A highly efficient protocol for regioselective ring-opening of epoxides with alcohols, water, acetic acid, and acetic anhydride catalyzed by SbF3

Article abstract of DOI:10.1080/10426507.2015.1135439

SbF₃as an efficient catalyst has been used for regioselective alcoholysis, acetolysis and hydrolysis of epoxides to the corresponding β-alkoxy, β-acetoxy alcohols, and 1,2-diols in high to excellent yields. This study also represents a convenient synthesis of vic-diacetates from ring-opening of epoxides with acetic anhydride.

Full text of DOI:10.1080/10426507.2015.1135439

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
A Highly Efficient Protocol for Regioselective Ring-
Opening of Epoxides with Alcohols, Water, Acetic
Acid and Acetic Anhydride Catalyzed by SbF3
Behzad Zeynizadeh, Masumeh Gilanizadeh & Farkhondeh Mohammad
Aminzadeh
To cite this article: Behzad Zeynizadeh, Masumeh Gilanizadeh & Farkhondeh Mohammad
Aminzadeh (2016): A Highly Efficient Protocol for Regioselective Ring-Opening of Epoxides with
Alcohols, Water, Acetic Acid and Acetic Anhydride Catalyzed by SbF , Phosphorus, Sulfur, and
3
Silicon and the Related Elements, DOI: 10.1080/10426507.2015.1135439
To link to this article: http://dx.doi.org/10.1080/10426507.2015.1135439
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ACCEPTED MANUSCRIPT
A Highly Efficient Protocol for Regioselective Ring-Opening of Epoxides with Alcohols,
Water, Acetic Acid and Acetic Anhydride Catalyzed by SbF3
Behzad Zeynizadeh*, Masumeh Gilanizadeh and Farkhondeh Mohammad Aminzadeh
Department of Chemistry, Faculty of Science, Urmia University, Urmia 5756151818, Iran
E-mail: bzeynizadeh@gmail.com
Abstract
SbF , as an efficient catalyst, has been used for regioselective alcoholysis, acetolysis and
3
hydrolysis of epoxides to the corresponding β-alkoxy, β-acetoxy alcohols and 1,2-diols in high to
excellent yields. This study also represents a convenient synthesis of vic-diacetates from ring-
opening of epoxides with acetic anhydride.
R
SbF (0.1 mmol)
3
RCH(Nu)CH OH + RCH(OH)CH Nu
2
2
Nu, reflux, 8-60 min
O
60-98%
-attacked
-attacked
Nu: ROH, AcOH, H O
2
R
SbF (0.3-0.4 mmol)
R
3
OAc
O
Ac O (1 mL), reflux
2
OAc
80-95%
Keywords β-Alkoxy alcohol; β-Acetoxy alcohol; 1,2-Diol; vic-Diacetate; Epoxide; SbF3
1
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INTRODUCTION
The ring strain and polarization of carbon-oxygen bonds make epoxides versatile synthetic
1
-3
intermediates in organic synthesis. Ring-opening of epoxides occurs under various conditions,
however, the convenient protocols are achieved in the presence of Lewis acids. In this situation,
reaction of epoxides with alcohols, acetic acid and water affords β-alkoxy, β-acetoxy alcohols
4
5
6
7
8
14
21
and 1,2-diols. DDQ, FeCl3, Fe(TFA)3, FeCl ·6H O/SiO , FeCl ·6H O/polystyrene,
3
2
2
3
2
9
10
11
12
13
Amberlyst-15, TiCl (OTf) and TiO(TFA) , CAN, Ce(OTf) , graphite oxide, Al(OTf) ,
3
2
4
3
15
16
17
18
19
20
Cp ZrCl , ZrO , ZrO(OTf)2, InCl , (NH ) [CeW O ], AlPW O , Sn(tpp)(OTf) ,
2
2
2
3
4 8
12 36
12 40
2
22
23
Sn(tpp)(BF4)2 and silica sulfuric acid are some of catalysts which have been used for
nucleophilic ring-opening of epoxides.
