CF3SO3H-SiO2 as catalyst for Ferrier rearrangement: An efficient procedure for the synthesis of pseudoglycosides

Article abstract of DOI:10.1016/j.tet.2012.11.019

An efficient method for the conversion of 2,4,6-tri-O-acetyl-D-glucal to 2,3-unsaturated glycosides by using triflic acid on SiO₂ as catalyst has been established. A series of 2,3-unsaturated glucosides were synthesized in good yield and high anomeric selectivity under transition metal-free conditions.

Full text of DOI:10.1016/j.tet.2012.11.019

Tetrahedron 69 (2013) 583e588
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
CF3SO3HeSiO2 as catalyst for Ferrier rearrangement: an efficient
procedure for the synthesis of pseudoglycosides
,
b
,
a
Peiran Chen a , Shaoshan Wang
*
a School of Chemistry, Chemical Engineering and Biotechnology, Donghua University, 2999 Renmin Road North, Songjiang District, Shanghai 201620, China
b Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, CAS, Shanghai 200032, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 28 July 2012
Received in revised form 30 October 2012
Accepted 6 November 2012
Available online 11 November 2012
An efficient method for the conversion of 2,4,6-tri-O-acetyl-D-glucal to 2,3-unsaturated glycosides by
using triflic acid on SiO2 as catalyst has been established. A series of 2,3-unsaturated glucosides were
synthesized in good yield and high anomeric selectivity under transition metal-free conditions.
Ó 2012 Elsevier Ltd. All rights reserved.
Keywords:
Type I Ferrier rearrangement
Triflic acideSiO2
Tri-O-acetyl-D-glucal
2,3-Unsaturated glycoside
Pseudoglycoside
1. Introduction
caused by the transition metals containing in the catalysts, which
leading to extensive work up. Therefore, there is still interest to find
2,3-Unsaturated glycosides or pseudoglycosides are recognized
as important chiral intermediates in the synthesis of biologically
active compounds1 and functional materials.2 One of the most
useful procedures to achieve 2,3-unsaturated glycosides directly
and efficiently is Type I Ferrier rearrangement, in which glycals are
reacted with nucleophiles promoted by acid catalyst. This reaction
was proposed to proceed through a cyclic allylic oxocarbonium
intermediate, which was formed via departure of leaving group on
the C-3 position of glycal via the action of the acid catalyst, followed
by nucleophilic substitution on the C-1 position via quasi-
equatorial orientation (Scheme 1).3
new efficient catalyst for milder and more efficient synthetic pro-
cess with good anomeric selectivity and yield by using stoichio-
metric amount of nucleophile under low catalyst load.
Herein, we report our results using triflic acid supported on
silica gel (CF3SO3HeSiO2) as a new transition metal-free and highly
efficient catalyst for Type I Ferrier rearrangement.
2. Results and discussion
2.1. Optimization of solvent
Catalyst plays a key role in Type I Ferrier rearrangement. A wide
Solvent played an important role in the reaction. Therefore,
optimization has been carried out. Table 2 shows the results.
By comparison of the results in entry 4 with the others in Table 1,
THF appeared to be the most proper solvent. When using solvent
with low polarity, such as toluene, lower conversion was achieved
and much longer reaction time was necessary (entry 5, Table 1). The
solvents with high hydrophilic character, such as acetone or aceto-
nitrile also led to relative low conversion (entries 2 and 3, Table 1).
range of Lewis acid catalysts,4 such as BF3$Et2O, FeCl3, Fe2(SO4)3,
Fe(NO3)3, InCl3, BiCl3, CeCl3, ZnCl2, Pd(OAc)2, ZrCl4, K5CoW12
-
O
40$3H2O, Bi(OTf)3, Er(OTf)3, Yb(OTf)3, Fe(OTf)3,TiCl4, AuCl3,
HBF4eSiO2, ZnCl2/Al2O3, Brønsted acid,5 such as H2SO4, MeOH/HCl,
H3PO4, PPh3/HBr, HClO4, phosphomolybdic acid (PMA), and other
catalysts6 like I2, IDCP, NIS and DDQ have been reported. However,
some of these reaction systems suffered from the drawbacks in
terms of large excess of nucleophile, stoichiometric amount of
catalyst, harsh reaction conditions, low yields, and those problems
2.2. Type I Ferrier rearrangement under the optimized
conditions
After the optimization, we have established our reaction con-
ditions: with CF3SO3HeSiO2 (10 mol %) as the catalyst and THF as
* Corresponding author. Tel.: þ86 21 67792594; e-mail address: prchen@dhu.
edu.cn (P. Chen).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2012.11.019

584
P. Chen, S. Wang / Tetrahedron 69 (2013) 583e588
..
