Gd(OTf)3 catalyzed preparation of 2,3-unsaturated O-, S-, N-, and C-pyranosides from glycals by Ferrier Rearrangement

Article abstract of DOI:10.1016/j.tet.2015.11.002

By using Gd(OTf)₃ as the catalyst, synthesis of 2,3-unsaturated-glycosides has been performed by Ferrier Rearrangement. A series of 2,3-unsaturated O-, S-, N-, and C-glycosides were obtained from 3,4,6-tri-O-acetyl-d-glucal, 3,4,6-tri-O-benzyl-d-glucal, and 3,4-di-O-acetyl-l-rhamnal under mild reaction conditions in good yields and high anomeric selectivities.

Full text of DOI:10.1016/j.tet.2015.11.002

Tetrahedron xxx (2015) 1e11
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Gd(OTf)3 catalyzed preparation of 2,3-unsaturated O-, S-, N-, and
C-pyranosides from glycals by Ferrier Rearrangement
,
b
,
a
Peiran Chen a , Jie Su
*
a Key Lab of Eco-Textile, Ministry of Education, 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:
By using Gd(OTf)3 as the catalyst, synthesis of 2,3-unsaturated-glycosides has been performed by Ferrier
Received 15 September 2015
Received in revised form 28 October 2015
Accepted 3 November 2015
Available online xxx
Rearrangement. A series of 2,3-unsaturated O-, S-, N-, and C-glycosides were obtained from 3,4,6-tri-O-
acetyl-
D-glucal, 3,4,6-tri-O-benzyl-D-glucal, and 3,4-di-O-acetyl-L-rhamnal under mild reaction condi-
tions in good yields and high anomeric selectivities.
Ó 2015 Elsevier Ltd. All rights reserved.
Keywords:
Ferrier Rearrangement
Gd(OTf)3
3,4,6-Tri-O-acetyl-
3,4,6-Tri-O-benzyl-
3,4-Di-O-acetyl- -rhamnal
D
-glucal
D
-glucal
L
2,3-Unsaturated glycosides
1. Introduction
2. Results and discussion
2,3-Unsaturated glycosides are of great importance in the
synthesis of biologically active molecules1 and new functional
materials2 as chiral intermediates owing to their regio- and stereo-
varieties that they provide for the subsequent transformations. As
one of the most useful procedures to achieve 2,3-unsaturated
glycosides directly and efficiently, Ferrier Rearrangement has
been widely investigated3 and a variety of reagents have been used
to promote this reaction, including Bronsted acids,4 Lewis acids,5
as well as other reagents such as oxidants, etc.6 Due to their
unique properties and high catalytic activities, lanthanide salts as
catalyst in Ferrier Rearrangement have recently gained more and
more applications, among which there could be mentioned
Dy(OTf)3, Er(OTf)3, Yb(OTf)3, Y(OTf)3, Sm(OTf)3, and Tm(OTf)3.7 In
our continuing efforts to search for more efficient catalysts for
Ferrier Rearrangement, we found gadolinium triflate is a highly
efficient catalyst for our purposes. Here we wish to report our
results.
2.1. Optimization of reaction conditions
Considering the effect of the counter anions of the salts on
catalytic capacity,5u,v different gadolinium salts have been
screened, including Gd(OAc)3$6H2O, GdBr3$xH2O, GdB6, Gd(NO3)3,
and Gd(OTf)3, among which Gd(OTf)3 was found to be the best one.
For the reaction solvent, we found acetonitrile gave the best result
among acetone, acetonitrile, THF, dichloromethane, and toluene.
Results are shown in Table 1 and Table 2.
2.2. Synthesis of 2,3-unsaturated glucosides with 3,4,6-tri-O-
acetyl-D-glucal
Synthesis of 2,3-unsaturated glucosides with 3,4,6-tri-O-acetyl-
-glucal (1) was discussed in this section. Results are summarized
D
in Table 3.
It could be seen that with tri-O-acetyl-
D-glucal (1) as starting
material, alcohols (including simple alcohols, chiral alcohols, and
phenols) gave the corresponding 2,3-unsaturated glucosides in
high yields with good anomeric selectivity. It was reported that
* Corresponding author. Tel.: þ86 21 67792594; e-mail address: prchen@dhu.
edu.cn (P. Chen).
when tri-O-acetyl-D-glucal was treated with p-methoxyphenol in
http://dx.doi.org/10.1016/j.tet.2015.11.002
0040-4020/Ó 2015 Elsevier Ltd. All rights reserved.
