A facile H2SO4/4 ? molecular sieves catalyzed synthesis of 2,3-unsaturated O -glycosides via ferrier-type rearrangement

Article abstract of DOI:10.1055/s-0029-1219539

A novel method for synthesizing 2,3-unsaturated glycosides has been developed using a metal-free catalytic system. This catalyst, sulfuric acid/4 molecular sieves can catalyze the reaction of 3,4,6-tri-O-acetyl-d-glucals and a wide range of alcohols at room temperature, affording 2,3-unsaturated glycosides in good -selectivity (α/β> 6:1) via a Ferrier-type rearrangement. Georg Thieme Verlag Stuttgart - New York.

Full text of DOI:10.1055/s-0029-1219539

LETTER
893
A Facile H SO /4 Å Molecular Sieves Catalyzed Synthesis of 2,3-Unsaturated
2
4
O-Glycosides via Ferrier-Type Rearrangement
a
a
a
a
a
b
a
a
H
J
SO /4Å
i
MS
C
a
talyzed
F
e
f
rrier-T
y
e
n
e
ment Zhou, Bo Zhang, Guofang Yang, Xuan Chen, Qingbing Wang, Zhongfu Wang, Jianbo Zhang,* Jie Tang
2
4
a
Department of Chemistry, East China Normal University, Shanghai 200062, P. R. of China
E-mail: jbzhang@chem.ecnu.edu.cn
b
School of Life Sciences, Northwest University, Xi’an 710069, P. R. of China
Received 13 November 2009
OAc
OAc
Abstract: A novel method for synthesizing 2,3-unsaturated glyco-
sides has been developed using a metal-free catalytic system. This
catalyst, sulfuric acid/4 Å molecular sieves can catalyze the reaction
of 3,4,6-tri-O-acetyl-D-glucals and a wide range of alcohols at room
temperature, affording 2,3-unsaturated glycosides in good a-selec-
tivity (a/b > 6:1) via a Ferrier-type rearrangement.
O
H2SO4, 4 Å MS
CH2Cl2 , r.t.,
O
AcO
AcO
AcO
+
ROH
1a–18a
OR
5
min
1b–18b
R = allyl, propargyl, benzyl, and cholesteryl
Scheme 1
Key words: Ferrier rearrangement, sulfuric acid, molecular sieves,
D-glucal, O-glycosides, glycosylation
In the beginning, we attempted to use sulfuric acid as the
sole catalyst in this experiment. Unfortunately, TLC indi-
cated numerous byproducts appeared in the reaction, re-
gardless the amount of sulfuric acid used. However, for
reactions with added 4 Å molecular sieves, TLC revealed
only the presence of one product. After many trials, it was
found that 0.3 equivalents amount of H SO and equal
Since Ferrier rearrangement was discovered in 1969, it
has received extensive attention in organic syntheses,
from which 2,3-unsaturated glycosides are readily ob-
tained from the corresponding glycal derivatives upon
1
,2
2
4
treatment with various reagents. The glycoside products
3
mass of 4 Å molecular sieves with respect to tri-O-acetyl
D-glucal were the optimal reaction conditions. When
smaller amount of H SO was used, the reaction failed to
as chiral intermediates have played an important role in
the synthesis of bioactive compounds, such as glycopep-
4
5
6
9
2
4
tide building blocks, oligosaccharides, uronic acids,
7
8
proceed. On the other hand, many side products appeared
when a larger amount of H SO was used.
modified carbohydrates, antibiotics, and nucleosides.
2
4
Besides, the unsaturated part of the sugar ring allows
many straightforward modifications such as hydrogena- As shown in Table1, glycosidation of tri-O-acetyl D-glu-
tion, hydroxylation, epoxidation, and aminohydroxyla- cal with primary, secondary, benzyl, allyl, and propargyl
tion, which contribute to their diversities and alcohols proceeded smoothly under the specified condi-
1
0
complexities.
tions. Additionally, complex alcohols such as cholesterol
also produced high yield of the product (85%, entry 18).
