Micellar media for the efficient ring opening of epoxides with CN-, N3-, NO3-, NO2-, SCN-, Cl- and Br- catalyzed with Ce(OTf)4

Article abstract of DOI:10.1039/b211697a

Micellar media are introduced for the efficient ring opening of epoxides with sodium salts of nucleophiles such as CN, N₃^-, NO₃^-, NO₂, SCN, Br and Cl^-, catalyzed with Ce(OTf)₄. This method is an efficient procedure for the synthesis of different β-substituted alcohols under mild reaction conditions. The reaction with SCN^- is an easy procedure for the high yielding preparation of epoxy sulfides.

Full text of DOI:10.1039/b211697a

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Micellar media for the efficient ring opening of epoxides with
؊
؊
؊
CN؊, N3 , NO3 , NO2 , SCN؊, Cl؊ and Br؊ catalyzed with
Ce(OTf)4
Nasser Iranpoor,*a Habib Firouzabadi*a and Marzieh Shekarizeb
a Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71454, Iran.
E-mail: iranpoor@chem.susc.ac.ir; firouzabadi@chem.susc.ac.ir.; Fax: ϩ98–711-2280926;
Tel: ϩ98–711-2284822
b Additive Department, Chemistry & Petrochemical Division, Research Institute of Petroleum
Industry, Tehran, Iran
Received 27th November 2002, Accepted 9th January 2003
First published as an Advance Article on the web 28th January 2003
Micellar media are introduced for the efficient ring opening of epoxides with sodium salts of nucleophiles such
as CNϪ, N3Ϫ, NO3Ϫ, NO2Ϫ, SCNϪ, BrϪ and ClϪ, catalyzed with Ce(OTf )4. This method is an efficient procedure
for the synthesis of different β-substituted alcohols under mild reaction conditions. The reaction with SCNϪ is
an easy procedure for the high yielding preparation of epoxy sulfides.
anion in metal–CN, the low yields of the products, long
Introduction
reaction times or unavailability of the reagent,28–32 we first
studied the effect of different micellar media for this important
transformation. The ring opening reaction of styrene oxide
with NaCN was studied in the micellar solution of sodium
dodecyl sulfate (SDS) as an anionic micelle, cetyl trimethyl-
ammonium bromide (CTAB) as a cationic micelle, and Triton
X-100 as a neutral micelle at different concentrations in the
presence of catalytic amounts of Ce(OTf )4. This reaction with
1.5 molar equivalents of NaCN in the presence of 10 mol%
Ce(OTf )4 was optimized in the above mentioned micellar media
at room temperature (Scheme 1).
It is well established that, in many cases, performing the
reactions in micellar media instead of organic solvents can alter
rates and the pathways of the reactions. Micelles can concen-
trate the reactants within their small volumes;1–3 stabilize sub-
strates, intermediates or products;4–7 and orient substrates;8–10
so that ionization potentials and oxidation–reduction proper-
ties,11,12 dissociation constants,13,14 physical properties, quantum
efficiencies and reactivities15,16 are changed. Therefore, we
may control the reaction rates, mechanism, regio- and stereo-
chemistry in the presence of micellar media.17–20 Although,
application of micelles in analytical chemistry is widely
studied,21,22 their synthetic applications as media in organic
reactions, especially in Lewis acid mediated reactions are not
well investigated.23
Recently, great attention has been paid to the development of
organic reactions in water to achieve green chemistry.23a,24 Ceric
triflate,25 Ce(OTf )4, is stable in water and could be considered
as a suitable catalyst for performing the organic reactions in
aqueous media.24 In continuation of our recent work,23b we
