H2SO4-SiO2: Highly efficient and novel catalyst for the Ferrier-type glycosylation

Article abstract of DOI:10.1016/j.cclet.2010.03.013

Sulfuric acid immobilized on silica gel is designed as a very useful catalyst for synthesis of 2,3-unsaturated glycopyranosides. This handy, metal-free, environment friendly transformation provides high yields and α-stereoselectivities in a very few amount (<0.02 eq.) of catalyst and in short reaction times (<10 min).

Full text of DOI:10.1016/j.cclet.2010.03.013

Available online at www.sciencedirect.com
Chinese Chemical Letters 21 (2010) 922–926
www.elsevier.com/locate/cclet
H2SO4-SiO2: Highly efficient and novel catalyst
for the Ferrier-type glycosylation
Jia Fen Zhou a, Xuan Chen a, Qing Bing Wang a, Bo Zhang a,
Li Yan Zhang a, Abdullah Yusulf a, Zhong Fu Wang b,
a
Jian Bo Zhang a, , Jie Tang
*
a Department of Chemistry, East China Normal University, Shanghai 200062, China
b School of Life Sciences, Northwestern University, Xi’an 710069, China
Received 4 December 2009
Dedicated to Professor Gengyuan Tian on the occasion of his 70th birthday.
Abstract
Sulfuric acid immobilized on silica gel is designed as a very useful catalyst for synthesis of 2,3-unsaturated glycopyranosides.
This handy, metal-free, environment friendly transformation provides high yields and a-stereoselectivities in a very few amount
(<0.02 eq.) of catalyst and in short reaction times (<10 min).
# 2010 Jian Bo Zhang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
Keywords: Glycosylation; H2SO4-SiO2; Ferrier rearrangement; O-glycosides
Double bond rearrangements in carbohydrate systems lead to various kinds of sugar transformations [1]. In these
productsoftransformations, 2,3-unsaturated-O-glycosideshavereceivedmuchattentioninrecentyears, becausetheyare
very useful chiral building blocks in the synthesis of a great deal of compounds: oligosaccharides [2], glycopeptides [3],
modified carbohydrates [4], nucleosides [5], and many bioactive natural products [6]. Besides, they are main building
blocks for diversity-oriented pilot library realization [7]. Recently, Boysen et al. reported that the 2,3-unsaturated
pyranoside could be converted into a new type of olefin phosphorus chelate ligand in asymmetric synthesis [8], which
established the further importance. The method widely employed to obtain the 2,3-unsaturated glycosides is Lewis acid-
catalyzed allylic rearrangement of glycals, which is well known as the Ferrier reaction [9]. Up till now, a variety of acids
have been used for transformation such as BF3ÁOEt2 [9a], IDCP [10], TMSOTf [11], I2 [12], Sc(OTf)3 [13], InCl3 [14],
Yb(OTf)3 [15], BiCl3 [16], Dy(OTf)3-immobilized in ionic liquids [17], ZnCl2 [18], FeCl3 [19], HClO4-SiO2 [20], NiCl5
[21], Er(OTf)3 [22], Fe2(SO4)3ÁxH2O [23] and ZnCl2/Al2O3 [24]. Recently, H2SO4-SiO2 as a silica-supported reagent
[25] has attracted much attention for its easy preparation, low cost, high efficiency and environmental benignness. In
addition, it has already been used in the area of sugar chemistry, e.g. acetalation–acetylation of sugars [26], synthesis of
* Corresponding author.
E-mail address: jbzhang@chem.ecnu.edu.cn (J.B. Zhang).
1001-8417/$ – see front matter # 2010 Jian Bo Zhang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
doi:10.1016/j.cclet.2010.03.013