The ring-opening of epoxides with water leading to the preparation of 1,2-diols is one of the
most convenient reactions, and the subsequent acetylation of these diols provides an efficient
2
4
means for protection and preparation of vic-diacetates. A literature review shows that this
transformation has been achieved by the reaction of epoxides and acetic anhydride in the
1
7
25
26
27
presence of ZrO(OTf)2, phosphomolybdic acid, molecular sieves 4Å, NaBH4, HY
28
29
30
31
32
33
34
zeolite, Bu P, LiClO , Er(OTf) , Bu NCl, Bu NOAc, (TBA) PFeW O ·3H O and
3
4
3
4
4
4
11 39
2
3
5
(
NH ) PMo O . Although most of the reported protocols are efficient and useful, however,
4 3 12 40
the drawbacks such as operational difficulty (refs: 17, 29 and 31), unavailability and high cost of
reagents (17, 25, 28, 31 and 35), limited scope of the utilized epoxides and nucleophiles (28 and
3
1) and the prolonged reaction times (28 and 29) put some restrictions to use the methods for any
practical applications.
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In line with the outlined strategies and in continuation of our research program directed to the
3
6-42
synthetic transformation of epoxides,
herein, we wish to introduce SbF for convenient ring-
3
opening of epoxides with primary, secondary and tertiary alcohols, acetic acid, water and acetic
anhydride to afford β-alkoxy, β-acetoxy alcohols and 1,2-diols as well as vic-diacetates in high to
excellent yields (Scheme 1).
RESULTS AND DISCUSSION
Antimony trifluoride, SbF , is sometimes called Swart's reagent. A literature review shows that
3
4
3
as well as some industrial applications, this reagent is usually used as fluorinating agent in
4
4,45
inorganic and organofluorine chemistry.
Although, the application of SbF for fast and
3
4
6
efficient reduction of nitro compounds with NaBH was successfully reported, however, the
4
catalytic activity of SbF in organic reactions was not frequently documented. Thus, introduction
3
of new synthetic methodo-logies catalyzed by SbF and our interest towards preparation of β-
3
alkoxy, β-acetoxy alcohols and 1,2-diols as key intermediates, encouraged us to study
alcoholysis, acetolysis and hydrolysis of epoxides with primary, secondary and tertiary alcohols,
acetic acid and water in the presence of SbF3.
Reaction conditions were primarily optimized by performing the alcoholysis of styrene oxide in
MeOH and in the presence of SbF . Different molar equivalents of the reactants as well as
3
performing the reaction at room temperature or reflux were examined in the typical experiment.
The obtained results showed that using 0.1 mmol of SbF per 1 mmol of the epoxide at reflux
3
was sufficient to convert styrene oxide to 2-methoxy-2-phenylethanol within 8 min in high
3
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regioselec-tivity and yield (Scheme 1, α-attacked). Encouraged by this success and in order to
study ring-opening of styrene oxide in different alcoholic media, we performed alcoholysis of the
model compound in refluxing EtOH, n-PrOH, i-PrOH and t-BuOH using 0.1 mmol SbF . The
3
summarized results in Table 1 show that the reaction of styrene oxide with primary, secondary
and tertiary alcohols was carried out successfully within 1560 min and 2-alkoxy-2-
phenylethanols were obtained in high regioselectivity. The results also show that the bulk
hindrance of alcoholic solvent decreases the rate enhancement of ring-opening reaction.
At the next, the reaction of other epoxides having different ring substitutions such as allyl,
phenyl and isopropyl glycidyl ethers, 1,2-epoxyoctane and cyclohexene oxide was carried out in
MeOH, EtOH, n-PrOH, i-PrOH and t-BuOH using 0.1 mmol SbF at reflux. Table 1 show that
3
all reactions took place successfully within 560 min to afford alkoxy alcohols in high
regioselectivity through solvolysis of the epoxide rings from less hindered position (Scheme 1,
β-attacked). In the case of cyclohexene oxide, the ring-opening reactions encountered with the
formation of racemic trans-β-alkoxy cyclohexanols in high yields.
The influence of SbF (0.1 mmol) in acetolysis and hydrolysis of epoxides was also studied by
3
ring-opening of aryl and alkyl substituted epoxides with acetic acid and water. Investigation of
the results reveals that acetolysis of epoxides took place in refluxing acetic acid as the same
manner of alcoholysis reactions. It means that styrene oxide as an aryl substituted epoxide
exclusively produces 2-acetoxy-2-phenylethanol (α-attacked), and alkyl substituted epoxides
gives the corresponding acetoxy alcohols via β-attacking of acetic acid (Scheme 1). In the case of
cyclohexene oxide, the racemic trans-β-acetoxy cyclohexanol was obtained as a sole product.