decided to study the ring opening reaction of epoxides with the
Ϫ
sodium salt of different anions such as CNϪ, N3Ϫ, NO3Ϫ, NO2
,
SCNϪ, BrϪ and ClϪ in micellar media with the aid of Ce(OTf )4
as catalyst. Due to the insolubility of metal salts of inorganic
nucleophiles in organic solvents, nucleophilic ring opening reac-
tions of epoxides is usually carried out in the presence of their
quaternary ammonium salts and mostly in aqueous organic
solvents and at high temperatures.26 The use of metal salts of
nucleophiles for ring opening of epoxides usually suffers from
some disadvantages. For example, Na, K, Cs and Cu salts of
bromide supported on silica-gel have been reported to react
with epoxides very sluggishly (48–720 h). These reactions pro-
duce a mixture of β-bromohydrins and diols. The ring opening
reaction of epoxides with LiCl and LiBr supported on silica-gel
has also been performed, but again the regioselectivity is not
good.27 However, the reactions of LiCl/silica-gel with epoxides
suffer from very long reaction times (13 and 22 days) and give a
mixture of regio-isomers together with the corresponding
diols.27
Scheme 1
When styrene oxide reacted with sodium cyanide in water
alone and in the presence of Ce(OTf )4 as catalyst (Table 1,
entry 1), a mixture of 1,2-cyanohydrines (2a ϩ 3a, R = Ph) was
obtained in 70% yield after 30 h with low regeioselectivity of 35
and 65% respectively. We then tried this reaction in micellar
solutions of SDS, CTAB and Triton X-100. The best result was
obtained in 0.1 M SDS solution. This concentration is slightly
more than the c.m.c. concentration (8.1 × 10Ϫ2 M) of SDS
micellar solution. Under these conditions (Table 1, entry 2), the
same mixture of regio-isomers was obtained in 92% yield after
4.5 h, but the regioselectivity was found to be much improved
(8% of 2a ϩ 92% of 3a). In CTAB solutions, the major product
was found to be the corresponding diol instead of 1,2-cyano-
hydrine. The use of 2% and 4% micellar solutions of Triton X-
100 as reaction media, in comparison with using water alone,
did not show any advantage. We therefore concluded the Triton
X-100 does not have any pronounced effect on the rate of
the reaction. The results of the reaction of styrene oxide with
cyanide ion in different micellar solutions are summarized in
Table 1.
Results and discussion
Considering the problems encountered in cyanolysis of
epoxides, such as the use of crown ethers to activate the cyanide
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 7 2 4 – 7 2 7
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 3
724

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Table 1 Reaction of styrene oxide (1a) with 1.5 molar equivalents of NaCN in the presence of 10 mol% Ce(OTf )4 in different micellar solutionsa at
room temperature
Media
Conc.
Time/h
Yield (%)b
Ratio of 2a/3aa
1
2
3
4
5
6
7
8
9
Waterc
SDS
SDS
SDS
SDS
CTAB
CTAB
Triton X-100
Triton X-100
–
30
4.5
10
15
10
3
1
30
25
70
92
87
85
19d
35/65
8/92
15/85
20/80
25/75
–
0.1 M
0.05 M
0.01 M
0.1 M
1.3 × 10Ϫ3 M
1.3 × 10Ϫ2 M
2%
–
–
e
e
–
80
75
30/70
30/70
4%
Ϫ3
Ϫ4
a The c.m.c. of SDS = 8.1 × 10 M,33a CTAB = 1.3 × 10Ϫ3 M,33a Triton X-100 = 3.0 × 10 M;33b 2a = 1-phenyl-2-cyanoethanol; 3a = 2-phenyl-
2-cyanoethanol. b Isolated yield. c The reaction was performed in the absence of micelles. d The reaction was performed in micellar solution of SDS
in the absence of Ce(OTf )4. e A mixture of 1,2- cyanohydrins was obtained in 10–15% yields together with 45% and 60% of 1,2-dihydroxy-
1-phenylethane for entries 5 and 6 respectively.