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2
P. Chen, J. Su / Tetrahedron xxx (2015) 1e11
Table 1
summarized in Table 5. By comparison of Table 3 with Table 5, it
could be seen that relatively higher reactive temperature (60 ꢀC)
was necessary in Table 5, which meant that O-benzyl sugar was
less reactive than O-acetyl sugar in the reactions. 3,4,6-Tri-O-
A comparative study of the catalytic effect of different metal chloride Lewis acid
catalysts in the Ferrier Rearrangement of glucal 1a
OAc
O
OAc
O
Gd-Lewis acid
benzyl-
reaction with the same nucleophiles (2) than 3,4,6-tri-O-acetyl-
glucal (1) However, in our observation, even in the case of 3,4,6-
tri-O-benzyl- -glucal, Gd(OTf)3 is a catalyst which appears to be
D
-glucal (6) took longer time and gave lower yield in the
OAc
+
EtOH
OEt
D
-
o
40 C
AcO
AcO
1
D
Entry
Lewis acid catalyst
Reaction time
Conversion (%)b
a:
bc
efficient enough to afford satisfactory outcome in both yield and
selectivity.
1
2
3
4
5
Gd(OAc)3$6H2O
GdBr3$xH2O
GdB6
Gd(OTf)3
Gd(NO3)3
24 h
24 h
24 h
18 h
24 h
NR
NR
NR
83
/
/
/
90:10
/
3. Conclusions
NR
The bold represents the best reaction condition in the table.
In summary, Gd(OTf)3 has been demonstrated to be a highly
efficient catalyst for the preparation of various 2,3-unsaturated
glycosides in the Ferrier Rearrangement. Under our reaction
a
Reaction conditions: tri-O-acetyl-D-glucal (1) (190 mg, 0.7 mmol), EtOH(5 mL),
catalyst (10 mol %), 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
conditions, 3,4,6-tri-O-acetyl-
D-glucal, 3,4-di-O-acetyl-L-rhamnal,
the 1H NMR spectra.
and 2,4,6-tri-O-benzyl- -glucal afforded corresponding O-, S-, N-,
D
and C-products in high to good yields with high anomeric
selectivities.
Table 2
Optimization of solventa for the Gd(OTf)3 catalyzed Ferrier Rearrangement reaction
system
4. Experimentals
OAc
O
OAc
O
Gd(OTf)3
(10mmol%)
4.1. Method and materials
OAc
+
EtOH
OEt
Solvent,
40oC
AcO
AcO
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
1
Entry
Solvent
Reaction time
Conversion (%)b
a:
bc
1
2
3
4
5
Acetonitrile
DCM
THF
Acetone
Toluene
30 min
24 h
24 h
24 h
24 h
91
Trace
NR
NR
NR
89:11
/
/
/
/
being designated as positive, all chemical shifts (d) were expressed
in ppm and coupling constants (J) are in Hz. Mass spectra were
recorded on a Finnigan-MAT-8430 instrument using EI ionization at
70 eV. High-Resolution mass spectral (ESI) analyses were per-
formed 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 measured on
The bold represents the best reaction condition in the table.
a
Reaction conditions: tri-O-acetyl-D-glucal (1) (190 mg, 0.7 mmol),
EtOH(1.0 equiv), Gd(OTf)3 (10 mol %), solvent (5 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.
a WRS-2A melting point apparatus. The glycals, 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.
CH2Cl2 using BF3$OEt2 as the catalyst, C-glycoside was obtained
exclusively.8 However, in our case, no such phenomenon occurred.
p-Methoxyphenol, 3-hydroxyl-benzaldehyde, and 2-naphthol gave
the corresponding normal O-glycosides as sole products in good
yield (entries 5, 6, and 7, Table 1), which could be confirmed by the
two ortho aromatic signals in the 1H NMR spectra of the products.
When thiols were used as nucleophiles, the corresponding 2,3-
unsaturaterd S-glycosides could also be obtained in high yields
with good anomeric selectivities (entries 8e10, Table 3). Similarly,
with TMS-activated C-donors, C-glucosides formed in high yields
and good selectivity (entry 18e20, Table 1).