O
O
Nu
O
R2
R2
R2
:Nu
..
R1
allyloxycarbenium ion
R1
R1
acid catalyst
:
LG
LG = leaving group
Scheme 1. Mechanism of Type I Ferrier rearrangement proposed by R. J. Ferrier.3
Table 1
effects of the nucleophiles in the reaction results has also been
examined. This reaction system has also demonstrated its appli-
cability in the preparative purposes of natural product analogs of
biological interest by the Ferrier rearrangement.
Optimization for solventa of the CF3SO3HeSiO2 catalyzed Ferrier rearrangement
reaction system
OAc
O
OAc
O
TfOH-SiO2
(10mmol%)
OAc
AcO
+
EtOH
OEt
Solvent,
4. Experimental
AcO
40oC
1
4.1. Method and materials
Entry
Solvent
Reaction time
Conversion (%)b
a:
bc
1
2
3
4
5
6
DCM
Acetone
Acetonitrile
THF
Toluene
10 min
15 min
10 min
10 min
45 min
3 h
80%
71%
62%
88%
68%
N.R.
7:1
20:1
8:1
17:1
17:1
/
1H and 13C NMR spectra were recorded on a Bruker AV-400
(400 MHz) spectrometer with Me4Si as internal standard. 19F
NMR spectra were obtained on a Bruker AM-300 (282 MHz)
spectrometer using CFCl3 as an external standard; downfield shifts
Diethyl ether
being designated as positive, all chemical shifts (d) were expressed
a
Reaction conditions: tri-O-acetyl-D-glucal (1) (150 mg, 0.56 mmol), EtOH
in parts per million and coupling constants (J) are in Hertz. Mass
spectra were recorded on a Finnigan-MAT-8430 instrument using
EI ionization at 70 eV. High-Resolution mass spectral (ESI) analyses
were performed on a Finnigan MAT 8430 spectrometer. IR spectra
were recorded on a Nicolet 380 spectrometer. Optical rotations
were measured by WZZ-2 polarimeter. Melting points were mea-
sured on a WRS-2A melting point apparatus. Glucal, epian-
(1.2 equiv),CF3SO3HeSiO2 (10 mol %), solvent (20 mL), 40 ꢀC.
b
Determined by analysis of the 1H NMR spectra of the reaction mixture.
The anomeric ratio was determined by integration of the anomeric hydrogen in
c
the 1H NMR spectra.
the solvent, the Ferrier rearrangement was performed between tri-
O-acetyle -glucal (1) (1 equiv) and various nucleophiles (1.2 equiv)
D
at 40 ꢀC. Results are summarized in Table 2. The structure and
stereochemistry of all the glycosidation products were character-
ized by 1H NMR, 13C NMR, IR, and MS data.
drosteron,
L
-menthol, (1R)-endo-(þ)-fenchol and the protected
glucose were purchased from Energy-Chemical Company. All the
solvents used in the reaction were purified by re-distillation.
Generally, this reaction system afforded 2,3-unsaturated glyco-
sides in high yield with good anomeric selectivity. The simple ali-
phatic alcohols (entries 1e4, Table 2) as nucleophiles gave the
products with relatively lower selectivity on the anomeric center,
while those with higher steric hindrance (entries 5 and 6, Table 2)
gave the products, which were good both in yield and in anomeric
selectivity. In the series of halo-substituted alcohols (entries 7e9,
Table 2), most of those nucleophiles gave satisfactory reaction re-
sults. The aryl alcohol (entries 9, 10, and 11, Table 2) nucleophiles
could also achieve good reaction outcomes, but as a relatively weak
4.2. General procedure for preparation of 2,3-unsaturated
glycosides
To a stirred solution of tri-O-acetyl-D-glucal (136 mg, 0.5 mmol) in
THF (5 mL) were added the corresponding alcohol or thiol (1.2 equiv)
and CF3SO3HeSiO2 (10 mol %) at ambient temperature. The reaction
mixture was stirred under 40 ꢀC and the extent of the reaction was
monitored by TLC analysis. The reaction mixture was diluted with
cooled sodium bicarbonate (satd, 20 mL) and extracted with DCM
(3ꢁ10 mL). The combined organics were dried over anhydrous
Na2SO4. The solvent was removed under vacuum. All the products
were purified by silica gel column chromatography (hexane/
EtOAc¼6/1).
nucleophile, a-trifluoromethyl benzylic alcohol (entry 11, Table 2)
gave the corresponding 2,3-unsaturated O-glycoside with relatively
low anomeric selectivity. Thiol (entry13, Table 2) could be used as
nucleophile in this reaction system and give the product in satis-
factory yield and selectivity.