Table 2 Reaction of epoxides with 1.5 equimolar amounts of NaCN
catalyzed with 0.1 equimolar of Ce(OTf )4 in SDS (0.1M)at room
temperature
The higher rate and regioselectivity of the reaction in anionic
micelle (SDS) could well be due to the different micellar
environmental factors. We suggest that in this medium, the
partial cationic character which is induced on the epoxide ring
due to the interaction of oxygen of the ring with Ce() could
be stabilized through the interaction with the anionic part of
the micelle on the surface. Triton X-100 as a neutral micelle can
just increases the solubility of the organic reactants and causes
a slight increase in the reaction rate. In the cationic micellar
media of CTAB, the cyanide anion interacts strongly with the
bromide anion of CTAB which results in deactivation of CNϪ
anion. This deactivation results in hydrolysis of the epoxide
as the major pathway rather than cyanolysis. We therefore,
applied the resulting optimized conditions for the cyanolysis
of structurally different epoxides with success. Different classes
of epoxides were converted to their corresponding β-hydroxy
nitriles in high yield and regioselectivity in 0.1 M aqueous SDS
solution (Table 2). Under these conditions, epoxides carrying
either electron-donating or withdrawing substituents produced
the desired β-hydroxy nitriles with high regioselectivity. We
continued this study to investigate the applicability of this
method to the ring opening of epoxides with other nucleophiles
such as halides, azide, nitrate, and nitrite anions.
Epoxide
Producta
(Time/h)/(Yield (%))b
PhCH(CN)CH2OHc
4.5 (85)
trans-2-Cyanocyclohexanol
C4H9CH(CN)CH2OHd
5 (85)
5 (70)
8 (90)
iPrOCH2CH(OH)CH2CNd
RCH(OH)CH2CNe
(R: CH2᎐᎐CHCH2O–)
8 (85)
7 (85)
ClCH2CH(OH)CH2CNe
Quaternary ammonium salts (R4NϩXϪ) are frequently used
as sources of halide ions for the preparation of vicinal halo-
hydrins from epoxides.26,34,35 To show the applicability and
advantages of this protocol, we successfully used the cheap and
readily available NaBr and NaCl in 0.1 M SDS solution for the
ring opening of structurally different epoxides in the presence
of Ce(OTf )4 as catalyst at room temperature (Table 3).
PhOCH2CH(OH)CH2CNe
10 (88)
a The products were isolated and identified by comparison with known
samples. b Isolated yield. c 2-Cyano-1-phenylethanol was formed in
7% yield. d GC yield. e In the case of epoxides carrying electron-
withdrawing groups, trace amounts (2–5%) of the other regio-isomer
was also observed.
β-Azido alcohols as important intermediates in organic
synthesis are prepared from the reaction of epoxides and azide
anions using different protocols.24c,36–38 Thus, we applied this
method to the synthesis of β-azido alcohols using azide anions
in 0.1 M SDS solution in the presence of catalytic amounts of
Ce(OTf )4. We, thereby, converted styrene oxide, cyclohexene
oxide and allyl 2,3-epoxypropyl ether as examples of aryl, alkyl
and electron-withdrawing substituted epoxides to their corre-
sponding β-azido alcohols within 5–10 min with high yields
(Table 3). In comparison with the recent report on azidolysis
of epoxides which takes 30–120 min using sodium azide and
0.5 molar equivalents of Oxone®,36 our presented method is
more efficient for this purpose.
Table 3, entries 10–12 show the results of this transformation
with different epoxides.
In the case of using NaNO2 as the source of the NO2 nucleo-
phile, β-nitro alcohols were obtained with good regioselectivity
in high yields (Scheme 2, Table 3, entries 13–15). Except in the
Scheme 2
We next studied the reaction of epoxides with nitrate and
nitrite anions using NaNO3 and NaNO2 as the source of nucleo-
philes in 0.1 M SDS in the presence of Ce(OTf )4 as catalyst.
The reaction rates for the formation of β-nitrato alcohols
obtained from the reaction of epoxides in SDS micellar solu-
tion with sodium nitrate were found to be much better than
the same reactions using tetra-n-butyl ammonium nitrate in
acetonitrile at 80 ЊC catalysed with ceric ammonium nitrate.40
case of styrene oxide, for which the β-nitro alcohol was formed
as the only product, the reaction of the other epoxides pro-
duced some β-nitrito alcohols (10–15%) as side products.
Sodium nitrite is an ambident nucleophile and it seems that in
SDS micellar solution, N-attack is more favored due to the
solvation of the O site.