All the rearrangements completed within five minutes at
ambient temperature, with excellent yields (80–99%) in
high α-selectivity (α/β > 6:1). The stereochemistry and
structure of the glycosylated products were elucidated by
NMR and mass spectral data.34 The same methodology
was also shown to be reliable on 20 mmol scale of tri-O-
acetyl D-glucal in the presence of benzyl alcohol (11a), in
which the yield was also excellent (99%).
Subsequent to BF ⋅OEt used firstly in this rearrange-
ment, a wide range of Lewis acids were applied as the
catalysts, such as SnCl , InCl3, Sc(OTf)3, FeCl3,
3
2
1
a
1
1
12
13
14
19
4
1
5
16
17
18
Yb(OTf)3,
LiBF ,
Dy(OTf)3,
BiCl3,
ZnCl2,
4
2
0
20b
21
Bi(NO ) ⋅5H O, Fe(NO ) ⋅9H O,
ZrCl4, HClO -
3
2
3
2
3 3
2
4
2
23
24
25
SiO , NbCl , Fe (SO ) ⋅xH O, and ZnCl /Al O . To
2
5
2
4 3
2
2
2
3
pursue a mild and efficient method for Ferrier rearrange-
ment, any further improvement must stay focused on ob-
taining cheap and easily accessible reagent and also
facilitating access to large amounts of 2,3-unsaturated In summary, H SO /4 Å MS is an efficient catalyst for the
2
4
glycosides.
preparation of 2,3-unsaturated glycosides. This method
has the advantages such as inexpensive catalyst, rapid re-
actions, high yields of products, and simple workup pro-
cedure. Further, the efficient applicability of this
methodology to gram-scale amounts of the starting tri-O-
acetyl D-glucal substrates makes this approach highly
practical.
Sulfuric acid is a simple and conventional acid catalyst in
chemistry. Moreover, it has been in widespread used in
the carbohydrate synthesis. Here we wish to report the
2
6
Ferrier-type reaction of acetylated D-glucal under the cat-
2
7
alyst of H SO /4 Å MS. (Scheme1).
2
4
SYNLETT 2010, No. 6, pp 0893–0896
x
x.
x
x.
2
0
1
0
Advanced online publication: 18.02.2010
DOI: 10.1055/s-0029-1219539; Art ID: W17709ST
©
Georg Thieme Verlag Stuttgart · New York

8
94
J. Zhou et al.
LETTER
Table 1 Ferrier Reaction of 3,4,6-Tri-O-acetyl-D-glycal with Alcohols in the Presence of the H SO /4 Å MS
2
4
Entry
1
Acceptors
MeOH
Products
Yield (%)a
9128
a/b Ratiosb
OAc
19:1
1
a
O
O
AcO
O
O
1
b
2
3
MeCH OH
2
OAc
OAc
9317
9229
6:1
2
a
AcO
2
b
MeCH CH OH
7:1
7:1
7:1
2
2
3
a
O
AcO
O
O
3
b
4
5
Me(CH ) CH OH
4
OAc
OAc
9017
2
2
2
a
O
AcO
4
b
Me(CH ) CH OH
88
2
3
2
5
a
O
AcO
O
5
b33
6
7
Me(CH ) CH OH
OAc
OAc
OAc
95
7:1
7:1
2
8
2
6
a
O
AcO
O
7
6
b33
(Me) CHOH
9129
2
7
a
O
AcO
O
7
b
8
9
9130
9217
11:1
7:1
OH
O
AcO
O
O
8
9
a
a
8
b
OH
OH
OAc
OAc
OAc
O
AcO
9
b
1
1
0
1
9317
13:1
7:1
O
O
AcO
1
0a
O
O
1
0b
PhCH OH
9917
2
1
1a
AcO
1
1b
1
1
2
3
OAc
OAc
88
7:1
OH
O
AcO
O
1
1
2a