We also explored the scope of this procedure for the preparation
of pseudoglycals connected with various biologically important
natural products. Formation of two disaccharides (entries 14 and
15, Table 2), one steroid glycoside (entry 16, Table 2) and two other
4.2.1. Ethyl 4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-hex-2-enopyr-
anoside (3a). Colorless oil;
½
a 2D5
þ113.1 (c 1.0, CHCl3,
ꢂ
þ80.3 (c 0.87, CHCl3,
a
:
b
¼50:3),{lit.:4k
½
a 3D1:7
ꢂ
a:b
¼9:1)}; 1H NMR
(400 MHz, CDCl3):
d
1.26 (t, J¼7.1 Hz, 3H), 2.09 (s, 3H), 2.11 (s, 3H),
natural product
(L
-menthol and (1R)-endo-(þ)-fenchol) 2,3-
3.55e3.63 (m,1H), 3.81e3.88 (m,1H), 4.11e4.29 (m, 3H), 5.06 (s,1H),
5.33 (dd, J¼9.7, 1.2 Hz, 1H), 5.83e5.91 (m, 2H) ppm; IR (film, cmꢃ1):
2980, 2894, 1740, 1450, 1376, 1232, 1114, 1049, 899, 828, 739; MS (EI
70eV) m/z: 257 ([Mþꢃ1]), 213 ([MþꢃOEt], 5),199 (1),185 (1), 213 (7),
156 (17), 153 (10), 114 (100), 111 (22), 86 (12), 81 (5), 43 (55).
unsaturated glycosides (entries 17 and 18, Table 2) in high yield
and good selectivity demonstrated the catalytic capability of
CF3SO3HeSiO2 in the synthesis of natural product analogs of bi-
ological interest by the Ferrier rearrangement.
enopyranoside (3b). White solid; mp¼37e38 ꢀC, ½aDꢂD25 þ59 (c 0.59,
3. Conclusion
4.2.2. n-Tetradecyl 4,6-di-O-acetyl-2,3-dideoxy-a- -erythro-hex-2-
We have established a practical procedure for Type I Ferrier
rearrangement with CF3SO3HeSiO2 as the catalyst. By using of this
catalyst, a series of alcohols and thiol were reacted with glucal
donor affording 2,3-unsaturated glycosides in high yield and good
anomeric selectivity. The influence of the inductive and the steric
CHCl3,
a
:
b
¼20:1), {lit.:7c
a
:
b
¼10:1}; 1H NMR (400 MHz, CDCl3):
d
0.89 (t, J¼6.5 Hz, 3H), 1.27 (s, 21H), 1.61 (dd, J¼14.3, 7.3 Hz, 3H),
2.09 (s, 3H), 2.11 (s, 3H) 3.51 (dd, J¼15.9, 6.9 Hz, 1H), 3.78 (dd,
J¼15.9, 7.2 Hz,1H), 4.12e4.26 (m, 3H), 5.04 (s, 1H), 5.33 (d, J¼9.9 Hz,
1H), 5.83e5.91 (m, 2H) ppm; IR (film, cmꢃ1): 2923, 2855, 1745,

P. Chen, S. Wang / Tetrahedron 69 (2013) 583e588
585
Table 2
a
Type I Ferrier rearrangement reaction of 3,4,6-tri-O-acetyl-
D
-glucal (1) with various nucleophiles catalyzed by CF3SO3HeSiO2
OAc
O
OAc
O
CF3SO3H-SiO2
(10 mmol%)
OAc
AcO
1
+
Nu
Nucleophile
THF, 40oC
AcO
2a~r
3a~r
c
Entry
1
Nucleophile
Reaction time
10 min
Product
Yieldb (%)
(a:b)
OAc
O
OEt
EtOH 2a
88
17:1
20:1
AcO
3a
OAc
O
OC14H29-n
3b
2
n-C14H29OH 2b
15 min
90
AcO
OAc
O
OH
3
4
15 min
2 h
86
87
7:1
O
2c
AcO
AcO
3c
OAc
O
O
OH
20:1
2d
3d
OAc
O
OH
5
6
6 h
70
90
a
a
only
O
2e
AcO
AcO
3e
OAc
O
OH
O
10 min
only