In the course of these studies, we also decided to investigate
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 7 2 4 – 7 2 7
725

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Table 3 Reaction of epoxides with 1.5 equimolar amounts of NaX (X = Cl, Br, N3, NO3, NO2) catalyzed with 0.1 molar equivalents of Ce(OTf ) in
SDS (0.1M) at room temperature
Entry
Epoxide
Nucleophile
Time (min)
Producta
Yield (%)b
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
1a
1b
1e
1a
1b
1e
1a
1b
1e
1a
1bc
1ec
1a
1b
1e
NaBr
NaBr
NaBr
NaCl
NaCl
NaCl
NaN3
NaN3
20
10
10
20
10
10
5
10
10
20
30
20
5
PhCH2(Br)CH2OH
85
88
87
83
85
87
90
89
95
87
85
78
90
78
75
trans-2-bromo-cyclohexanol
CH2᎐᎐CHCH2OCH2CH(OH)CH2Br
PhCH2(Cl)CH2OH
trans-2-chloro-cyclohexanol
CH2᎐᎐CHCH2OCH2CH(OH)CH2Br
PhCH2(N3)CH2OH
trans-2-azido-cyclohexanol
CH2᎐᎐CHCH2OCH2CH(OH)CH2N3
PhCH2(ONO2)CH2OH
trans-2-nitrato-cyclohexanol
CH2᎐᎐CHCH2OCH2CH(OH)CH2ONO2
PhCH2(NO2)CH2OH
NaN3
NaNO3
NaNO3
NaNO3
NaNO2
NaNO2
NaNO2
10
10
trans-2-nitro-cyclohexanol
CH2᎐᎐CHCH2OCH2CH(OH)CH2NO2
a Products were identified by comparison of their spectral data with those in the literature.26,31,36,39,40 b Isolated yield. c The corresponding β-nitrito
alcohols were also obtained in 10–15% yield.
Table 4 Conversion of styrene oxide to styrene sulfide with NaSCN
(1.5 equimolar.) in the presence of 10 mol% of Ce(OTf )4 in different
micellar solutions
Table 5 Conversion of epoxides to epoxy sulfidesa with NaSCN in the
presence of Ce(OTf ) as catalyst at room temperature
Epoxide
Mole ratio of Sub./Cat./SCNϪ Time/h Yield (%)b
Micelle
Concentration
Time/h
Yield (%)a
1/0.05/1.5
1/0.05/1.5
1/0.05/1.5
1/0.1/1.5
0.5
0.5
4
92
89
91
89
–
SDS
SDS
CTAB
Titon X-100
–
0.1
0.01
8 × 10Ϫ4
2%
7
0.5
2
5
5
70
100
77
55
70
a GC yield of styrene sulfide.
1
the epoxy sulfide syntheses from epoxides in the presence of
Ce(OTf )4 as catalyst using NaSCN as sulfurating agent in SDS
micellar solution. We first studied the effect of SDS, CTAB and
Triton X-100 micellar solutions for the reaction of styrene
oxide and NaSCN at room temperature in the presence of the
catalyst. The best results were obtained in 0.1 M SDS solution
and styrene sulfide was formed in almost quantitative yield
after 0.5 h (Table 4).
1/0.1/1.5
3
8
95
80
1/0.05/1.5
Different classes of epoxides were then converted to their
corresponding epoxy sulfides using the above mentioned reac-
tion conditions. Allyl, isopropyl, and phenyl glycidyl ethers, as
examples of epoxides carrying electron-withdrawing groups,
and styrene oxide and 1,2-epoxy hexane, as examples of
epoxides carrying aryl and alkyl groups were converted effic-
iently to their corresponding epoxy sulfides in excellent yields
(Table 5). In our previous report for the conversion of epoxides
to epoxy sulfides in organic solvents, the catalytic activity of
Ce(OTf )4 was reported to be strongly diminished due to
its complexation with SCNϪ, therefore, we had to support
Ce(OTf )4, on poly(4-vinyl pyridine).32 However, in SDS
micellar solution, this problem has been eliminated for the
synthesis of epoxy sulfides from epoxides with SCNϪ. It is
worthy of mention that in all the reactions we have studied in
SDS micellar solution, the sodium salts of nucleophiles were
found to be more reactive than their potassium, ammonium or
quaternary ammonium analogs.