3a
1
2b33
8929
7.6:1
OH
O
AcO
O
1
3b
Synlett 2010, No. 6, 893–896 © Thieme Stuttgart · New York

LETTER
H SO /4 Å MS Catalyzed Ferrier-Type Rearrangement
895
2
4
Table 1 Ferrier Reaction of 3,4,6-Tri-O-acetyl-D-glycal with Alcohols in the Presence of the H SO /4 Å MS (continued)
2
4
Entry
Acceptors
Products
Yield (%)a
9031
a/b Ratiosb
6:1
1
1
4
5
MeOCH CH OH
OAc
2
2
1
4a
O
O
O
AcO
OMe
O
O
O
1
4b
NCCH CH OH
OAc
OAc
92
9:1
2
2
1
5a
AcO
CN
Cl
1
5b33
1
1
6
7
HOCH CH Cl
8429
80
7.6:1
11:1
2
2
1
6a
AcO
1
6b
Cl CCH OH
OAc
OAc
3
2
1
7a
O
Cl
AcO
O
Cl
Cl
1
7b33
1
8
C H
8532
>19:1
8
17
O
AcO
OChol
1
8b
HO
1
8a
a
Isolated yields.
The a/b ratios were determined by H NMR.
b
1
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synlett.
(4) (a) Schmidt, R. R.; Angerbauer, R. Carbohydr. Res. 1979,
72, 272. (b) Dorgan, B. J.; Jackson, R. F. W. Synlett 1996,
859.
(5) Wieczorek, E.; Thiem, J. Polish J. Chem. 1999, 73, 1111.
Acknowledgment
(6) (a) Schmidt, R. R.; Angerbauer, R. Carbohydr. Res. 1981,
89, 159. (b) Angerbauer, R.; Schmidt, R. R. Carbohydr. Res.
We thank the analytic center of East China Normal University for
data measurement. The authors gratefully thank Editor Hak-Fun
Chow, Professor Liangping Wu, Mr. Xiangguang Tian, and Mr.
Xiaohu Wang for their comments. This project was supported by
Shanghai Rising-Star Program (06QA14018) and University Stu-
dents Innovative Activities Project of Shanghai Municipal Educati-
on Commission (KY2008-09S).
1
981, 89, 193.
(
7) (a) Schmidt, R. R.; Angerbauer, R. Angew. Chem., Int. Ed.
Engl. 1977, 16, 783. (b) Yadav, J. S.; Reddy, B. V. S.
Synthesis 2002, 511.
(
8) Kartika, R.; Frein, J. D.; Taylor, R. E. J. Org. Chem. 2008,
7
3, 5592.
9) (a) Schmidt, R. R.; Angerbauer, R. Carbohydr. Res. 1979,
2, 272. (b) Bracherro, M. P.; Cabrera, E. F.; Gomez, G. M.;
Peredes, L. M. R. Carbohydr. Res. 1998, 308, 181.
10) (a) Stevens, C. L.; Filippi, J. B.; Taylor, K. G. J. Org. Chem.
966, 31, 1292. (b) Isobe, M.; Ichikawa, Y.; Funabashi, Y.;
Mio, S.; Goto, T. Tetrahedron 1986, 42, 2863.
c) Chapleur, Y.; Moufid, N. J. Chem. Soc., Chem. Commun.
(
7
References and Notes
(
1
(
1) (a) Ferrier, R. J.; Prasad, N. J. Chem. Soc. C. 1969, 570.
b) Ferrier, R. J. Adv. Carbohydr. Chem. Biochem. 1970, 24,
99. (c) Ferrier, R. J. Top. Curr. Chem. 2001, 215, 153.
d) Ferrier, R. J.; Zubkov, O. A. Org. React. 2003, 62, 569;
(
1
(
(
1989, 39. (d) Marco-Contelles, J. Tetrahedron Lett. 1994,
35, 5059. (e) Jiang, Y.; Ichikawa, Y.; Isobe, M. Synlett 1995,
285. (f) Banaag, A. R.; Tius, M. A. J. Org. Chem. 2008, 73,
8133. (g) Fernandes, A.; DellOlmo, M.; Tatibouet, A.;
and references therein.
