Rongalite promoted highly regioselective synthesis of β-hydroxy sulfides by ring opening of epoxides with disulfides

Article abstract of DOI:10.1016/j.tet.2009.04.085

Rongalite promotes cleavage of disulfides generating thiolate anions that then undergo facile ring opening of epoxides in the presence of K₂CO₃ to afford α-addition products 3 with good to excellent yields. The important f

Full text of DOI:10.1016/j.tet.2009.04.085

Tetrahedron 65 (2009) 5240–5243
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RongaliteÒ promoted highly regioselective synthesis of
by ring opening of epoxides with disulfides
b-hydroxy sulfides
,
a
a
,
,
Wenxue Guo a, Jiuxi Chen a , Dengze Wu , Jinchang Ding b, Fan Chen a, Huayue Wu a
*
*
a College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325027, China
b Wenzhou Vocational and Technical College, Wenzhou 325035, China
a r t i c l e i n f o
a b s t r a c t
RongaliteÒ promotes cleavage of disulfides generating thiolate anions that then undergo facile ring
Article history:
Received 25 February 2009
Received in revised form 1 April 2009
Accepted 24 April 2009
opening of epoxides in the presence of K2CO3 to afford a-addition products 3 with good to excellent
yields. The important features of this methodology are broad substrates scope, high yielding, reasonably
rapid reaction rate, high regioselectivity and no requirement of metal catalysts. It should be noted that
Available online 3 May 2009
the thiolate anion attacks the epoxides derived from styrene to produce the corresponding
products 3 with high regioselectivity, instead of the -addition regioisomer 4 that could be formed from
the attack of the nucleophile at the benzylic position.
a-addition
b
Keywords:
RongaliteÒ
Ó 2009 Elsevier Ltd. All rights reserved.
b-Hydroxy sulfides
Epoxides
Disulfides
Regioselectivity
1. Introduction
of unpleasant odor substrates6–10 and expensive, toxic or metallic
catalysts,12,14–16 long reaction times,12–15 unsatisfactory yields14,15
as well as elevated temperature.13,15,16 Therefore, developing ver-
satile approaches to synthesize b-hydroxy sulfides selectively still
remains a highly desired goal in organic synthesis.
Epoxides are important precursors in organic synthesis1 and their
reactions with different nucleophiles (e.g., amines, thiols, alcohols,
etc.) have been the subject of extensive studies.2 Among them,
thiolysis of epoxides has attracted comparatively more attention
since it produces
organic chemistry,3 especially in the fields of pharmaceuticals4 and
natural products chemistry.5 Classical synthesis of
-hydroxy sul-
In continuation of our researches in developing novel synthetic
routes for the formations of carbon–carbon and carbon-heteroatom
bonds,9,10,17 we herein report a highly efficient and regioselective
b-hydroxy sulfides as important intermediates in
b
synthesis of b
-hydroxy sulfides by RongaliteÒ (sodium formalde-
fides involves the ring opening of an epoxide by an excess of thiol,
which inevitably incurs unpleasant odor, either catalyzed by Lewis
hyde sulfoxylate, NaHSO2$CH2O$2H2O as an inexpensive reagent)
promoted thiolysis of epoxides with disulfides (Scheme 1).
7
acid,6 PBu3 or under microwave irradiation conditions.8 Recently,
we have studied the thiolysis reaction of epoxides in ionic liquids
without any catalyst9 or with gallium(III) triflate as a catalyst.10
In addition, disulfide bond cleavage could lead to interesting
products by the reaction of the resulting nucleophilic sulfur11 spe-
cies to a variety of organic substrates. Thus, the method has been
K2CO3
OH
O
NaHSO2·CH2O·2H2O
S
R1
R
+
RSSR
2
R1
DMF, r.t., 5 min
β
α
R
R2
( C-α )
1 R1>R2
2
3
developed in recent years for the synthesis of b-hydroxy sulfides by
Scheme 1. Ring opening of epoxides with disulfides.