4
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Further examination also showed that ring-opening of the utilized epoxides with water in a
mixture of H O/CH CN (1.5:0.5 ml) as the solvents of choice and in the presence of SbF (0.1
2
3
3
mmol) provided a good synthetic method for hydrolysis of epoxides to the corresponding 1,2-
diols. Table 1 shows that all acetolysis and hydrolysis reactions were carried out within 1040
min giving the products in 6098% yields.
Direct preparation of vic-diacetates from epoxides was another goal that has been successfully
achieved by SbF . Optimization experiments showed that solvolysis of styrene oxide in refluxing
3
Ac O and in the presence of 0.3 mmol SbF took place efficiently to afford 1,2-diacetoxy-1-
2
3
phenylethane in high yield. In the case of alkyl substituted epoxides, this transformation was also
carried out perfectly using 0.30.4 mmol SbF in acetic anhydride at reflux. The results of this
3
investigation are illustrated in Table 2. As seen, vic-diacetates were obtained in 8095% yields
when the reactions were taken place within 2 h.
Product analysis revealed that only one diastereomer with trans 1,2-diacetoxy groups was
prepared by the reaction of cyclohexene oxide with acetic anhydride. Stereochemical assignment
1
was achieved by: i) comparison of the obtained H NMR spectrum with one of authentic sample
4
7
reported in the literature, and ii) hydrolysis of rac-trans-1,2-diacetoxycyclohexane to white
4
8
crystalline rac-trans-1,2-cyclohexanediol (mp 101103 °C, found: 101104 °C, lit. ) (Scheme
2
).
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The usefulness of SbF in nucleophilic ring-opening of epoxides was highlighted by a
3
comparison of the obtained results for methanolysis of 2,3-epoxypropylphenyl ether and
preparation of 1,2-diacetoxy-1-phenylethane from styrene oxide catalyzed by SbF and other
3
reported reagents (Tables 3 and 4). A case study shows that in viewpoints of availability and
cheapness of the catalysts, selectivity and yield of products, SbF shows a more or comparable
3
efficiency towards the other reagents. In addition, the green aspects of SbF are also
3
considerable: this reagent, as a white solid compound, is stable under air atmosphere to afford its
handling without any precaution. Because of good solubility in water, its work-up and removing
from the reaction mixture is also carried out very easily.
Our experience in SbF -catalyzed ring opening of styrene oxide with MeOH also showed that
3
under non-solvolytic conditions, the reaction was not efficient and the progress of the reaction
encountered with poor yield after 120 min (Scheme 3). This result revealed that the current
protocol is useful only for nucleophiles that can be used as a solvent of choice.
In summary, we have shown that SbF can be used as an efficient catalyst for nucleophilic ring-
3
opening of epoxides with alcohols, acetic acid, water and acetic anhydride to afford β-alkoxy, β-
acetoxy alcohols, 1,2-diols and vic-diacetates. All reactions were carried out with 0.10.4 mmol
of SbF to afford the products in high to excellent yields. The cheapness and availability of the
3
catalyst, excellent regioselectivity, applicability to a wide range of epoxides, high yields and easy
work-up procedure are the advantages which make SbF a synthetically useful catalyst in nucleo-
3
philic ring-opening of various epoxides.
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EXPERIMENTAL
General
All reagents and substrates were purchased in high purity from Merck Company and were used
1
13
without further purification. FTIR and H, C NMR spectra were recorded on Thermo Nicolet
Nexus 670 and Bruker Avance 300 MHz spectrometers, respectively. The products were
1
13
characterized by their FTIR and H, C NMR spectra and compared with data reported in
literature. All yields refer to isolated pure products. TLC was applied for the purity determination
of the substrates, products and the reaction monitoring over silica gel 60 F254 aluminum sheet.
