Efficient conversion of epoxides to 1,3-dioxolanes catalyzed by bismuth(III) salts

Article abstract of DOI:10.1081/SCC-100106198

Epoxides react with acetone in the presence of catalytic amounts of bismuth(III) salts including BiCl₃, Bi(TFA)₃ and Bi(OTf)₃ affording the corresponding 1,3-dioxolanes in excellent yields.

Full text of DOI:10.1081/SCC-100106198

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EFFICIENT CONVERSION OF EPOXIDES TO 1,3-
DIOXOLANES CATALYZED BY BISMUTH(III) SALTS
a
a
a
I. Mohammadpoor-Baltork , A. R. Khosropour & H. Aliyan
a
Department of Chemistry, Isfahan University, Isfahan, 81744, Iran
Published online: 22 Aug 2006.
To cite this article: I. Mohammadpoor-Baltork , A. R. Khosropour & H. Aliyan (2001) EFFICIENT CONVERSION OF EPOXIDES
TO 1,3-DIOXOLANES CATALYZED BY BISMUTH(III) SALTS, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 31:22, 3411-3416, DOI: 10.1081/SCC-100106198
To link to this article: http://dx.doi.org/10.1081/SCC-100106198
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SYNTHETIC COMMUNICATIONS, 31(22), 3411–3416 (2001)
EFFICIENT CONVERSION OF EPOXIDES
TO 1,3-DIOXOLANES CATALYZED BY
BISMUTH(III) SALTS
I. Mohammadpoor-Baltork,* A. R. Khosropour,
and H. Aliyan
Department of Chemistry, Isfahan University,
Isfahan 81744, Iran
ABSTRACT
Epoxides react with acetone in the presence of catalytic
amounts of bismuth(III) salts including BiCl , Bi(TFA) and
Bi(OTf) affording the corresponding 1,3-dioxolanes in excel-
3
3
3
lent yields.
1
,3-Dioxolanes are among the most widely used protecting groups
1
,2
for carbonyl compounds. They are also useful intermediates, particularly
in carbohydrate and steroid chemistry, and are very well suited for GLC
3
and mass spectral analysis of diols. The formation of these compounds
starting from epoxides and carbonyl compounds can occur in two ways;
a) by hydrolysis of the epoxides to the corresponding diols, followed
by acetalization, and b) by direct condensation of epoxides with carbonyl
*
Corresponding author.
3
411
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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3
412
MOHAMMADPOOR-BALTORK, KHOSROPOUR, AND ALIYAN
compounds. In the latter reaction no water is formed, which makes
direct condensation, in some cases, a more suitable method than other
procedures involving removal of water to shift the equilibrium. Direct
conversion of epoxides to their corresponding 1,3-dioxolanes in the
presence of acetone has been reported with only a few reagents. Among
these, anhydrous copper sulfate has been used for the preparation of 1,3-
dioxolanes, but in most cases, the yields of the products are low and
3
4
5
6
the reaction times are relatively long. KSF clay, HBF4; RuCl3;
7
TiO(TFA)2 and TiCl (OTf ) have also been used as catalysts for this
3
purpose. Among Lewis acids, BF .OEt has been successfully used for
3
2
the conversion of only ethylene and propylene oxides to their 1,3-dioxolanes
8
in the presence of different carbonyl compounds. Some other Lewis acids
9 10
do not give the desired products; FeCl3 and Me SiCl give the cor-
3
1
1,12
responding halohydrins, anhydrous zinc and magnesium halides
afford the rearranged products, both SnCl and TiCl give little or no 1,3-
4
4
8
dioxolane.
Recently we have reported that BiCl can be used as an effective
3
1
catalyst for the conversion of epoxides to thiiranes, deprotection of
3
1
,1-diacetates and alcoholysis, acetolysis and hydrolysis of epoxides.
4
15
1
1
6
In the course of our studies on Bi(III) catalysis, we now report an
efficient method for the conversion of epoxides to their 1,3-dioxolanes
in the presence of acetone catalyzed by BiCl , Bi(TFA) and Bi(OTf )
3
3
3
(
Scheme 1).
Scheme 1.
As shown in Table 1, various types of epoxides react efficiently with
acetone in the presence of catalytic amounts of BiCl , Bi(TFA) and
Bi(OTf ) affording the corresponding 1,3-dioxolanes in excellent yields.
3
3
3
The experimental results show that Bi(OTf ) is more efficient than BiCl
3
3
and Bi(TFA) for this purpose.
3
In conclusion, high yields of the products and easy workup, stability,
non-toxicity and availability are worthy to be mentioned for the presented
catalysts.