2f
3f
OAc
O
O
Cl
O
OH
O
7
8
9
20 min
10 min
20 min
87
82
82
8:1
Cl
AcO
2g
3g
OAc
Br
Br
Br
O
OH
Br
Br
Br
O
a
a
only
AcO
2h
3h
OAc
O
CF3
O
CF3CH2OH 2i
only
AcO
3i
OAc
O
OH
10
11
15 min
10 min
88
80
10:1
O
AcO
2j
3j
OAc
O
OH
a
only
O
2k
AcO
3k
OAc
O
CF3
OH
O
12
25 min
67
3:1
CF3
AcO
(continued on next page)
2l
3l

586
P. Chen, S. Wang / Tetrahedron 69 (2013) 583e588
Table 2 (continued )
c
Entry
Nucleophile
Reaction time
25 min
Product
OAc
Yieldb (%)
78
(
a:b)
SH
O
13
14
a
only
S
2m
AcO
AcO
3m
O
O
O
OAc
O
O
HO
O
4 h
71
63
13:1
O
O
O
O
O
O
3n
2n
O
O
O
O
O
O
OAc
O
O
O
15
5 h
a
only
HO
O
O
O
AcO
2o
3o
O
H
H
O
OAc
O
H
H
H
H
H
H
16
17
2 h
84
73
a
a
only
only
O
HO
AcO
H
H
2p
3p
HO
OAc
O
15 min
O
AcO
2q
3q
OAc
O
O
18
10 min
72
a
only
OH
2r
AcO
3r
D
-glucal (1) (150 mg, 0.56 mmol), nucleophile (1.2 equiv), CF3SO3HeSiO2 (10 mol %), THF (5 mL), 40 ꢀC.
a
Reaction conditions: tri-O-acetyl-
b
c
Isolated yield.
The anomeric ratio was determined by integration of the anomeric hydrogen in the 1H NMR spectra.
1468, 1373, 1237, 1044, 899, 832, 730; MS (ESI) m/z: 549.2
([MþNa]þ,100), 213 (30), 153 (17).
CDCl3): d 1.30 (s, 9H), 2.09 (s, 6H), 4.14e4.25 (m, 3H), 5.28 (d,
J¼9.0 Hz, 1H), 5.33 (s, 1H), 5.80 (dd, J¼39.1, 9.9 Hz, 2H) ppm; IR
(film, cmꢃ1): 2974, 2357, 1744, 1445, 1373, 1235, 1098, 1039, 897,
774, 716, 607; MS (ESI) m/z: 309.1 ([MþNa]þ, 25), 213.1 (100), 153.1
(40), 111.1 (26).
4.2.3. Isopropyl 4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-hex-2-
a 25
enopyranoside (3c). Colorless oil; ½ ꢂD þ142 (c 0.71, CHCl3,
a
:b
¼7:1), {lit.:4k
½
a 3D1:7
ꢂ
þ115.3 (c 1.0, CHCl3,
a:b
¼7:3)}; 1H NMR
(400 MHz, CDCl3):
d
1.16 (d, J¼6.0 Hz, 3H),1.24 (d, J¼6.3 Hz, 3H), 2.06
4.2.6. Cyclohexyl 4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-hex-2-
(s, 3H), 2.07 (s, 3H), 3.94e4.00 (m,1H), 4.11e4.23 (m, 3H), 5.11 (s,1H),
5.28 (d, J¼9.5 Hz,1H), 5.77e5.89 (m, 2H) ppm; IR (film, cmꢃ1): 3043,
2933, 2859, 1743, 1552, 1446, 1376, 1372, 1230, 1094, 1037, 742, 596;
MS (ESI) m/z: 290.0 ([MþNH4]þ,38), 212.9 (100), 153.1 (60).
enopyranoside (3f). Colorless oil; ½a D25
ꢂ
þ91 (c 0.8, CHCl3,
a only),
{lit.:4k
½
a 3D1:7
ꢂ
þ110.7 (c 1.0, CHCl3,
a
:
b
¼9:1)}; 1H NMR (400 MHz,
CDCl3):
d: 1.18e1.32 (m, 5H), 1.54 (d, J¼9.6 Hz, 1H), 1.74 (s, 2H),
1.88e1.96 (m, 2H), 2.08 (s, 6H), 3.65 (s, 1H), 4.16e4.21 (m, 3H), 5.17
(s, 1H), 5.30 (d, J¼9.4 Hz, 1H), 5.80e5.88 (m, 2H) ppm; IR (film,
cmꢃ1): 3047, 2933, 2858,1744,1446, 1372, 1230, 1037, 972, 902, 742,
607; MS (EI 70 eV) m/z: 311 (Mþꢃ1), 253, 239 (1), 213 (24), 210 (18),
168 (27), 153 (42), 128 (33), 111 (88), 86 (68), 55 (26), 43 (100), 41
(13).
