39, 429-430.
(
d) B a¨ ckvall, J.-E.; Ericsson, A. J. Org. Chem. 1994, 59, 5850-5851. (e)
Ogawa, A.; Ikeda, T.; Kimura, K.; Hirao, T. J. Am. Chem. Soc. 1999, 121,
108-5114.
3) Disulfenylation of alkene: (a) Caserio, M. C.; Fisher, C. L.; Kim, J.
5
(
K. J. Org. Chem. 1985, 50, 4390-4393. (b) Kondo, T.; Uenoyama, S.;
Fujita, K.; Mitsudo, T. J. Am. Chem. Soc. 1999, 121, 482-483. (c) Usugi,
S.-i.; Yorimitsu, H.; Shinokubo, H.; Oshima, K. Org. Lett. 2004, 6, 601-
6
03. Disulfenylation of alkyne: (d) Kuniyasu, H.; Ogawa, A.; Miyaura,
S.-i.; Ryu, I.; Kambe, N.; Sonoda, N. J. Am. Chem. Soc. 1991, 113, 9796-
9
803. (e) Arisawa, M.; Yamaguchi, M. Org. Lett. 2001, 3, 763-764. (f)
Ananikov, V. P.; Beletskaya, I. P.; Aleksandrov, G. G.; Eremenko, I. L.
Organometallics 2003, 22, 1414-1421. (g) Ananikov, V. P.; Kabeshov,
M. A.; Beletskaya, I. P.; Khrustalev, V. N.; Antipin, M. Y. Organometallics
2
005, 24, 1275-1283. (h) Mono, A. V.; Nogueira, C. W.; Barbosa, N. B.
V.; Menezes, P. H.; Rocha, J. B. T.; Zeni, G. J. Org. Chem. 2005, 70,
257-5268.
4) Usually, a reaction of epoxide with thiol gives two regio-isomers.
a) Takeuchi, H.; Kitajima, K.; Yamamoto, Y.; Mizuno, K. J. Chem. Soc.,
5
(9) Bewick A.; Mellor, J. M.; Milano, D.; Owton, W. M. J. Chem. Soc.,
Perkin Trans. 1 1985, 1045-1048.
(10) (a) Taniguchi, N.; Onami, T. J. Org. Chem. 2004, 69, 915-920.
(b) Taniguchi, N. J. Org. Chem. 2004, 69, 6904-6906. (c) Taniguchi, N.
Synlett 2005, 1687-1690. (d) Taniguchi, N.; Onami, T. Synlett 2003, 829-
832.
(
(
Perkin Trans. 2 1993, 199-203. (b) Toshimitsu, A.; Hirosawa, C.; Nakano,
K.; Mukai, T.; Tamao, K. Phosphorus, Sulfur Silicon Relat. Elem. 1997,
1
20, 355-356.
10.1021/jo060834l CCC: $33.50 © 2006 American Chemical Society
7
874
J. Org. Chem. 2006, 71, 7874-7876
Published on Web 08/25/2006

TABLE 1. Copper-Catalyzed 1,2-Hydroxysulfenylation of Styrene
with Disulfide
TABLE 2. Copper-Catalyzed 1,2-Actoxysulfenylations of Alkynes
with Disulfides
entry
ROH
[Cu] (mol %)
3 (%)d
a
1
MeOH
n-PrOH
H2O
CuI (10)
CuI (10)
CuI (10)
CuI (10)
CuI (5)
0
trace
0
74
92
a
2
a
3
a,b,c
4
(HOCH2)2
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
5
6
e
CuI (5)
55
52
7
8
9
CuBr (5)
CuCl (5)
CuCl2 (5)
CuOAc (5)
Cu(OAc)2 (5)
none
trace
trace
trace
trace
0
10
11
12
a
The reaction was carried out at 100 °C. DMF was not used. c The
b
d
reaction was performed for 48 h. Isolated yields after silica gel chroma-
tography. The reaction was carried out in AcOH (0.3 mL).
e
disulfide were consumed completely. However, the use of CuBr
decreased the yield to 52% (Table 1, entry 7). Although other
copper salts (CuCl, CuCl2, CuOAc, and Cu(OAc)2 were
investigated, these showed no effects (Table 1, entries 8-11).
In the absence of a copper-catalyst, the reaction was not
promoted at all (Table 1, entry 12).
On the basis of the described result, we next carried out a
copper-catalyzed 1,2-acetoxysulfenylation of various alkenes 1
using disulfides 2 in DMF-AcOH. As shown in Table 2, the
reaction between the terminal akenes 1 with disulfides 2 could
regio-selectively afford the corresponding 1,2-acetoxysulfides
in good yields (Table 2, entries 1-9). Furthermore, the use of
trans-â-methylstyrene or intramolecular alkene gave derivatives
having anti-stereochemistry between the phenylthio and acetoxy
groups (Table 2, entries 10-16). The use of diphenyl
diselenide (2g) could also afford the same results (Table 2,
entries 7, 14, and 17). Thus we were able to perform a copper-
catalyzed 1,2-acetoxysulfenylation of alkene with disulfide in
good yield.
a Reaction conditions: alkene (0.3 mmol), (R3Y) (0.15 mmol), and CuI-
2
bpy (1:1, 5 mol %) in DMF (0.2 mL) and AcOH (0.2 mL) were treated at
9
0 °C. b Isolated yields after silica gel chromatography.
