Ferric sulphate hydrate-catalyzed, microwave-assisted synthesis of 2,3-unsaturated O-glycosides via the Ferrier reaction

Article abstract of DOI:10.1080/00397910701555402

Fe2(SO4)3·xH2O catalyzes the Ferrier reaction of per-O-acetylated/benzylated glycals with alcohols to give 2,3-unsaturated α-glycosides in a few minutes under microwave irradiation. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910701555402

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Ferric Sulphate Hydrate–Catalyzed,
Microwave‐Assisted Synthesis of
2,3‐Unsaturated O‐Glycosides via the Ferrier
Reaction
Guisheng Zhang a & Qingfeng Liu a
a Henan Key Laboratory for Environmental Pollution Control , School of
Chemical and Environmental Science, Henan Normal University , Xinxiang,
Henan, China
Published online: 05 Oct 2007.
To cite this article: Guisheng Zhang & Qingfeng Liu (2007) Ferric Sulphate Hydrate–Catalyzed,
Microwave‐Assisted Synthesis of 2,3‐Unsaturated O‐Glycosides via the Ferrier Reaction, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 37:20,
3485-3492, DOI: 10.1080/00397910701555402
To link to this article: http://dx.doi.org/10.1080/00397910701555402
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Synthetic Communicationsw, 37: 3485–3492, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701555402
Ferric Sulphate Hydrate–Catalyzed,
Microwave-Assisted Synthesis
of 2,3-Unsaturated O-Glycosides via
the Ferrier Reaction
Guisheng Zhang and Qingfeng Liu
School of Chemical and Environmental Science, Henan Key Laboratory
for Environmental Pollution Control, Henan Normal University,
Xinxiang, Henan, China
.
Abstract: Fe2(SO4)3 xH2O catalyzes the Ferrier reaction of per-O-acetylated/
benzylated glycals with alcohols to give 2,3-unsaturated a-glycosides in a few
minutes under microwave irradiation.
Keywords: Ferrier rearrangement, ferric sulphate hydrate, 2,3-unsaturated
O-glycosides
Ferrier rearrangement has gained great significance since 1969 in the area of
carbohydrate chemistry because it can give access to 2,3-unsaturated-O-
glycosides[1]. 2,3-Unsaturated glycosides, which can be obtained from the
reaction of glycal with nucleophilic agents mediated by Lewis acids via the
Ferrier rearrangement, can be used as intermediates for a variety of
reactions such as Sharpless cis-oxyamination, epoxidation, or hydroxylation.
The derivatives of 2,3-unsaturated glycosides can be used as important
intermediates in glycopeptide blocks,[2] oligosaccharides,[3] modified
Received January 26, 2007
Address correspondence to Guisheng Zhang, School of Chemical and Environ-
mental Science, Henan Key Laboratory for Environmental Pollution Control, Henan
Normal University, Xinxiang, Henan 453007, China. E-mail: zgs6668@yahoo.com
3485

3486
G. Zhang and Q. Liu
carbohydrates,[4] some important antibiotics,[5] nucleosides,[6] natural
product–like compounds,[7] and various natural products.[8]
In recent years, more and more reagents have been described to form
2,3-unasturated-O-glycosides from glycals, such as montmorillonite K-10,[9]
SnCl4,[10] 2,3-dichloro-5,6-dicyano-1,4-quinone (DDQ),[11] K5CoW12O40
.
[14]
[17]
3H2O,[12] InCl3,[13] BF3 OEt2,
BiCl3,[15] Dy(OTf)3,[16] CeCl3 7H2O,
.
.
ZnCl2,[18] ZrCl4,[19] FeCl3,[20] N-iodosuccinimide (NIS),[21] Sc(OTf)3,[22]
I2,[23] HClO4-SiO2,[24] ceric ammonium nitrate (CAN),[25] Bi(NO3)3
.
[26b]
5H2O,[26] Fe(NO3)3 9H2O,
and NbCl5.[27] However, some of the
.
catalysts are very expensive and moisture sensitive. Furthermore, all these
methods have some drawbacks of generality, varied stereoselectivity and
yields, long reaction times, and harsh reaction conditions. Therefore, the
search for newer and more economic synthetic methodologies with greater
efficiency and convenient procedures continues.
Herein, we report the ferric sulphate hydrate–catalyzed, microwave-induced
Ferrier rearrangement of 3,4,6-tri-O-acetyl-D-glucal and 3,4,6-tri-O-benzyl-D-
glucal with alcohols in an open vessel, giving 2,3-unsaturated glycosides with
high a-selectivity (Scheme 1).
In our experiment, per-O-acetylated/benzylated glucal in the presence of
.
an alcohol was treated with 10 mol% of Fe2(SO4)3 xH2O in anhydrous aceto-
nitrile and irradiated with microwaves in an open vessel for a few minutes to
afford the corresponding 2,3-unsaturated glycosides in good yields with very
.
high a-selectivity as summarized in Table 1. Fe2(SO4)3 xH2O used in the
experiments was purchased from the Beijing Chemical Factory (A. R.
.
grade). The moles of Fe2(SO4)3 xH2O are calculated based on the formula:
M Fe2(SO4)3 ꢀ xH2O ¼ 0.5 ꢁ (WFe2(SO4)3 ꢀ xH2O ꢁ Fe(III)%/55.8).
As shown in Table 1, both peracetyl and perbenzyl glycals underwent the
Ferrier reaction with primary and secondary alcohols to afford 2,3-unsaturated-
O-glycosides in good yields with a-selectivity. However, in the literature most
of the Ferrier reaction of 3,4,6-tri-O-acetyl-D-glucal gave 2,3-unsaturated gly-
cosides as a mixture of a- and b-anomers except montmorillonite K-10[9b] and
NbCl5.[27] It is noteworthy that 3,4,6-tri-O-benzyl-D-glucal also underwent
the Ferrier reaction under these conditions to afford the corresponding 2,3-
unsaturated-O-glycosides in excellent yields with exclusively a-selectivity
(entries 10–13). To the best of our knowledge, there was only CAN[25b]
available for the Ferrier rearrangement of 3,4,6-tri-O-benzyl-D-glucal to
form 2,3-unsaturated-O-glycosides. The reaction of perbenzyl glucal with
Scheme 1.