4.2.4. sec-Butyl 4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-hex-2-
enopyranoside (3d). Colorless oil;
½
a 2D5
ꢂ
þ121 (c 0.72, CHCl3,
a
:b
¼20:1), {lit.:5b
(a:
b
¼11:1)}; 1H NMR (400 MHz, CDCl3):
d
0.85e1.03 (m, 3H), 1.15 (d, J¼5.9 Hz, 2H), 1.25 (d, J¼6.1 Hz, 1H),
1.47e1.59 (m, 2H), 2.09 (s, 6H), 3.70e3.79 (m, 1H), 4.17e4.25 (m,
3H), 5.13 (s, 1H), 5.30 (d, J¼9.5 Hz, 1H), 5.79e5.93 (m, 2H) ppm; IR
(film, cmꢃ1): 3047, 2969, 2929, 1744, 1451, 1373, 1229, 1103, 1034,
904, 731; MS (ESI) m/z: 309.1 ([MþNa]þ, 37), 213.1 (100), 153.1 (57).
4.2.7. 2-(2-Chloroethoxyl)-ethoxyl 4,6-di-O-acetyl-2,3-dideoxy-a-D-
erythro-hex-2-enopyranoside (3g). Colorless oil; ½a D25
þ75.8 (c 0.86,
ꢂ
CHCl3,
a
:b
¼8:1); 1H NMR (400 MHz, CDCl3):
d 2.08 (s, 3H), 2.09 (s,
3H) 3.63 (t, J¼5.4 Hz, 2H), 3.80e3.67 (m, 5H), 3.92 (d, J¼7.6 Hz, 1H),
4.2.5. tert-Butyl 4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-hex-2-
4.12e4.27 (m, 3H), 5.08 (s, 1H), 5.32 (d, J¼9.6 Hz, 1H), 5.75e5.99 (m,
enopyranoside (3e). Colorless oil;
½
a 2D5
ꢂ
þ104 (c 0.75, CHCl3,
2H) ppm; 13C NMR (101 MHz, CDCl3):
d 20.76, 20.92, 42.70, 62.96,
a
only), {lit.:7d
½
a 3D1:7
ꢂ
þ100.69 (c 0.75, CHCl3)}; 1H NMR (400 MHz,
65.28, 66.94, 67.71, 70.50, 71.35 94.60, 127.66, 129.24, 170.23,

P. Chen, S. Wang / Tetrahedron 69 (2013) 583e588
587
170.72; IR (film, cmꢃ1): 2941, 2885, 1742, 1443, 1372, 1233, 1111,
1044, 976, 902, 739, 663, 607; MS (ESI) m/z: 354.1 ([MþNH4]þ,100);
213.0 (21); HR-ESI C14H21O7Cl1Na1 [MþNa]þ calcd 359.08759,
found 359.08,680.
CHCl3,
a
), {lit.:6 (
a
:
b
¼8:1)}; 1H NMR (400 MHz, CDCl3):
d
1.26e1.44
(m, 5H), 1.61 (d, J¼10.6 Hz, 1H), 1.76 (d, J¼8.8 Hz, 2H), 2.03 (d,
J¼11.7 Hz, 2H), 2.09 (s, 3H), 2.10 (s, 3H), 2.91 (t, J¼10.1 Hz, 1H),
4.16e4.36 (m, 3H), 5.35 (d, J¼9.3 Hz, 1H), 5.66 (s, 1H), 5.76 (d,
J¼10.2 Hz, 1H), 5.93 (d, J¼10.0 Hz, 1H) ppm; IR (film, cmꢃ1): 2929,
2854, 1744, 1643, 1446, 1371, 1233, 1048, 967, 830, 792, 604; MS
(ESI) m/z: 346.1 ([MþNH4]þ, 100), 213.1 (30), 153.1 (10).
4.2.8. 2,2,2-Tribromomethyl ethoxyl 4,6-di-O-acetyl-2,3-dideoxy-a-
D
-erythro-hex-2-enopyranoside (3h). Colorless oil; ½a D25
þ88 (c 0.75,
ꢂ
CHCl3, a d 2.11 (s, 6H), 3.50e3.55(m,
only); 1HNMR (400 MHz, CDCl3):
7H), 3.95 (d, J¼9.4 Hz,1H), 4.09 (d, J¼8.9 Hz,1H), 4.24 (s, 2H), 5.05 (s,
4.2.14. 6-O-(4,6-Di-O-acetyl-2,3-dideoxy-
a
-
a
D
-erythro-hex-2-enop-
-galactopyranose
1H), 5.34 (d, J¼9.7 Hz, 1H), 5.87 (dd, J¼39.6, 10.3 Hz, 2H) ppm; 13C
yranosyl)-1,2:3,4-di-O-isopropylidene-
-
D
NMR (101 MHz, CDCl3):
d
20.83, 20.94, 34.49, 43.39, 62.80, 65.03,
(3n). White solid; mp¼132e133 ꢀC; ½a D25
ꢂ
þ14.2 (c 0.83, CHCl3,
67.33, 67.44, 94.52, 126.99, 129.76, 170.14, 170.72; IR (film, cmꢃ1):
3015, 2957, 2892,1743,1425,1372,1229,1043, 906, 853, 738, 665, 609,
533; MS (ESI) m/z: 558.8 (100) 556.7 ([MþNa]þ, 40); 213.0 (10); HR-
ESI C15H21O6Br3Na1 [MþNa]þ calcd 556.87701, found 556.87805.