(2) (a) Fraser-Reid, B. Acc. Chem. Res. 1985, 18, 347.
(
1
b) Tolstikov, A. G.; Tolstikov, G. A. Russ. Chem. Rev.
993, 62, 579. (c) Li, J. J. Name Reactions, 3rd ed.;
Imberty, A.; Philouze, C.; Rollin, P. Tetrahedron Lett. 2008,
9, 3484.
4
Springer: Berlin, 2002, 119. (d) Zhang, J. Glycoscience, 2nd
ed.; Fraser-Reid, B.; Tatsuta, K.; Thiem, J., Eds.; Springer:
Heidelberg, 2008, 375.
(
(
11) (a) Grynkiewiez, G.; Priebe, W.; Zamojski, A. Carbohydr.
Res. 1979, 68, 33. (b) Bhate, P.; Horton, D.; Priebe, W.
Carbohydr. Res. 1985, 144, 331.
(
3) (a) Schreiber, S. L. Science 2000, 287, 1964. (b) Kubota,
12) (a) Babu, B. S.; Balasubramanian, K. K. Tetrahedron Lett.
H.; Lim, J.; Depew, K. M.; Schreiber, S. L. Chem. Biol.
2000, 41, 1271. (b) Nagaraj, P.; Ramesh, N. G. Tetrahedron
2002, 9, 265. (c) Burke, M. D.; Berger, E. M.; Schreiber,
Lett. 2009, 50, 3970.
S. L. Science 2003, 302, 613. (d) Hotha, S.; Tripathi, A.
J. Comb. Chem. 2005, 7, 968.
(
13) Yadav, J. S.; Reddy, B. V.; Murthy, C. V.; Kumar, G. M.
Synlett 2000, 1450.
(14) Masson, C.; Soto, J.; Bessodes, M. Synlett 2000, 1281.
Synlett 2010, No. 6, 893–896 © Thieme Stuttgart · New York

8
96
J. Zhou et al.
LETTER
(
(
(
15) Takhi, M.; Rahman, A.; Adel, A. H.; Schmidt, R. R.
Tetrahedron Lett. 2001, 42, 4053.
16) Babu, B. S.; Balasubramnaian, K. K. Synth. Commun. 1998,
reduced pressure, the crude products were purified by silica
gel column chromatography (PE–EtOAc = 10:1).
(34) Selected Spectral Data
29, 4299.
n-Pentyl 4,6-Di-O-acetyl-2,3-dideoxy-a-D-erythro-hex-2-
17) Yadav, J. S.; Reddy, B. V.; Reddy, J. S. J. Chem. Soc.,
Perkin Trans. 1 2002, 2390.
enopyranoside (5b)
1
H NMR (500 MHz, CDCl ): δ = 0.91 (t, J = 6.7 Hz, 3 H),
3
(
(
18) Swamy, N. R.; Venkateswarlu, A. Synthesis 2002, 598.
19) Bettadaiah, B. K.; Srinivas, P. Tetrahedron Lett. 2003, 44,
1.34–1.37 (m, 4 H), 1.59–1.63 (m, 2 H), 2.07–2.10 (m, 6 H),
3.48–3.53 (m, 1 H), 3.75–3.80 (m, 1 H), 4.09–4.27 (m, 3 H,
H-5, H-6a, H-6b), 5.03 (s, 1 H, H-1), 5.30–5.32 (dd, 1 H,
7257.
1
3
(
20) (a) Banik, B. K.; Adler, D.; Nguyen, P.; Srivastava, N.