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EPOXIDES AND 1,3-DIOXOLANES
3413

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3
414
MOHAMMADPOOR-BALTORK, KHOSROPOUR, AND ALIYAN
EXPERIMENTAL
Bi(TFA) and Bi(OTf ) were prepared according to the described
3
3
1
7
procedures.
Conversion of Epoxides to 1,3-Dioxolanes
General Procedure
To a solution of epoxide (1 mmol) in acetone (3 mL) was added the
catalyst (0.2 mmol of BiCl , 0.2–0.4 mmol of Bi(TFA) and 0.01–0.03 mmol
of Bi(OTf ) ). The reaction mixture was stirred under reflux condition for
3
3
3
the appropriate time according to Table 1. The progress of the reaction
was followed by TLC or GLC. After completion of the reaction, a saturated
aqueous solution of sodium bicarbonate (10 mL) was added and the mixture
was extracted with CHCl (2 ꢀ 10 mL). The organic extracts were dried
3
over anhydrous MgSO . Evaporation of the solvent followed by chromato-
4
graphy on a short column of silica-gel gave the pure product, yields 87–99%
(
Table 1).
2
0
18 20
n
1
Compound 2a: n ¼ 1:5270 ðlit:
¼ 1:5273Þ; H-NMR (CDCl )
D
D
3
d: 7.25 (5H, s), 5 (1H, dd), 4.23 (1H, dd), 3.62 (1H, dd), 1.48 (3H, s), 1.4
(
1
3H, s); IR (neat): 3060, 2990, 2870, 1600, 1495, 1450, 1365, 1230, 1150,
ꢁ
1
055, 945, 850, 755, 700 cm .
20
19 20
n
1
Compound 2b: n ¼ 1:4465 ðlit:
¼ 1:448Þ; H-NMR (CDCl3)
D
D
d: 4.34–4.05 (2H, m), 2.58–2.07 (4H, m), 1.35 (6H, s), 1.24–1 (4H, m); IR
(
7
neat): 2980, 2930, 2870, 1440, 1355, 1260, 1180, 1080, 960, 885, 835,
.
ꢁ1
80 cm
20
1
Compound 2c: n ¼ 1:2495; H-NMR (CDCl ) d: 4.2–3.3 (3H, m),
D
3
1
1
.72–1.13 (16H, m), 0.95–0.7 (3H, t); IR (neat): 2970, 2915, 2860, 1460,
.
ꢁ
1
375, 1250, 1160, 1050, 950, 850, 730 cm
ꢂ
20
ꢂ
1
Compound 2d: mp 63 C (lit. mp 64–65 C); H-NMR (CDCl3)
d: 7.47–6.72 (5H, m), 4.65–3.64 (5H, m), 1.42 (3H, s), 1.3 (3H, s); IR
(
1
KBr): 3070, 2990, 2920, 1600, 1585, 1490, 1445, 1344, 1240, 1210, 1170,
ꢁ1
035, 910, 810, 747 cm .
20
21 20
n
1
Compound 2e: n ¼ 1:4170; ðlit:
¼ 1:4168Þ; H-NMR (CDCl )
D
D
3
d: 4.37–3.3 (6H, m), 1.37 (3H, s), 1.27 (3H, s), 1.2–1 (6H, d); IR (neat): 2970,
2
ꢁ
1
930, 2870, 1460, 1380, 1365, 1260, 1125, 1070, 1030, 920, 850, 735 cm .
2
0
22 20
D
1
Compound 2f: n ¼ 1:4318 ðlit:
n
¼ 1:4320Þ; H-NMR (CDCl3)
D
d: 5.95–4.7 (3H, m), 4.35–3.32 (7H, m), 1.33 (3H, s), 1.25 (3H, s); IR
(
7
neat): 3050, 3000, 2920, 2850, 1455, 1360, 1320, 1250, 1090, 920, 840,
55 cm .
ꢁ1

ORDER
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EPOXIDES AND 1,3-DIOXOLANES
3415
1
5
23 15
n
1
Compound 2g: nD ¼ 1:4359 ðlit:
¼ 1:4357Þ; H-NMR (CDCl )
D
3
d: 4.34–3.12 (5H, m), 1.32 (3H, s), 1.2 (3H, s); IR (neat): 2960, 2900,
860, 1450, 1375, 1250, 1165, 1080, 1025, 935, 870, 740 cm .
ꢁ1
2
ACKNOWLEDGMENT
We are thankful to the Isfahan University Research Council for
partial support of this work.
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Received in Japan August 28, 2000

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