a
:
b
¼13:1), {lit.:5g
½
a 2D5
d
ꢂ
¼þ16.8 (c 1.0, CHCl3,
a:
b
¼5:1)}; 1H NMR
(400 MHz, CDCl3):
1.34 (s, 3H),1.35 (s, 3H),1.45 (s, 3H),1.54 (s, 3H),
2.09 (s, 3H) 2.12 (s, 3H), 3.74e3.79 (m, 1H), 3.86e3.88 (m, 1H),
4.00e4.03 (m, 1H), 4.15e4.18 (m, 2H), 4.26e4.34 (m, 3H), 4.63 (d,
J¼7.9 Hz, 1H), 5.10 (s, 1H), 5.33 (d, J¼9.8 Hz, 1H), 5.53 (d, J¼4.8 Hz,
1H), 5.74e5.95 (m, 2H) ppm; IR (film, cmꢃ1): 2996, 2927, 1741, 1642,
1454, 1377, 1226, 1050,1005, 902, 806, 687, 645; MS (ESI) m/z: 490.1
([MþNH4]þ,100), 495.1 ([MþNa]þ,72); 213.1 (12).
4.2.9. 2,2,2-Trifluoroethyl 4,6-di-O-acetyl-2,3-dideoxy-
a
-
D
-erythro-
þ65 (c 0.66, CHCl3,
a:b
55:45)}; 1H NMR
¼
hex-2-enopyranoside (3i). Colorless oil; ½a D25
ꢂ
a
only), {lit.:6e
½
a 2D5
ꢂ
þ79 (c 0.8, MeOH
(400 MHz, CDCl3): d: 2.11 (s, 6H), 3.96e4.13 (m, 3H), 4.18e4.28 (m,
2H), 5.12 (s, 1H), 5.35 (d, J¼9.8 Hz, 1H), 5.87 (d, J¼10.1 Hz, 1H), 5.97
4.2.15. 3-O-(4,6-Di-O-acetyl-2,3-dideoxy-
a
-
D
-erythro-hex-2-enopy-
-glucofuranose
only), {lit.:6d
a 2D1
only)}; 1H NMR (400 MHz, CDCl3):
a d 1.32 (s, 3H), 1.34
(d, J¼10.2 Hz, 1H) ppm; 19F NMR (282 MHz,CDCl3):
d: ꢃ74.27 (t,
ranosyl)-l,2:5,6-di-O-isopropylidene-a-D
J¼8.6 Hz) ppm; IR (film, cmꢃ1): 2955, 1746, 1433, 1375, 1282, 1235,
1163, 1070, 990, 902, 836, 735, 661, 596, 473; MS (ESI) m/z: 330.1
([MþNH4]þ,100), 282.2 (20), 213.1 (45), 153.1 (20), 111.1 (13).
(3o). Colorless oil; ½a D25
ꢂ
þ57 (c 0.66, CHCl3,
a
½ ꢂ
þ47.0 (c 0.8,
(s, 3H), 1.42 (s, 3H), 1.51 (s, 3H), 2.10 (s, 3H) 2.13 (s, 3H), 3.97e4.01
(m, 1H), 4.08e4.24 (m, 6H), 4.34 (s, 1H), 4.64 (s, 1H), 5.28 (s, 2H),
5.84 (d, J¼10.1 Hz, 1H), 5.90 (d, J¼4.4 Hz, 2H), ppm; IR (film, cmꢃ1):
2984, 2937, 2369, 1744, 1448, 1374, 1228, 1155, 1036, 848, 733, 642,
606; MS (ESI) m/z: 495.0 ([MþNa]þ,100); 256.0 (25).