4.2. General experimental procedure of Ferrier rearrange-
ment of 3,4,6-tri-O-acetyl-
D-glucal, 3,4-di-O-acetyl-L-rhamnal
or 3,4,6-tri-O-benzyl- -glucal catalyzed with Gd(OTf)3
D
To a stirred solution of 3,4,6-tri-O-acetyl-
0.7 mmol), 3,4-di-O-acetyl- -rhamnal (150 mg, 0.7 mmol) or 3,4,6-
tri-O-benzyl- -glucal (292 mg, 0.7 mmol) and the corresponding
D-glucal (190 mg,
L
D
nucleophile (1.0 equiv) in CH3CN (5 mL) were added Gd(OTf)3
(10 mol %) at ambient temperature. The mixture was stirred under
40 ꢀC for the appropriate amount of time (Tables 3e5), 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 chro-
matography (hexane/EtOAc¼6/1).
2.3. Synthesis of 2,3-unsaturated glycosides with 3,4-di-O-
acetyl-
L-rhamnal
Synthesis of 2,3-unsaturated glycosides with 3,4-di-O-acetyl-
L-
rhamnal (4) was summarized in Table 4. It could be seen that all of
O-, S-, N-, C-donors gave good outcomes in terms of yields and
selectivities.
4.2.1. Ethyl 4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-hex-2-
10
2.4. Synthesis of 2,3-unsaturated glucosides with 3,4,6-tri-O-
enopyranoside (3a). White solid; mp¼70e72 ꢀC; [
a
]
¼þ87.2 (c
D
25
benzyl-
D
-glucal
1.06, CHCl3,
a:
b
¼89:11) {lit.:5u
[
a]
¼þ122.7 (c 0.88, CHCl3,
D
a:b
¼17:1)}; 1H NMR (400 MHz, CDCl3)
d 5.90e5.80 (m, 2H), 5.31 (d,
Synthesis of 2,3-unsaturated glucosides with 3,4,6-tri-O-ben-
zyl- -glucal (6) was discussed in this section. Results are
J¼9.6 Hz,1H), 5.04 (s,1H), 4.28e4.08 (m, 3H), 3.83 (dq, J¼9.6, 7.1 Hz,
1H), 3.57 (dq, J¼9.5, 7.1 Hz, 1H), 2.09 (s, 3H), 2.07 (s, 3H), 1.24 (t,
D
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P. Chen, J. Su / Tetrahedron xxx (2015) 1e11
3
Table 3
Gd(OTf)3 catalyzed synthesis of 2,3-unsaturated glucosides by Ferrier Rearrangement of 3,4,6-tri-O-acetyl-
D
-glucal (1) with nucleophiles (2)a
OAc
OAc
O
O
Gd(OTf)3/MeCN
OAc
Nu
+
Nucleophile
40oC
OAc
OAc
1
2
3
c
Entry
1
Nucleophile (2)
Reaction time
Product (3)
Yieldb/(
a:b)
OAc
O
30 min
91% (89:11)
OCH CH
2
3
OH
OAc
3a
OAc
O
OCH Ph
OH
2
2
3
4
25 min
15 min
30 min
92% (
a
only)
only)
OAc
3b
OAc
O
O
92% (
a
HO
OAc
3c
3d
3e
87% (88:12)
OAc
O
OH
O
OMe
5
6
45 min
79% (
a
only)
only)
MeO
OHC
OAc
OAc
O
CHO
OH
O
30 min
70% (
a
OAc
3f
OAc
O
OH
O
7
8
9
25 min
30 min
20 min
48% (89:11)
OAc
3g
OAc
O
SH
S
82% (
a
only)
OAc
3h
OAc
O
SH
S
OMe
74% (
a
only)
OAc
MeO
(continued on next page)