the reaction of epoxides with disulfides using different promoting
agents. These promoting agents include tetrathiomolybdate,12
NaBH4/Amberlite IRA 400,13 ytterbium(III) chalcogenolate com-
plexes,14 InI–InCl3,15 Zn–Bi(OTf)3 or Zn–Bi(TFA)3.16 However, these
methods usually suffer from one or more limitations such as the use
2. Results and discussion
The model ring opening reaction of 2-phenyloxirane 1a with
1,2-diphenyldisulfide 2a was conducted to screen the optimal re-
action conditions and the results were listed in Table 1. Initially, the
effect of solvents was tested. Among all the solvents screened,
(acetonitrile, water, HMPA, and DMF), DMF afforded an interesting
* Corresponding authors. Tel./fax: þ86 577 8836 8280.
E-mail addresses: jiuxichen@wzu.edu.cn (J. Chen), huayuewu@wzu.edu.cn
(H. Wu).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.04.085

W. Guo et al. / Tetrahedron 65 (2009) 5240–5243
5241
a
Table 1
Table 2
Screening conditions for the thiolysis of 2-phenyloxirane with 1,2-
diphenyldisulfidea
Ring opening of epoxides with disulfides in the presence of RongaliteÒ and K2CO3
SR
.
.
O
NaHSO
2 H O, K CO
2
2 3
2 CH2O
SR
+
R2
( C-α )
Ph
R1
OH
OH
R1
S
+
RSSR
O
2
R1
R
DMF, r.t., 5 min
α
β
+
PhSSPh
+
S
R2
( C-β )
OH
α
β
Ph
3a ( C-α )
Ph
Ph
Ph
1 R1>R2
4
2
3
1a
2a
4a ( C-β )
Entry
Epoxide
R
Product
Yieldb (%)
Entry
RongaliteÒ (equiv)
Base
Solvent
Yieldb (%)
R1
R2
1
2
3
4
5
6
7
8
2
2
2
2
2
3
3
3
3
3
3
d
1
2
3
3
3
3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
d
CH3CN
Toluene
HMPA
H2O
11
NR
Trace
NR
79
6
NR
6
10
1
2
3
4
5
6
7
8
C6H5
C6H5
C6H5
C6H5
H
C6H5
3a
3b
3c
3d
3e
3f
3g
3h
3i
3j
3k
3l
3m
3n
3o
3p
3q
3r
98
99
97
83
97
95
94
91
84
95
95
98
95
80
95
84
83
93
97
94
81
99
85
87
83
91
H
H
H
H
H
H
H
H
H
H
H
H
H
H
p-(CH3)C6H4
p-(Cl)C6H4
p-(F)C6H4
o-(NH2)C6H4
C6H5
p-(CH3)C6H4
p-(Cl)C6H4
p-(F)C6H4
o-(NH2)C6H4
C6H5
p-(CH3)C6H4
p-(Cl)C6H4
p-(F)C6H4
o-(NH2)C6H4
C6H5
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
C6H5
K3PO4
Et3N
p-(Cl)C6H4
p-(Cl)C6H4
p-(Cl)C6H4
p-(Cl)C6H4
p-(Cl)C6H4
C6H5OCH2
C6H5OCH2
C6H5OCH2
C6H5OCH2
C6H5OCH2
–(CH2)4–
–(CH2)4–
ClCH2
ClCH2
ClCH2
ClCH2
ClCH2
n-C6H13
n-C6H13
n-C6H13
n-C6H13
9
KF$2H2O
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
10
11
12
13
14
15
16
17
18
5
9
98
NRc
64
83
35d
87e
98f
89g
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
p-(CH3)C6H4
C6H5
H
H
H
H
H
H
H
H
H
NR¼No reaction.
p-(CH3)C6H4
p-(Cl)C6H4
p-(F)C6H4
o-(NH2)C6H4
C6H5
p-(CH3)C6H4
p-(Cl)C6H4
p-(F)C6H4
3s
3t
a
All reactions were run with 1a (0.4 mmol), 2a (0.2 mmol), and solvent (2 mL) at
room temperature for 5 min.
3u
3v
3w
3x
3y
3z
b
Isolated total yield of 3a, the regioisomer 4a was not detected.
c
Without RongaliteÒ
0.2 equiv of K2CO3.