4.2.10. Benzyl 4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-hex-2-
enopyranoside (3j). Colorless oil;
½
a 2D5
þ56.34 (c 1.0, CHCl3,
ꢂ
þ77 (c 0.84, CHCl3,
a:b
¼10:1), {lit.:4k
½
a 3D1:7
ꢂ
a:b
¼9:1)}; 1H NMR
(400 MHz, CDCl3): d 2.09 (s, 3H), 2.11 (s, 3H), 4.13e4.27 (m, 3H), 4.61
(d, J¼11.6 Hz,1H). 4.82 (d, J¼11.5 Hz,1H), 5.15 (s,1H), 5.35 (d, J¼9.1 Hz,
1H), 5.85e5.92 (m, 2H), 7.32e7.37 (m, 5H) ppm; IR (film, cmꢃ1): 3031,
2929, 2874,1738,1597,1493,1451,1374,1237,1034, 808, 740, 698, 598,
471; MS (EI 70 eV) m/z: 319 (Mþꢃ1), 213 (6), 187 (8), 176 (9), 153 (7),
111 (26), 109 (6), 94 (18), 91 (100), 81 (8), 65 (7), 43 (58).
4.2.16. Epiandrosteronyl-4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-
hex-2-enopyranoside (3p). White solid; mp¼125e126 ꢀC; ½a D25
ꢂ
þ84
¼9:1),
d 0.69 (m, 1H), 0.84
(c 0.91, CHCl3,
a
only), {lit.:4v
½
a 2D5
ꢂ
þ105 (c 0.53, CHCl3,
a:b
mp¼124e126 ꢀC}; 1H NMR (400 MHz, CDCl3):
(s, 3H), 0.87 (s, 3H), 0.93e1.03 (m, 2H), 1.15e1.22 (m, 1H), 1.24e1.34
(m, 5H), 1.39e1.97 (m, 12H) 2.09 (s, 3H), 2.11 (s, 3H), 2.45 (dd,
J¼19.2, 8.7 Hz, 1H), 3.60e3.68 (m, 1H), 4.16e4.27 (m, 3H), 5.18 (s,
1H), 5.32 (d, J¼9.3 Hz, 1H), 5.81e5.90 (m, 2H) ppm; IR (film, cmꢃ1):
3047, 2933, 2851, 1743, 1640, 1453, 1373, 1228, 1037, 897, 828, 744,
600; MS (ESI) m/z: 525.2 ([MþNa]þ,100), 212.9 (22).
4.2.11. (2-Naphthyl)-methyl
4,6-di-O-acetyl-2,3-dideoxy-
a
-
D
-er-
ythro-hex-2-enopyranoside (3k). White solid; mp¼72 ꢀC, ½a D25
ꢂ
þ42
(c 0.73 CHCl3,
a
only), {lit.:7e mp¼72 ꢀC, ½a 2D3
ꢂ
þ12 (c 1.0, CHCl3,
a
:b
¼9:1)}; 1H NMR (400 MHz, CDCl3):
d 2.10 (s, 3H), 2.11 (s, 3H),
4.17e4.29 (m, 3H), 4.78 (d, J¼11.9 Hz,1H), 4.99 (d, J¼11.8 Hz,1H), 5.20
(s, 1H), 5.36 (d, J¼9.2 Hz, 1H), 5.88e5.95 (m, 2H), 7.49e7.51 (m, 3H),
7.83e7.86 (m, 4H) ppm; IR (film, cm-1): 3053, 2926, 2876,1947,1741,
1506, 1423, 1375, 1230, 1044, 963, 901, 860, 817, 742, 606, 535, 474;
MS (ESI) m/z: 393.0 ([MþNa]þ,100), 212.9 (25),153.1 (60),111.2 (20).
4.2.17.
enopyranoside (3q). Colorless oil;
only), {lit.:4s
a 2D4
þ142.5 (c 0.5, CHCl3,
(400 MHz, CDCl3):
0.78 (d, J¼6.7 Hz, 3H), 0.91e1.11 (m, 8H),
L
-Methyl 4,6-di-O-acetyl-2,3-dideoxy-
a 2D5
þ151 (c 0.63, CHCl3,
only)}; 1H NMR
a-D-erythro-hex-2-
½
ꢂ
a
½
ꢂ
a
d
1.20e1.48 (m, 3H), 1.52e1.78 (m, 3H), 2.08 (s, 3H), 2.11 (s, 3H), 2.20
(d, J¼12.2 Hz,1H), 3.41e3.46 (m, 1H), 4.17e4.26 (m, 3H), 5.11 (s, 1H),
5.29 (d, J¼8.9 Hz, 1H), 5.88 (d, J¼10.1 Hz, 2H) ppm; IR (film, cmꢃ1):
2952, 2925, 2864, 1746, 1580, 1454, 1373, 1233, 1038, 911, 741; MS
(ESI) m/z: 391.2 ([MþNa]þ,100); 213.0 (25), 153.1 (14).