11
SCHEME 3. A Reactivity of PhSCu
For the purpose of investigation of this reaction mechanism,
we carried out a reaction of styrene with (PhS)2 in the absence
of oxygen. When the reaction was carried out under nitrogen
atmosphere, 3aa was obtained in only 8% yield (Scheme 2).
6
5% yield.13 This fact shows that disulfide is produced by the
SCHEME 2. Reaction of Styrene with (PhS)
Absence of Oxygen
2
in the
decomposition of PhSCu under acidic conditions. In the presence
of oxygen, it could afford 3aa in good yields by the addition of
n-Bu4NI (Scheme 3). In addition, the use of PhSH afforded
3
1
4
1
5
aa in only 5% yield (Scheme 4). Therefore, oxygen is
necessary for the present reaction; disulfide can be reproduced
from PhSCu under acidic conditions rather than the generation
of thiol.
Then, the reactivity of PhSCu(I) considered as an intermediate
was examined.12 Although this complex could not perform
sulfenylation of styrene under nitrogen, (PhS)2 was obtained in
SCHEME 4. Reaction between Benzenethiol with Styrene
(11) These stereochemistry were decided by a comparison between 1,2-
acetoxysulfide of entry 13 or 16 and authentic samples. These authentic
compounds were prepared by acetylation of the hydroxyl group after
solvolysis of cis-epoxides: Ruano, J. L. G.; Mart ´ı nez, M. C.; Rodriguez, J.
H.; Olef ´ı rowicz, E. M.; Eliel, E. L. J. Org. Chem. 1992, 57, 4215-4224.
From these results, a reaction mechanism is considered as
follows (Figure 1). After the CuI-catalyst acted on the disulfide
(
12) Organic Syntheses; John Wiley & Sons: New York, 1973; Collect.
Vol. V, pp 107-110.
J. Org. Chem, Vol. 71, No. 20, 2006 7875

1
,2-acetoxysulfides and enables the use of both organosulfide-
groups in disulfide. Furthermore, the present procedure is also
available for diselenide.
Experimental Section
Typical Procedure. Reaction of Styrene with Diphenyl Disulfide
in DMF-AcOH. To a mixture of CuI (2.9 mg, 0.015 mmol), bpy
(2.3 mg, 0.015 mmol), DMF (0.2 mL), and AcOH (0.2 mL) were
added diphenyl disulfide (32.8 mg, 0.15 mmol) and styrene (31.2
mg, 0.3 mmol), and the mixture was stirred at 90 °C for 18 h in
air. After evaporation of the solvent, the residue was dissolved in
FIGURE 1. A plausible reaction mechanism.
as a Lewis acid or co-oxidant in air, reaction of intermediates
Et
chloride and dried over anhydrous magnesium sulfate. Chroma-
tography on silica gel (20% Et O in hexane) gave 1-acetoxy-1-
phenyl-2-phenylthioethane (Table 2, entry 1) (75.1 mg, 92%). H
NMR (270 MHz, CDCl ): δ 2.01 (s, 3H), 3.23 (dd, J ) 13.8 and
.3 Hz, 1H), 3.40 (dd, J ) 13.8 and 7.9 Hz, 1H), 5.88 (dd, J ) 7.9
2 2
O. The solution was washed with H O and saturated sodium
1
6
5
with styrene 1 gives sulfonium ion 4 and PhSCu(I) 7.
2
Sequentially, 1,2-acetoxysulfide 3 was obtained in DMF-
AcOH. PhSCu 7 gives disulfide 2 and Cu(I)ILn again under
acidic conditions in air because 7 cannot carry out sulfenylation
of alkene.
In conclusion, we achieved copper-catalyzed 1,2-hydrox-
ysulfenylation of alkene using disulfide and acetic acid in air.
This reaction regio- and anti-selectively gives the corresponding
1
3
5
13
and 5.3 Hz, 1H), 7.15-7.39 (m, 10H). C NMR (67.5 MHz,
CDCl
3
): δ 20.9, 40.0, 74.5, 126.5, 126.6, 128.4, 128.5, 128.9, 130.1,
-1
135.6, 138.9, 170.0. IR (neat): 3061, 3033, 1743, 1583 cm . Anal.
16 2
Calcd for C16H O S: C, 70.56; H, 5.92. Found: C, 70.35; H, 5.83.
(
13) The treatment of PhSCu (0.3 mmol), bpy (0.3 mmol) in DMF (1.0
Acknowledgment. This work was supported by Meiji Seika
Co. Ltd.
mL), and H2O (1.0 mL) at 100 °C for 18 h afforded (PhS)2 in only 5%
yield. But the use of AcOH instead of H2O gave disulfide in 66% yield.
Consequently, it is difficult to produce (PhS)2 from PhSCu under neutral
conditions.
14) n-Bu4NI was added as a source of I- because Cu(OAc) cannot
Supporting Information Available: Experimental procedures
(
1
13
promote the 1,2-acetoxysulfenylation of alkene with disulfide.
and analytical data ( H and C NMR spectra). This material is
available free of charge via the Internet at http://pubs.acs.org.
(
15) Additive products of PhSH were not detected under this condition.
(16) Takeuchi, H.; Hiyama, T.; Kamai, N.; Oya, H. J. Chem. Soc., Perkin
Trans. 2 1997, 2301-2305.
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876 J. Org. Chem., Vol. 71, No. 20, 2006