1
13
The Supplemental Materials file contains sample H and C NMR for some of the known
products (Figures S 1 – S 8)
Alcoholysis, Acetolysis and Hydrolysis of Epoxides Catalyzed by SbF : A General
3
Procedure
In a round-bottomed flask (15 mL) equipped with a magnetic stirrer and condenser, SbF (0.1
3
mmol) was added to a solution of epoxide (1 mmol) in an appropriate alcohol, acetic acid (1.5
mL) or a mixture of H O/CH CN (1.5:0.5 mL). The reaction mixture was stirred under reflux for
2
3
the mentioned time in Table 1. After completion of the reaction, distilled water (5 mL) was
added and the mixture was stirred for additional 5 min. The mixture was extracted with EtOAc
(2 × 5 mL) and then dried over anhydrous sodium sulfate. The eluted product was concentrated
7
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under reduced pressure and then subjected to chromatography on a glass column (10 cm length,
0
.5 cm diameter) of silica gel 60 (230400 mesh) to give the pure product in excellent yield
(6098%, Table 1).
Conversion of Epoxides to vic-Diacetates Catalyzed by SbF : A General Procedure
3
In a round-bottomed flask (15 mL) equipped with a magnetic stirrer and condenser, SbF3
(0.30.4 mmol) was added to a solution of epoxide (1 mmol) in acetic anhydride (1 mL). The
reaction mixture was stirred under reflux for 2 h. After completion of the reaction, an aqueous
solution of NaHCO (5%, 5 mL) was added and the mixture was stirred for additional 5 min. The
3
mixture was extracted with EtOAc (2 × 5 mL) and then dried over anhydrous sodium sulfate.
The eluted product was concentrated under reduced pressure and then subjected to
chromatography on a glass column (10 cm length, 0.5 cm diameter) of silica gel 60 (230400
mesh) to give the pure product in excellent yield (8095%, Table 2).
ACKNOWLEDGMENT
The authors gratefully acknowledge the financial support of this work by the research council of
Urmia University.
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a
Table 1. Alcoholysis, acetolysis and hydrolysis of epoxides catalyzed by SbF3
Time Yield
Entry
Epoxide
Product
ROH
b
Ref.
(min) (%)
1
2
3
4
5
6
7
MeOH
EtOH
n-PrOH
i-PrOH
t-BuOH
AcOH
8
93
92
95
98
89
98
85
19,23
19
19,23
19,23
19
15
20
60
60
10
15
OH
O
OR
21
21,23
c
c
c
c
c
H O/CH CN
2
3
8
9
MeOH
EtOH
n-PrOH
i-PrOH
t-BuOH
AcOH
10
15
30
50
50
15
20
89
81
96
85
83
98
75
19,23
19
19,23
19,23
19,23
21
1
1
1
1
1
0
1
2
3
4
OH
O
O
O
OR
H O/CH CN
21,23
2
3
1
1
1
1
1
2
2
5
6
7
8
9
0
1
MeOH
EtOH
n-PrOH
i-PrOH
t-BuOH
AcOH
15
20
25
30
40
20
40
92
91
84
85
80
98
85
19,23
19
19,23
19,23
19,23
21
O
OR
O
O
OH
H O/CH CN
21,23
2
3
2
2
2
2
2
2
2
2
3
4
5
6
7
8
MeOH
EtOH
n-PrOH
i-PrOH
t-BuOH
AcOH
15
20
25
40
50
15
20
87
85
95
85
90
80
70
19,21
19,21
19,21
19,21
19,21
21
O
OR
O
O
OH
H O/CH CN
21
2
3
2
3
3
3
3
3
3
9
0
1
2
3
4
5
MeOH
EtOH
n-PrOH
i-PrOH
t-BuOH
AcOH
20
30
40
60
60
20
30
88
84
85
97
80
91
80
19,21
19,21
19,21
19,21
19,21
21
OR
O
OH
H O/CH CN
21
2
3
1
3
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3
3
3
3
4
4
4
6
7
8
9
0
1
2
MeOH
EtOH
n-PrOH
i-PrOH
t-BuOH
AcOH
5
84
85
90
84
89
85
19,23
19
19,23
19
19
21
10
20
20
25
10
20
OH
OR
O
c
H O/CH CN
60
21,23
2
3
a
b
All reactions were carried out with a molar ratio of epoxide/SbF (1:0.1) at reflux. Yields
refer to isolated pure products. A mixture of H O/CH CN (1.5:0.5 mL) was used as a solvent.