.
Table 1. Fe2(SO4)3 xH2O-catalyzed, microwave-assisted synthesis of 2,3-unsaturated Ferrier rearranged products
Entry
1
Substrate
Alcohol
Product
Timea (min)
5
Yield (%)b
89
2
3
4
5
6
7
5
6
7
5
8
7
92
88
93
91
90
88
(continued)

Table 1. Continued
Entry
8
Substrate
Alcohol
Product
Timea (min)
9
Yield (%)b
92
9
10
11
12
13
7
5
6
4
6
91
87
88
84
86
CH3OH
aAll reactions were irradiated at middle low level in a domestic microwave oven (2450 MHz, 700 W).
1
bIsolated yields; all products were characterized by H NMR and only a observed.

2,3-Unsaturated O-Glycosides
3489
methanol, allyl alcohol, and cyclohexanol in the presence of CAN, formed
2-deoxy products as the major products along with the Ferrier products in
yields of 38%, 23%, and 18%, respectively. In all cases, various a/b ratios
of the glyosides were observed; a products were the major ones. In our
.
methodology, Fe2(SO4)3 xH2O-catalyzed Ferrier rearrangement of 3,4,6-
tri-O-benzyl-D-glucal with methanol, allyl alcohol, and cyclohexanol gave
2,3-unsaturated a-glycosides as the only products in excellent yields of
87%, 88%, and 84%, respectively. No formation of 2-deoxy hexopyranosides
was observed.
.
In addition, we have found that Fe2(SO4)3 xH2O can be reused several
times without loss of activity by filtering the catalyst, washing with acetone,
and drying. Take ethanol for example: the yields of glycosides promoted by
catalyst recovered four times were 89%, 87%, 85%, and 86%, respectively.
In summary, in this article we describe an efficient, economic, ecofriendly
method for the synthesis of O-glycosides from glycals and alcohols using a
catalytic amount of ferric sulphate hydrate under mild reaction conditions.
Our present methodology has the following advantages: (a) the catalyst,
.
Fe2(SO4)3 xH2O, can be easily recovered and reused. (b) The reaction has
short reaction times and generally good yields. (c) The catalyst is nontoxic
and friendly to the environment. In conclusion, we have developed a mild
and ecofriendly approach to the 2,3-unsaturated glycosides.
EXPERIMENTAL
1H NMR spectra were recorded on a Bruker AC-400 NMR spectrometer in
solutions of CDCl3 using tetramethylsilane as the internal standard. Aceto-
nitrile was distilled from P2O5 followed by distillation from CaH2 prior to
use. All reagents were obtained from commercial sources and used without
further purification.
General Procedure
To a mixture of glycal (0.5 mmol) and alcohol (1.5 mmol) in anhydrous aceto-
.
nitrile (1–2 mL), Fe2(SO4)3 xH2O (0.05 mmol) was added, and the mixture
was irradiated with microwaves at the medium low level (2450 MHz, 700 W)
for the specified period of time in an open vessel. The reaction was monitored
using thin-layer chromatography (TLC). After completion of the reaction, the
reaction mixture was filtered, and the filtrate was concentrated under reduced
pressure. The products were purified by silica-gel column chromatography
and characterized by 1H NMR spectroscopy; the spectroscopic data are com-
parable with the literature data (1–9,[26b] 10–12,[25b] and 13.[28]) The catalyst
can be reused for several times without loss of activity.

3490
G. Zhang and Q. Liu
ACKNOWLEDGMENTS
This work was supported by the Natural Science Foundation of China (No.
20672031) and the Program for New Century Excellent Talents in University
of Henan Province.
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