1 equiv of K2CO3.
3 equiv of K2CO3.
At 50 ꢀC.
.
d
e
f
g
a
All reactions were run with epoxide 1 (0.5 mmol), disulfide 2 (0.2 mmol),
NaHSO2$CH2O$2H2O (0.6 mmol), K2CO3 (0.3 mmol) and DMF (2 mL) at room tem-
perature for 5 min.
result, where 1a undergoes the cleavage with 2a to produce only a-
b
Isolated yield of 3, the regioisomer 4 was not detected.
addition products 3a in 79% yield with Cs2CO3 as a base (Table 1,
entry 5). Encouraged by this promising result, we further optimized
the reaction conditions including the effect of bases, reaction
temperature, and the amount of RongaliteÒ.
obvious effect on the yield. When less nucleophilic thiophenol
(R¼p-FC6H4) (Table 2, entries 4, 9, 14, 21, and 26) was used, the
reactions could also work efficiently compared to electron-rich
thiophenol (R¼p-MeC6H4) (Table 2, entries 2, 7, 12, 17, 19, and 24)
under the same conditions. On the other hand, the chemoselective
thiolysis in the presence of unprotected reactive functional groups
such as -NH2 also proved to be successful. The corresponding
products of 3e, 3j, 3o, and 3z were obtained in high yields (Table 2,
entries 5, 10, 15, and 26).
It was found that 3a was not obtained in the absence of a base
(Table 1, entry 7). Among the screened bases, KF$2H2O, Et3N, and
K3PO4 provided only 5%,10%, and 6% yield of 3a, respectively (Table 1,
entries 8–10). However, it was satisfying to find that the reaction
could reach to completion in as short as 5 min and afforded 3a in 98%
yield regiospecifically when the combination of K2CO3 and DMF
was employed at room temperature in the presence of 3 equiv of
RongaliteÒ (Table 1, entry 11). Moreover, the yield was significantly
affected by the amount of RongaliteÒ (Table 1, entries 11–14) and
K2CO3 (Table 1, entries 11, 15–17). The results indicated that the yield
was decreased to some extent when 2 equiv of RongaliteÒ was added,
and no reaction was observed even for longer time in the absence
of RongaliteÒ (Table 1, entry 12). Decreasing the amount of K2CO3
(Table 1, entries 15–16) in the system reduced the yield slightly. The
yieldwasdecreased to some extentwhen thereactionwascarried out
at the elevated temperature (Table 1, entry 18). As a result, the model
reaction was carried out under optimized conditions with 3 equiv of
RongaliteÒ and 1.5 equivofK2CO3 atroomtemperatureinDMF, which
led to the desired product 3 with 98% yield and high regioselectivity.
With the optimal conditions in hand, the scope of both disulfides
and epoxides was explored and the results are summarized inTable 2.
In all cases, RongaliteÒ-catalyzed reactions proceeded smoothly and
gave the corresponding products in good to excellent yields. The
highly regioselective nucleophilic attack of thiophenols occurred al-
It should be especially noted that the epoxides derived from sty-
rene, such as 2-phenyloxirane underwent cleavage with disulfide to
afford only one corresponding a-addition products 3a–3e in our pro-
1
cedure (Table 2, entries 1–5). Their structures were confirmed by H
NMR and 13C NMR spectral data in comparison with those reported in
literature.9,18 This regioselectivity is not similar to that obtained from
thiolysis of epoxides in the presence of ytterbium(III) chalcogenolate
16
complexes,14 InI–InCl3,15 Zn–Bi(OTf)3 or Zn–Bi(TFA)3 in which the
regioisomer 4 as the major product was formed from attack of the
nucleophile at the benzylic position. Similarly, the thiolysis of 2-(4-
chlorophenyl)oxirane with disulfide was also examined and the cor-
responding
a-addition products 3f–3j were obtained with high
regioselectivity in excellent yields (Table 2, entries 6–10). On the other
hand, the ring opening of symmetrical epoxide, such as cyclohexene
oxide with disulfides to produce the corresponding b-hydroxy sulfides
with high stereoselectivity in good yields (Table 2, entries 16 and 17).