4.2.12. 2,2,2-Trifluoro-1-phenyl ethyl 4,6-di-O-acetyl-2,3-dideoxy-a-
D
-erythro-hex-2-enopyranoside (3l). Colorless oil; ½a D25
þ61 (c 0.58,
ꢂ
CHCl3,
a:
b
¼3:1); 1H NMR (400 MHz, CDCl3): d a-anomer: 2.13 (s,
6H), 4.24e4.32 (m, 3H), 4.93 (s, 1H), 5.11 (dd, J¼12.8, 6.2 Hz, 1H),
5.28e5.37 (m, 1H), 5.81 (d, J¼9.9 Hz, 1H), 5.98 (d, J¼10.8 Hz, 1H),
7.35e7.55 (m, 5H) ppm;
b
-anomer: 1.91 (s, 1H), 2.06 (s, 1H), 3.49 (d,
4.2.18. (þ)-endo-Fenacholyl
4,6-di-O-acetyl-2,3-dideoxy-a-D-er-
J¼12.2 Hz, 0.3H), 3.72 (d, J¼8.4 Hz, 0.3H), 3.93 (d, J¼12.3 Hz, 0.3H),
ythro-hex-2-enopyranoside (3r). White solid; mp¼74e76 ꢀC; ½a D25
ꢂ
4.99 (d, J¼6.5 Hz, 0.3H), 5.01 (d, J¼6.5 Hz, 0.3H), 5.39 (s, 0.3H). 13
C
þ65.1 (c 0.64, CHCl3,
a
only), {lit.:4s
½
a 2D4
ꢂ
þ48.7 (c 0.5, CHCl3,
NMR (101 MHz, CDCl3): d a-anomer: 20.66, 20.91, 62.67, 65.05,
a d: 0.89 (s, 3H), 1.00 (t,
only)}; 1H NMR (400 MHz, CDCl3):
67.77, 75.77, 77.71, 91.71,126.52, 128.51, 128.72, 129.84, 130.48,
J¼11.6 Hz, 1H), 1.06 (s, 3H), 1.13 (s, 3H), 1.27e1.42 (m, 1H), 1.50 (d,
J¼10.1 Hz, 1H), 1.56 (s, 1H), 1.78e1.65 (m, 3H), 2.10 (s, 6H), 3.47 (s,
1H), 4.13e4.28 (m, 3H), 5.00 (s, 1H), 5.30 (d, J¼9.5 Hz, 1H),
5.84e5.93 (m, 2H) ppm; IR (film, cmꢃ1): 3043, 2951, 2875, 1741,
1461, 1373, 1244, 1044, 972, 908, 832, 747, 603; MS (ESI) m/z: 389.1
([MþNa]þ,100); 213.1 (25).
131.91, 170.25, 170.70;
b-anomer: 20.54, 20.58, 61.87, 64.82, 67.42,
75.77, 78.02, 96.12, 126.44, 127.74, 128.44, 129.28, 130.34, 133.69,
170.08, 170.53; 19F NMR (282 MHz, CDCl3):
d
ꢃ76.34 (d, J¼6.7 Hz),
ꢃ76.69 (d, J¼6.6 Hz) ppm; IR (film, cmꢃ1): 2966, 2361, 1745, 1448,
1374, 1234, 1175, 1045, 988, 910, 759, 705, 608; MS (ESI) m/z: 406.1
([MþNH4]þ, 100); 213.1 (30); HR-ESI C18H19O6F3Na1 [MþNa]þ calcd
411.10408,found 411.10259.
Acknowledgements
4.2.13. Cyclohexyl 4,6-di-O-acetyl-2,3-dideoxy-
a
-
D
-erythro-hex-2-
This work is financially supported by a grant of The National
Natural Science Foundation of China (NSFC, Grant No. 21272305),
eno-1-thio-a-D
-pyranoside (3m). Colorless oil; ½a D25
ꢂ
þ79 (c 0.80,

588
P. Chen, S. Wang / Tetrahedron 69 (2013) 583e588
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Natural Science Foundation of Shanghai Municipality (Grant No.
12ZR1400200) and The Fundamental Research Funds for the Na-
tional Universities (11D10508).
Supplementary data
Supplementary data include 1H NMR, 19F NMR spectra of all the
products; 13C NMR, HRMS of the new compounds. Supplementary
data related to this article can be found online at http://dx.doi.org/
10.1016/j.tet.2012.11.019.
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