3i
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4
P. Chen, J. Su / Tetrahedron xxx (2015) 1e11
Table 3 (continued )
c
Entry
Nucleophile (2)
Reaction time
Product (3)
Yieldb/(
a:b)
OAc
O
SH
10
25 min
86% (a only)
S
OAc
3j
OAc
O
S
O
O
N
H
S
NH
2
11
12
13
30 min
20 min
50 min
74% (93:7)
72% (93:7)
71% (90:10)
O
O
OAc
3k
OAc
O
O
S
O
S
N
Cl
NH
2
H
O
O
OAc
Cl
3l
OAc
O
O
S
O
N
CH2Ph
H
S
NH
O
2
OAc
O
3m
OAc
O
S
O
O
S
N
H
CH3
CH3
OBn
O
14
20 min
84% (95:5)
H C
NH
2
O
3
OAc
O
3n
OAc
O
O
S
O
S
N
15
16
H C
NH CH
20 min
76% (
a
only)
only)
3
3
MeO
OAc
O
3o
OAc
O
O
O
N
C
90 min
72% (a
H
O
C NH2
OAc
3p
OAc
O
O
N
O
17
5 h
71% (a only)
O
HN
OAc
3q
OAc
O
TMS
18
40 min
88% (a only)
OAc
3r
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P. Chen, J. Su / Tetrahedron xxx (2015) 1e11
5
Table 3 (continued )
c
Entry
Nucleophile (2)
Reaction time
Product (3)
Yieldb/(
a:b)
OAc
O
O
19
20
20 min
90 min
81% (
a
a
only)
only)
O
TMS
OAc
3s
OAc
O
TMSCN
85% (
CN
OAc
3t
a
General reaction conditions: tri-O-acetyl-D
-glucal (1) (190 mg, 0.7 mmol), nucleophile (2) (1.0 equiv), Gd(OTf)3 (10 mol %), MeCN (5 mL), 40 ꢀC.
b
c
Isolated yield.
The anomeric ratio was determined by integration of the anomeric hydrogen in the 1H NMR spectra.
Table 4
Gd(OTf)3 catalyzed synthesis of 2,3-unsaturated glycosides by Ferrier Rearrangement of 3,4-di-O-acetyl-
L
-rhamnal (4) with nucleophiles (2)a
AcO
Me
AcO
Me
O
O
Gd(OTf) /MeCN
3
Nu
Nucleophile
+
o
40 C
OAc
4
2
5
c
Entry
1
Nucleophile (2)
Reaction time
Product (5)
Yieldb/(
a:b)
AcO
Me
O
O
OH
Ph
30 min
20 min
85% (
a
a
only)
only)
5a
AcO
Me
O
SH
O
S
2
3
4
71% (
5b
AcO
Me
O
O
NH
O
S
Me
S
NH2
30 min
20 min
20 min
87% (
a
a
only)
only)
O
O
H3C
5c
AcO
Me O
O
S
N
S
Me
Me
H C
NH CH
77% (
O
3
3
O
5d
5
O
65% (97:3)
AcO
Me
O
O
TMS
5e
a
General reaction conditions: 3,4-di-O-acetyl-L
-rhamnal (4) (150 mg, 0.7 mmol), nucleophile (2) (1.0 equiv), Gd(OTf)3 (10 mol %), MeCN (5 mL), 40 ꢀC.
b
c
Isolated yield.
The anomeric ratio was determined by integration of the anomeric hydrogen in the 1H NMR spectra.
J¼7.1 Hz, 3H) ppm; IR (film, cmꢂ1): 2923, 2843, 1740, 1623, 1458,
1371, 1335, 1039, 979, 902; MS(ESI) m/z: 276.1 ([MþNH4]þ,100).
1H), 4.31e4.24 (m, 1H), 4.21e4.12 (m, 2H), 2.13 (s, 3H), 2.11 (s, 3H)
ppm; IR (film, cmꢂ1): 3030, 2931,1738,1605,1488,1355,1232,1040,
907; MS(ESI) m/z: 338.2 ([MþNH4]þ, 100).