In conclusion, the use of SDS micellar media together with
ceric triflate as a stable Lewis acid in aqueous solutions provides
excellent conditions for the ring opening of epoxides with dif-
ferent anionic nucleophiles. The absence of organic solvent,
acceleration of the reactions rates, increase of the yields of the
products and high regioselectivity of the reactions are strong
points of performing ionic reactions in SDS micellar media.
Another useful feature of the present protocol is the use of
a Epoxy sulfides were identified by comparison of their physical data
with those of known samples.41 b Isolated yield of epoxy sulfide.
easily available and very cheap sodium salts of nucleophiles
instead of expensive and usually hygroscopic quaternary
ammonium salts.
Experimental
Chemicals were either prepared in our laboratories or pur-
chased from Merck, Fluka and Aldrich Chemical Companies.
All yields refer to isolated products after column chromato-
graphy unless otherwise stated. The products were charac-
terized by comparison of their physical data with those of
known samples or by their spectral data. IR spectra were run on
a Perkin Elmer 781 spectrophotometer. NMR spectra were
recorded on a Bruker Avance DPX-250. Mass spectra were
recorded on a Shimadzu GCMS-QP 1000 EX.
The purity of the substances and the progress of the
reactions were accomplished by TLC on silica-gel polygram
SILG/UV254 plates or by a Shimadzu Gas Chromatograph
GC-10A instrument with a flame-ionization detector using
a column of 15% carbowax 20 M chromosorb-w acid washed
60–80 mesh.
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 7 2 4 – 7 2 7
726

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prepared. Ce(OTf )4 (73.6 mg, 0.1 mmol) was added to this
solution and the reaction mixture was stirred at room temper-
ature for 10 h. The reaction was monitored by TLC. After
completion of the reaction, the mixture was extracted with
chloroform (4 × 10 cm3). The emulsion was broken by adding
small portions of NaCl. The organic layer was dried with
anhydrous Na2SO4. The solvent was evaporated and the crude
product was chromatographed on a short column of silica
gel eluted with petroleum ether (60–80) to give trans-2-
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a solution of allyl 2,3-epoxypropyl ether (114 mg, 1 mmol) and
NaNO3 (127.5 mg, 1.5 mmol) in SDS (0.1 M, 3 cm3), Ce(OTf )4
(73.6 mg, 0.1 mmol) was added and the reaction was monitored
by TLC. After completion of the reaction, the mixture was
extracted with chloroform (4 × 10 cm3) and the emulsion was
broken by adding small portions of NaCl. The organic layer
was dried with anhydrous Na2SO4. The solvent was evaporated
and the crude product was chromatographed on silica gel
to give the corresponding β-nitrato alcohol in 78% yield (b.p.
82–84 ЊC/2 Torr, lit.40 85 ЊC/2 Torr).
Reaction of styrene oxide (1a) with sodium chloride. To a
solution of styrene oxide (120 mg, 1 mmol) in SDS (0.1 M,
3 cm3) and NaCl (91 mg, 1.5 mmol), Ce(OTf )4 (73.6 mg,
0.1 mmol) was added. The reaction mixture was stirred for
20 min at room temperature. After completion of the reaction,
water (10 cm3) was added and extracted with chloroform
(4 × 10 cm3). NaCl was added in portions to break the
emulsion. The organic layer was dried with anhydrous Na2SO4.
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Conversion of styrene oxide (1a) to styrene epoxy sulfide. To
a solution of styrene oxide (120 mg, 1 mmol) in SDS (0.1 M,
3 cm3) and NaSCN (123 mg, 1.5 mmol), Ce(OTf )4 (73.6 mg,
0.1 mmol) was added. The reaction mixture was stirred for
30 min at room temperature. After completion of the reaction,
water (10 cm3) was added and extracted with chloroform
(4 × 10 cm3). NaCl was added in small portions to break the
emulsion of SDS solution and CHCl3. The organic layer was
dried with anhydrous Na2SO4. The solvent was evaporated.
After chromatography on a short column of silica gel using
CCl4 as eluent, the pure styrene sulfide was obtained in 92%
yield (b.p. 89–91 ЊC/5 Torr, lit.41 85–88 ЊC/5 torr).
Acknowledgements
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We are thankful to Shiraz University Research Council for
partial support of this work.
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O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 7 2 4 – 7 2 7
727