J.F. Zhou et al. / Chinese Chemical Letters 21 (2010) 922–926
923
Scheme 1. Synthesis of 2,3-unsaturated glycopyranosides catalyzed with sulfuric acid on silica gel.
Table 1
Glycosidation in different solvents and temperatures.
Entry
Solvent
Temperature (8C)
Time (min)
Yield (%)a
1
2
3
4
CH2Cl2
CH2Cl2
MeCN
MeCN
25
40
25
80
140
70
75
76
36
93
160
5
a
Isolated yields.
O-isopropylidene sugar derivatives [27], and glycosylation of free monosaccharides [28]. In this note, we wish to
recommendH2SO4-SiO2 effectively catalyzed Ferrier reaction. Fortunately, the reaction used H2SO4-SiO2 as the catalyst
obtained excellent yields and short reaction time (Scheme 1).
Firstly, the glycosidation of 3,4,6-tri-O-acetyl-D-glucal (20 mg) with benzyl alcohol catalyzed by H2SO4-SiO2
(1.5 mg, 0.9 mmol H+/g) was served as the model reaction to optimize the desired solvent and temperature. The
preliminary results, which were summed up in the Table 1, showed that glycosidation of 3,4,6-tri-O-acetyl-D-
glucal with benzyl alcohol can obtain the best results at 80 8C in MeCN with respect to the yield and reaction
time.
Secondly, we examined the influence of dosage of H2SO4-SiO2 on the preceding glycosidation, which was
summarized in Table 2. When smaller amount of catalyst was used, the reaction precedes much slower (entry 1). On
the other hand, although the transformation performed much faster while catalyzed by more catalyst, many by-
products were observed in the reaction mixture (entry 3). The table showed that the best results were achieved when
the reaction was processed with 0.02 eq. H2SO4-SiO2.
According to the optimized condition, this method was extended to other O-nucleophiles including primary,
secondary, propargyl, allylic and complex alcohols, such as ethylene glycol monomethyl ether (Table 3, entry 13). All
reactions took place in less than 10 min with high yields. Except Cholesterol poorly soluble in acetonitrile, which led
to the yield of the product of D-glucal and cholesterol being low (73%). When the solvent was changed into
dichloromethane, the yield obviously increased (85%) (Table 3, entry 14). In most cases, two anomers of 2,3-
unsaturated products (a and b) were obtained; while the a anomer was the primary product, which were characterized
1
by analysis of spectral data (IR, H NMR and MS).
Table 2
Comparison of results of Ferrier transformation with different dosages H2SO4-SiO2 [32].
Entry
Dosage of catalysts (eq.)a
Time (min)
Yield (%)b
1
2
3
0.007
0.02
0.07
30
5
87
93
78
2
a
Corresponding to D-glucal.
b
Isolated yields.

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J.F. Zhou et al. / Chinese Chemical Letters 21 (2010) 922–926
In conclusion, we have introduced a highly efficient, convenient and environment friendly methodology to easily
generate 2,3-unsaturated glycosides. In addition, the short reaction time, high yields, and sparing dosage (as less than
0.02 eq.) of catalyst inspired us to report this method. Furthermore, the reaction mixture does not need any workup;
merely requires filtration to remove solid-support catalyst and purification by flash column chromatography. These
features, combined with the fairly cheap catalyst, make this method an attractive alternative to existing methodologies
for the preparation of 2,3-unsaturated glycosides.
Table 3
H2SO4-SiO2 catalyzed Ferrier transformation.
Entry
1
Acceptors
Products
Time (min)
5
Yield (%)a
93
a:b ratiob
PhCH2OH
5:1 [22,33]
2
3
CH3OH
5
5
88
4.4:1 [29]
5.2:1 [22]
CH3CH2OH
100
4
CH3CH2CH2OH
10
92
4.5:1 [31]
5.0:1 [22]
5
6
7
CH3(CH2)2CH2OH
10
10
10
87
95
91
>19:1 [22]
>19:1 [22]
5.0:1 [22]
10.0:1 [31]
8
9
(CH3)2CHOH
10
10
96
96
10
11
10
10
91
92
4.0:1 [19]
5.7:1 [31]
12
n-C8H17OH
10
88
2.5:1 [29]

J.F. Zhou et al. / Chinese Chemical Letters 21 (2010) 922–926
925
Table 3 (Continued )
Entry
Acceptors
Products
Time (min)
10
Yield (%)a
87
a:b ratiob
13
H3COCH2CH2OH
7.0:1 [30]
14
40 (40c)
73 (85c)
>19:1 [16]
a
Isolated yields.
a:b ratios were based on the integration of the corresponding anomeric protons in the 1H NMR (500 MHz) spectrum.
Dichloromethane as the solvent.
b
c
Acknowledgments
We thank the analytic center of East China Normal University for data measurement. The project was supported by
Shanghai Rising-Star Program (No. 06QA14018) and University Students Innovative Activities Project of Shanghai
Municipal Education Commission (No. KY2008-09S).
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[32] Preparation of H2SO4-SiO2 catalyst: the silica gel (5 g, 200–300 mesh) was added in dry Et2O (50 mL) and the mixture was stirred into a pulp.
Then concd. H2SO4 (250 mL) is added in the contents. After stirred 5 minutes, the solvent was evaporated, and the remains were dried at 120 8C
for 3 h to gain the free flowing powder of H2SO4–silica. The loading capacity of H2SO4 on silica gel is 0.9 mmol H+/g.
[33] General procedure of Ferrier transformation. To a stirred solution of 3,4,6-tri-O-acetyl-D-glucal (0.074 mmol, 20 mg) and alcohols
(0.11 mmol) in anhydrous MeCN 0.5 mL at 80 8C was added H2SO4–SiO2 (1.5 mg). After completion of the reaction (monitored by
TLC), the mixture was filtered, and rinsed with CH2Cl2 (2 mL). The solvent was evaporated under reduced pressure; and then the reaction
product was purified by column chromatography (400 mesh silica) to afford pure corresponding 2,3-unsaturated glycoside. The structures of
products were identified through comparison of these spectra data with those in the known literatures. The analytical data for all described
compounds are available in the editorial office of CCL.