Only the products of trans-isomer were formed based on 1H NMR
spectrum. If the epoxide is unsymmetrical, attack by the thiolate anion
occurs primarily at the less substituted carbon atom. For example, 2-
(chloromethyl)oxirane or 2-hexyloxirane reacts with the thiolate anion
selectively at its primary carbon atom (Table 2, entries 18–26).
most exclusively on the less hindered a-carbon of the oxirane ring.
A series of aromatic disulfides bearing either electron-donating
or electron-withdrawing groups on the aromatic ring were in-
vestigated. The substitution groups on the aromatic ring had no

5242
W. Guo et al. / Tetrahedron 65 (2009) 5240–5243
Finally, to extend the scope of this reaction, the thiolysis of chiral
epoxide, such as (R)-2-(chloromethyl)oxirane (99% ee) was also
examined using the present protocol. It was found that optically
used as the solvent. Mass spectrometric analysis was performed on
GC–MS analysis (SHIMADZU GCMS-QP2010). Optical rotations
were measured with Autopol IV RUDOLPH RESEARCH ANALYTICAL
(U.S.A.) automatic polarimeter in chloroform solution. Enantio-
mertic excesses (ee) were determined with a HPLC apparatus fitted
with a Chiralcel OJ-H (Daicel, Germany) chiral column. Elemental
analysis was determined on a Carlo–Erba 1108 instrument.
pure epoxide was converted into the corresponding
b-hydroxy
sulfide 3s0 without any racemization or inversion (Scheme 2).
OH
K2CO3
NaHSO2 CH2O 2H2O
.
.
O
Cl
S
4.2. General procedure for synthesis of b-hydroxy sulfides
+
Me
S
Cl
DMF, r.t., 5 min
2
Me
(R), 95% yield, 98% ee 3s'
A mixture of epoxides 1 (0.4 mmol), disulfide 2 (0.2 mmol),
RongaliteÒ (3 equiv), and K2CO3 (1.5 equiv) in DMF (2 mL) was
stirred at room temperature for 5 min under air. The reaction
mixture washed with water, extracted with ethyl acetate, the or-
ganic phase was separated and dried over anhydrous sodium sul-
fate, filtered and the solvent was evaporated under vacuum. The
residue was purified by flash column chromatography (ethyl ace-
tate or hexane/ethyl acetate) to afford the desired product 3.
(R)
Scheme 2. The thiolysis of chiral epoxides.
According to the previous proposed mechanism,19 RongaliteÒ
promotes mainly the cleavage of disulfides and produces the thio-
late anion, which undergoes ring opening of epoxides in the
presence of K2CO3. A tentative mechanism for the formation of b-
hydroxy sulfides was proposed in Scheme 3. RongaliteÒ can be
readily decomposed into HCHO and HSOꢁ2 anion (A). Intermediate
(A) then reacts with RSSR (2) to generate two radical intermediates
(B and D) and the thiolate anion (C). The radical (B) can also be
converted into the anion (C) by reacting with intermediate (D).
Finally, the nucleophilic attack of the thiolate anion (C) to the less
hindered position of the epoxide (1) affords the target product.
4.2.1. 2-(4-Fluorophenylthio)-1-phenylethanol (3d)
(Table 2, entry 4)
1H NMR (CDCl3, 300 MHz)
d 7.44–7.31 (m, 7H), 7.05–6.99 (m,
2H), 4.69 (dd, J¼9.2, 3.7 Hz, 1H), 3.25 (dd, J¼13.7, 3.7 Hz, 1H),
3.11–3.03 (m, 1H), 2.89 (br s, 1H, OH); 13C NMR (75 MHz, CDCl3)
1
3
d
162.1 (d, JC–F¼245.8 Hz), 142.0, 133.1 (d, JC–F¼8.0 Hz), 129.9,
(d, 4JC–F¼3.2 Hz) 128.5, 128.0, 125.8, 116.2 (d, 2JC–F¼21.8 Hz), 71.7,
45.1; IR (KBr, cmꢁ1): 3433, 3032, 2922, 1594, 1532, 1490, 1441; MS
(EI, 70 eV) m/z (%): 248 (Mþ, 12), 142 (100). Anal. Calcd for
C14H13FOS: C, 67.72; H, 5.28. Found: C, 67.66; H, 5.33.