3
c
2
3
1
4
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a
Table 2. Conversion of epoxides to vic-diacetates catalyzed by SbF3
SbF3
mmol)
Yield
(%)
Entry
Epoxide
vic-Diacetate
b
Ref.
(
1
0.3
89
85
95
25,26
OAc
O
OAc
OAc
O
O
0.3
0.4
25,26
25,26
O
O
OAc
OAc
2
3
O
O
OAc
4
5
OAc
0.4
0.3
90
85
25,26
25,26
O
O
O
OAc
OAc
OAc
O
OAc
6
7
8
0.3
0.3
0.3
80
90
87
26
O
OAc
Cl
OAc
Cl
25,26
25,26
O
OAc
O
OAc
O
O
OAc
a
All reactions were carried out with 1 mmol of epoxide in refluxing Ac O (1.0 mL)
2
b
within 2 h. Yields refer to isolated pure products.
1
5
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Table 3. Comparison of methanolysis of 2,3-epoxypropylphenyl ether catalyzed by SbF and
3
other reported reagents
Catalyst
MeOH
PhO
PhO
OMe
O
OH
Conditio Time Yield Selectivity
Entry
Catalyst
Mol%
Ref.
n
(min)
(%)
92
94
99
98
93
99
74
(%)
100
100
100
100
100
100
100
1
2
3
4
5
6
7
SbF3
Fe(TFA)3
10
10
10
43
5
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
50 ºC
15

6
120
105
330
20
20
540
TiCl (OTf)
10
10
12
17
18
3
TiO(TFA)2
Ce(OTf)4
ZrO(OTf)2
InCl3
0.75
20
Amberlyst-
8
0.1 g
24-28 ºC
50
95
97
9
1
5/sonication
Graphite oxide
AlPW O
9
0.01 g
r.t.
r.t.
Reflux
Reflux
120
15
10
5
72
94
95
99
100
100
100
100
13
20
19
21
1
1
1
0
1
2
3
4
1.9
1
2
40
(NH ) [CeW O ]
4
8
12 36
Sn(tpp)(OTf)2
1
6
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Table 4. Comparison of the conversion of styrene oxide to 1,2-diacetoxy-1-phenylethane
catalyzed by SbF and other reported reagents
3
Ph
Ph
Catalyst
OAc
O
Ac O
2
OAc
Entry
Catalyst
SbF3
PMA
PMA-SiO2
MS 4 Å
NaBH4
Mol%
30
1
Condition Time (h)
Yield (%)
Ref.

1
2
3
4
5
6
7
8
9
Reflux
r.t.
r.t.
Reflux
Reflux
Reflux
r.t.
2
0.25
0.08
2
1.5
3
89
95
98
90
96
83
90
98
0
25
25
26
27
32
28
29
31
17
30
35
5
0.15 g
20
Bu NCl
5
4
HY Zeolite
Bu3P
Er(OTf)3
ZrO(OTf)2
LiClO4
0.05 g
10
0.1
0.75
50
12
Reflux
r.t.
24
2
1
1
1
0
1
2
50 ºC
r.t.
r.t.
1 min
2-5
1
99
66
98
(NH ) PMo O
10
4
3
12 40
1
7
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ACCEPTED MANUSCRIPT
R
SbF3
RCH(Nu)CH OH + RCH(OH)CH Nu
2
2
Nu, reflux
O
Nu: ROH, AcOH, H O
(-attacked)
(-attacked)
2
R
SbF3
R
OAc
O
Ac O (1 mL), reflux
2
OAc
Scheme 1. Ring-opening of epoxides with alcohols, acetic acid, water and acetic anhydride catalyzed by SbF3
1
8
ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
OAc
K CO , MeOH-H O
OH
2
3
2
40 min, reflux, 90%
OAc
OH
rac-trans-1,2-diacetate
rac-trans-1,2-diol
Scheme 2. Hydrolysis of trans-1,2-diacetoxycyclohexane to trans-1,2-cyclohexanediol
1
9
ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
Ph
SbF (0.3 mmol)
3
RCH(OMe)CH OH
2
RCH(OH)CH OMe
2
+
MeOH
3 mmol)
CH CN (1.5 mL), reflux
O
3
(
120 min, 15%
Scheme 3. SbF -catalyzed ring-opening of styrene oxide with MeOH
3
under non-solvolytic conditions
2
0
ACCEPTED MANUSCRIPT