Heterocycles 2003, 61, 101. (b) Naik, P. U.; Nara, S. J.;
Harjani, J. R.; Salunkhe, M. M. J. Mol. Catal. A: Chem.
J = 9.6 Hz, H-4), 5.83–5.89 (m, 2 H, H-2, H-3) ppm. C
NMR (125 MHz, CDCl ): δ = 13.94, 20.69, 20.88, 22.40,
3
28.31, 29.32, 62.99, 65.27, 66.81, 68.87, 94.31, 127.92,
2
005, 234, 35.
128.89, 170.22, 170.71 ppm. ESI-MS: m/z = 323.10 [M +
Na ].
+
(
(
21) Smitha, G.; Reddy, S. C. Synthesis 2004, 834.
22) Agarwal, A.; Rani, S.; Vankar, Y. D. J. Org. Chem. 2004,
n-Decyl 4,6-Di-O-acetyl-2,3-dideoxy-a-D-erythro-hex-2-
69, 6137.
enopyranoside (6b)
1
(
(
23) Hotha, S.; Tripathi, A. Tetrahedron Lett. 2005, 46, 4555.
24) Zhang, G.; Liu, Q.; Shi, L.; Wang, J. Tetrahedron 2008, 64,
H NMR (500 MHz, CDCl ): δ = 0.86 (t, 3 H), 1.26–1.35 (m,
3
16 H), 2.07–2.09 (m, J = 9.2 Hz, 6 H), 3.49 (m, 1 H), 4.09–
4.26 (m, 3 H, H-5, H-6a, H-6b), 5.01 (s, 1 H, H-1), 5.29–5.32
(dd, J = 1.3, 9.7 Hz, 1 H, H-4), 5.83–5.88 (m, 2 H, H-2, H-
339.
(
(
25) Gorityala, B. K.; Lorpitthaya, R.; Bai, Y.; Liu, X. W.
Tetrahedron Lett. 2009, 65, 5844.
26) (a) Kaczmarek, J.; Preyss, M.; Liinnberg, H.; Szafranek, J.
Carbohydr. Res. 1995, 279, 107. (b) Kaczmarek, J.;
Kaczynski, Z.; Trumpakaj, Z.; Szafranek, J.; Bogalecka, M.;
Lonnberg, H. Carbohydr. Res. 2000, 325, 16. (c) Chao, C.
S.; Chen, M. C.; Lin, S. C.; Mong, K. K. T. Carbohydr. Res.
1
3
3) ppm. C NMR (125 MHz, CDCl ): δ = 14.00, 20.69,
3
20.87, 22.58, 25.67, 26.16, 29.23, 29.36, 29.47, 31.81,
32.70, 62.92, 64.37, 66.80, 68.94, 94.32, 127.90, 128.88,
170.27, 170.76 ppm. ESI-MS: m/z = 393.20 [M + Na ].
+
2-Ethylhexyl 4,6-Di-O-acetyl-2,3-dideoxy-a-D-erythro-
hex-2-enopyranoside (12b)
1
2008, 343, 957.
H NMR (500 MHz, CDCl ): δ = 0.86–0.91 (m, 6 H), 1.26–
3
(
27) Oberdorfer and co-workers have demonstrated similar
Ferrier rearrangement using D-galactal for the construction
of the (2R)-2-hydroxy-6,8-dioxabicyclo[3.2.1]oct-3-ene via
an intramolecular pathway in 40% yield: Oberdorfer, F.;
Haeckel, R.; Lauer, G. Synthesis 1998, 201.