OCH2SO2H
HCHO
+
HSO2
A
RSSR
+
HSO2
A
+
RS
C
RS
B
+ HSO2
D
2
4.2.2. 1-(4-Chlorophenyl)-2-(4-chlorophenylthio)ethanol (3h)
(Table 2, entry 8)
+
HSO2
RS
B
+ SO2
+
RS
C
H
1H NMR (CDCl3, 300 MHz)
d
7.32–7.22 (m, 8H), 4.66 (dd, J¼9.0,
D
J¼3.9, 1H), 3.21 (dd, J¼13.8, 3.9 Hz, 1H), 3.07–3.00 (m, 2H); 13C NMR
(75 MHz, CDCl3)
d 140.3, 133.5, 133.1, 132.8, 131.4, 129.6, 129.1, 128.5,
O
O
OH
127.0, 126.8, 125.1, 70.9, 43.8; IR (KBr, cmꢁ1): 3218, 3069, 2923, 1577,
1545,1455,1417; MS (EI, 70 eV) m/z (%): 298 (Mþ,12),158 (100). Anal.
Calcd for C14H12Cl2OS: C, 56.20; H, 4.04. Found: C, 56.15; H, 3.98.
H
SR
+
SR
R1
R2
RS
C
R1
R1
1 R1 > R2
R2
R2
Scheme 3. A possible mechanism.
4.2.3. 1-(4-Chlorophenyl)-2-(4-fluorophenylthio)ethanol (3i)
(Table 2, entry 9)
3. Conclusion
In summary, a highly regioselective synthesis of
sulfides has been developed by ring opening of epoxides by disul-
fides promoted by inexpensive RongaliteÒ. Especially, the epoxides
resulting from styrenes undergo the ring opening and the corre-
1H NMR (CDCl3, 300 MHz)
d 7.42–7.37 (m, 2H), 7.31–7.22 (m,
4H), 7.01 (t, J¼6.7 Hz, 2H), 4.64 (dd, J¼9.0, 3.9 Hz, 1H), 3.19 (dd,
b
-hydroxy
J¼3.8, 13.8 Hz, 1H), 3.04–2.97 (m, 2H, including br s, OH); 13C NMR
(75 MHz, CDCl3)
d
162.2 (d, 1JC–F¼246.2 Hz), 140.4, 133.6, 133.3 (d,
4
2
3JC–F¼8.0 Hz), 129.5 (d, JC–F¼3.3 Hz), 128.6, 127.2, 116.3 (d, JC–F
¼
21.8 Hz), 71.0, 45.0; IR (KBr, cmꢁ1): 3223, 3064, 2922, 1588, 1545,
1460, 1407; MS (EI, 70 eV) m/z (%): 282 (Mþ, 10), 142 (100). Anal.
Calcd for C14H12ClFOS: C, 59.47; H, 4.28. Found: C, 59.51; H, 4.23.
sponding a-addition products 3 were obtained in good to excellent
yields. Besides, the present method allows the reaction to be car-
ried out under mild conditions and completed in short time
(5 min), which is an additional advantage of this protocol. Efforts to
explore the detailed mechanism and further applications of the
present system in other transformations using disulfide as a re-
action partner are ongoing in our group.
4.2.4. 2-(2-Aminophenylthio)-1-(4-chlorophenyl)ethanol (3j)
(Table 2, entry 10)
1H NMR (CDCl3, 300 MHz)
d 7.48–7.44 (m, 1H), 7.33–7.19 (m, 6H),
6.79 (t, J¼7.6 Hz, 2H), 4.53 (dd, J¼9.4, 3.2 Hz,1H), 4.42 (br s, 2H, NH2),
3.60 (br s,1H, OH), 3.13 (dd, J¼13.4, 3.3 Hz,1H), 2.91–2.84 (m,1H); 13C
4. Experimental section
4.1. General
NMR (75 MHz, CDCl3) d 148.5, 141.0, 136.6, 133.5, 130.6, 128.7, 119.5,
117.0, 115.7, 71.5, 44.7. IR (KBr, cmꢁ1): 3406, 3283, 3063, 2920, 1659,
1612, 1507, 1476; MS (EI, 70 eV) m/z (%): 279 (Mþ,14),139 (100). Anal.