1.33 (m, 8 H), 1.34–1.42 (m, 1 H), 2.09–2.10 (m, J = 5.7 Hz,
6 H), 3.36–3.38 (q, 1 H), 3.54–3.55 (d, 1 H), 3.70–3.71 (t, 1
H), 4.08–4.25 (m, 3 H, H-5, H-6a, H-6b), 5.00 (s, 1 H, H-1),
5.29–5.31 (dd, J = 9.7 Hz, 1 H, H-4), 5.82–5.94 (m, 2 H, H-
1
3
2, H-3) ppm. C NMR (125 MHz, CDCl ): δ = 11.02, 13.99,
3
(
(
(
28) Boga, S. B.; Balasubramanian, K. K. ARKIVOC 2004, (viii),
20.67, 20.87, 22.94, 23.68, 28.93, 30.49, 39.57, 63.03,
65.28, 66.87, 72.64, 94.45-94.53, 127.95, 128.74, 170.21,
170.71 ppm. ESI-MS: m/z = 365.14 [M + Na ].
87.
+
29) Naik, P. U.; Nara, S. J.; Harjani, J. R.; Salunkhe, M. M.
J. Mol. Catal. A: Chem. 2005, 234, 35.
30) (a) Tilve, R. D.; Alexander, M. V.; Khandekar, A. C.;
2-Cyanoethyl 4,6-Di-O-acetyl-2,3-dideoxy-a-D-erythro-
hex-2-enopyranoside (15b)
1
Samant, S. D.; Kanetkar, V. R. J. Mol. Catal. A: Chem.
H NMR (500 MHz, CDCl ): δ = 2.08–2.10 (m, J = 10.0 Hz,
3
2
004, 223, 237. (b) Roy, S. C.; Lesley, S. J.; Dilek, S.; Nino,
6 H), 2.64–2.71 (m, 2 H), 3.76–3.97 (m, 2 H), 4.12–4.22 (m,
3 H, H-5, H-6a, H-6b), 5.07 (s, 1 H, H-1), 5.29–5.31 (dd, 1
H, J = 1.0, 9.5 Hz, H-4), 5.81–5.93 (m, 2 H, H-2, H-3) ppm.
M. WO 2005070911, 2005.
(
31) Surya Kiran, N.; Malla Reddy, S.; Srinivasulu, M.;
Venkateswarlu, Y. Synth. Commun. 2008, 38, 170.
32) Swami, N. R.; Venkateswarlu, A. Synthesis 2002, 598.
33) General Experimental Procedure
1
3
C NMR (125 MHz, CDCl ): δ = 18.96, 20.56, 20.72, 62.69,
3
(
(
63.26, 64.85, 67.14, 94.60, 117.58, 126.70, 129.57, 170.13,
170.59 ppm. ESI-MS: m/z = 306.07 [M + Na ].
+
Typically, H SO (0.3 equiv, 16 μL) was added to the
Trichloroethyl 4,6-Di-O-acetyl-2,3-dideoxy-a-D-erythro-
2
4
mixture of D-glucal (1 mmol, 272 mg), 4 Å MS (272 mg) and
alcohol (1.5 equiv) in CH Cl , and the reaction mixture was
hex-2-enopyranoside (17b)
1
H NMR (500 MHz, CDCl ): δ = 2.07–2.13 (m, J = 10.8 Hz,
2
2
3
stirred for 5 min at r.t. After the reaction was completed, the
reaction mixture was filtered and washed with CH Cl . The
6 H), 4.17–4.18 (d, 2 H), 4.27–4.36 (m, 3 H, H-5, H-6a, H-
6b), 5.31 (s, 1 H, H-1), 5.37–5.38 (dd, J = 9.2 Hz, 1 H, H-4),
2
2
1
3
combined organic layer was washed with sat. NaHCO3
solution (10 mL) and sat. brine (10 mL), and then dried over
anhyd Na SO . After evaporation of the solvent under
5.97–6.00 (m, 2 H, H-2, H-3) ppm. C NMR (125 MHz,
CDCl ): δ = 20.76, 20.87, 62.66, 65.01, 67.49, 76.15, 79.61,
3
96.37, 126.38, 130.20, 170.39, 170.92 ppm. ESI-MS: m/z =
2
4
+
3
82.94 [M + Na ].
Synlett 2010, No. 6, 893–896 © Thieme Stuttgart · New York