Calcd for C14H14ClNOS: C, 60.10; H, 5.04. Found: C, 60.14; H, 4.99.
Chemicals and solvents were either purchased or purified by
standard techniques. Melting points were uncorrected and recor-
ded on Digital Melting Point Apparatus WRS-1B. IR spectra were
recorded on an AVATAR 370 FI-Infrared Spectrophotometer. NMR
spectroscopy was performed on both a Bruck-300 spectrometer
operating at 300 MHz (1H NMR) and 75 MHz (13C NMR). TMS
(tetramethylsilane) was used as an internal standard and CDCl3 was
4.2.5. 1-(2-Aminophenylthio)-3-phenoxypropan-2-ol
(3o) (Table 2, entry 15)
White solid, mp 65–68 ꢀC; 1H NMR (CDCl3, 300 MHz)
d 7.50–7.47
(m, 1H), 7.35 (t, J¼7.5 Hz, 2H), 7.19 (t, J¼1.1 Hz, 1H), 7.04–6.92 (m,
3H), 6.77 (t, J¼7.7 Hz, 2H), 4.4 7 (br s, 2H, NH2), 4.07–4.01 (m, 3H),
3.39 (br s, 1H, OH), 3.15–2.95 (m, 2H); 13C NMR (75 MHz, CDCl3)

W. Guo et al. / Tetrahedron 65 (2009) 5240–5243
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´
`
`
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69.0, 39.0; IR (KBr, cmꢁ1): 3405, 3333, 3055, 2928, 1660, 1593, 1514,
1454; MS (EI, 70 eV) m/z (%): 275 (Mþ, 40), 125 (100). Anal. Calcd for
C15H17NO2S: C, 65.43; H, 6.22. Found: C, 65.49; H, 6.29.
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4.2.6. 1-(p-Tolylthio)octan-2-ol (3x) (Table 2, entry 24)
1H NMR (CDCl3, 300 MHz)
d
7.27 (d, J¼8.1 Hz, 2H), 7.07 (d,
J¼7.9 Hz, 2H), 3.58 (s, 1H), 3.06 (dd, J¼13.5, 3.3 Hz, 1H), 2.79–2.72
(m, 1H), 2.47 (s, 1H), 2.28 (s, 3H), 1.49–1.23 (m, 10H), 0.84 (t,
J¼6.1 Hz, 3H); 13C NMR (75 MHz, CDCl3)
d 136.8, 131.4, 130.8, 129.8,
69.2, 42.9, 36.0, 31.7, 29.2, 25.6, 22.5, 21.0,14.0; IR (KBr, cmꢁ1): 3287,
3023, 2983, 2884, 2835, 1725, 1560, 1472, 1431; MS (EI, 70 eV) m/z
(%): 252 (Mþ, 34), 138 (100). Anal. Calcd for C15H24OS: C, 71.37; H,
9.58. Found: C, 71.45; H, 9.62.
5. (a) Hammarstro¨m,S.; Samuelsson, B.; Clark, D. A.;Goto, G.;Marfat, A.;Mioskowski,
C.; Corey, E. J. Biochem. Biophys. Res. Commun. 1980, 92, 946; (b) Luly, J. R.; Yi, N.;
Soderquist, J.; Stein, H.; Cohen, J.; Perun, T. J.; Plattner, J. J. J. Med. Chem. 1987, 30,
1609.
4.2.7. 1-(4-Fluorophenylthio)octan-2-ol (3z) (Table 2, entry 26)
1H NMR (CDCl3, 300 MHz)
d 7.41–7.37 (m, 2H), 7.02–6.96 (m,
6. (a) Maiti, A. K.; Biswas, G. K.; Bhattacharyya, P. J. Chem. Res., Synop. 1997, 325;
(b) Mojtahedi, M. M.; Ghasemi, M. H.; Abaee, M. S.; Bolourtchian, M. ARKIVOC
2005, xv, 68; (c) Iida, T.; Yamamoto, N.; Sasai, H.; Shibasaki, M. J. Am. Chem. Soc.
1997, 119, 4783; (d) Wu, M. H.; Jacobson, E. N. J. Org. Chem. 1998, 63, 5252; (e)
Wu, J.; Hou, X. L.; Dai, L. X.; Xia, L. J.; Tang, M. H. Tetrahedron: Asymmetry 1998,
9, 3431; (f) Yadav, J. S.; Reddy, B. V. S.; Baishya, G. Chem. Lett. 2002, 906; (g)
Fringuelli, F.; Pizzo, F.; Tortoioli, S.; Vaccaro, L. Tetrahedron Lett. 2003, 44, 6785;
(h) Chandrasekhar, S.; Reddy, C. R.; Babu, B. N.; Chandrasekhar, G. Tetrahedron
Lett. 2002, 43, 3801; (i) Cossy, J.; Bellosta, V.; Hamoir, C.; Desmurs, J.-R. Tetra-
hedron Lett. 2002, 43, 7083.
2H), 3.66–3.58 (m, 1H), 3.07 (dd, J¼13.5, 3.5 Hz, 1H), 2.84–2.77 (m,
1H), 2.49 (s, 1H), 1.52–1.26 (m, 10H), 0.87 (t, J¼6.3 Hz, 3H); 13C NMR
(75 MHz, CDCl3)
d
162.0 (d, 1JC–F¼245.5 Hz), 132.9(d, 3JC–F¼8.0 Hz),
130.3, 116.1 (d, 2JC–F¼21.8 Hz), 69.3, 43.4, 36.0, 31.7, 29.2, 25.5, 22.5,
14.0; IR (KBr, cmꢁ1): 3279, 2926, 1678, 1654, 1624, 1575; MS (EI,
70 eV) m/z (%): 256 (Mþ, 30), 142 (100). Anal. Calcd for C14H21FOS:
C, 65.59; H, 8.26. Found: C, 65.63; H, 8.20.
7. Fan, R. H.; Hou, X. L. J. Org. Chem. 2003, 68, 726.
Acknowledgements
8. Pironti, V.; Colonna, S. Green. Chem. 2005, 7, 43.
9. Chen, J. X.; Wu, H. Y.; Jin, C.; Zhang, X. X.; Xie, Y. Y.; Su, W. K. Green. Chem. 2006,
8, 330.
10. Su, W. K.; Chen, J. X.; Wu, H. Y.; Jin, C. J. Org. Chem. 2007, 72, 4524.
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13. Yoon, N. M.; Choi, J.; Ahn, J. H. J. Org. Chem. 1994, 59, 3490.
14. Jennifer, D.; Fiona, M.; David, J. P. Tetrahedron Lett. 2000, 41, 4923.
15. Ranu, B. C.; Mandal, T. Can. J. Chem. 2006, 84, 762.
We thank the National Key Technology R&D Program (No.
2007BAI34B00), the National Natural Science Foundation of China
(No. 20471043) and Natural Science Foundation of Zhejiang Prov-
ince (No. Y4080107) for financial support.
Supplementary data
16. Khodaei, M. M.; Khosropour, A. R.; Ghozati, K. J. Braz. Chem. Soc. 2005, 16, 673.
17. (a) Chen, J. X.; Wu, H. Y.; Zheng, Z. G.; Jin, C.; Zhang, X. X.; Su, W. K. Tetrahedron
Lett. 2006, 47, 5383; (b) Chen, X. A.; Zhang, C. F.; Wu, H. Y.; Yu, X. C.; Su, W. K.;
Ding, J. C. Synthesis 2007, 20, 3233; (c) Chen, J. X.; Su, W. K.; Wu, H. Y.; Liu, M. C.;
Jin, C. Green. Chem. 2007, 9, 972; (d) Chen, J. X.; Wu, D. Z.; He, F.; Liu, M. C.; Wu,
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Supplementary data associated with this article can be found in
the online version, at doi:10.1016/j.tet.2009.04.085.
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