4.2.2. Benzyl 4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-hex-2-
10
enopyranoside (3b). Colorless oil; [
a]
¼þ58.5 (c 1.26, CHCl3,
4.2.3. (þ)-endo-Fenacholyl 4,6-di-O-acetyl-2,3-dideoxy-
a-D-eryth-
D
25
a
only) {lit.:5x
(400 MHz, CDCl3)
[a
]
¼þ68.3 (c 1.02, CHCl3,
a:
b
¼9:1)}; 1H NMR
rohex-2-enopyranoside
(3c). White solid; mp¼75e76 ꢀC;
D
10
24
d
7.42e7.30 (m, 5H), 5.95e5.85 (m, 2H), 5.36 (d,
[a]
¼þ64.6 (c 1.12 CHCl3,
a
only) {lit.:5t
[a]
¼þ48.7 (c 0.5 CHCl3,
D
D
J¼9.4 Hz, 1H), 5.16 (s, 1H), 4.83 (d, J¼11.7 Hz, 1H), 4.63 (d, J¼11.7 Hz,
a
only)}; 1H NMR (400 MHz, CDCl3)
d
5.87 (s, 2H), 5.30 (d, J¼9.5 Hz,
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6
P. Chen, J. Su / Tetrahedron xxx (2015) 1e11
Table 5
Gd(OTf)3 catalyzed synthesis of 2,3-unsaturated glucosides by Ferrier Rearrangement of 3,4,6-tri-O-benzyl-
D
-glucal (6) with nucleophiles (2)a
OBn
OBn
O
O
Gd(OTf)3/MeCN
OBn
Nu
+
Nucleophile
60oC
OBn
OBn
6
2
7
c
Entry
1
Nucleophile (2)
Reaction time
Product (7)
Yieldb/(
a:b)
OBn
O
O
OH
70 min
60 min
60 min
30 min
40 min
90 min
90 min
70% (a only)
OBn
7a
OBn
O
O
CH2Ph
OH
2
3
4
5
6
7
91% (88:12)
69% (93:7)
46% (92:8)
57% (96:4)
73% (80:20)
70% (85:15)
OBn
7b
OBn
O
S
CH2Ph
SH
OBn
7c
7d
7e
OBn
O
SH
S
OMe
OBn
MeO
OBn
O
SH
S
CF3
OBn
F C
3
OBn
O
O
O
S
N
H
S
OMe
NH
2
O
O
OBn
MeO
7f
OBn
O
O
S
O
S
N
H
CH
3
H C
NH
2
3
O
OBn
O
7g
OBn
O
MeO
O
S
N
S
CH
3
8
H C
NH CH
60 min
68% (a only)
3
3
O
OBn
O
7h
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P. Chen, J. Su / Tetrahedron xxx (2015) 1e11
7
Table 5 (continued )
c
Entry
Nucleophile (2)
Reaction time
Product (7)
Yieldb/(
a:b)
OBn
O
C
O
O
N
H
OBn
O
C NH2
9
5 h
66% (89:11)
OBn
7i
OBn
O
O
O
N
O
O
10
36 h
48% (
a
only)
HN
OBn
7j
OBn
O
TMS
11
25 min
68% (
a
only)
only)
OBn
O
7k
OBn
O
12
13
30 min
71% (a
O
TMS
OBn
7l
OBn
O
TMSCN
130 min
67% (80:20)
CN
OBn
7m
a
General reaction conditions: 2,4,6-tri-O-benzyl-D
-glucal (6) (292 mg, 0.7 mmol), nucleophile (2) (1.0 equiv), Gd(OTf)3 (10 mol %), MeCN (5 mL), 60 ꢀC.
b
c
Isolated yield.
The anomeric ratio was determined by integration of the anomeric hydrogen in the 1H NMR spectra.
1H), 5.00 (s, 1H), 4.29e4.22 (m, 1H), 4.19e4.12 (m, 2H), 3.47 (s, 1H),
2.10(s, 6H),1.79e1.63(m, 3H),1.53e1.36(m, 2H),1.13(s,3H),1.12e1.07
(m, 1H), 1.06 (s, 3H), 1.04e0.95 (m, 1H), 0.89 (s, 3H) ppm; IR (film,
cmꢂ1): 3036, 2927, 2853,1737,1443,1377,1045, 970, 908; MS(ESI) m/
z: 389.0 ([MþNa]þ, 100).
(s, 3H) ppm; IR (film, cmꢂ1): 2930, 1739, 1615, 1495, 1387, 1220,
1035, 970; MS (ESI) m/z: 359.0 ([MþNa]þ, 56).
4.2.6. 3-Formylphenyl 4,6-di-O-acetyl-2,3-dideoxy-1-O-a-D-erythro-
10
hex-2-enopyranoside (3f). White solid; mp¼72e74 ꢀC, [
a]
D
¼þ121.4
10
(c 0.93, CHCl3, a only), {lit.:7i
[a]
¼þ139.7 (c 0.85 CHCl3, a ¼40:1)};
:b
D
4.2.4. 6-O-(4,6-Di-O-acetyl-2,3-dideoxy-
enopyranosyl)-1,2:3,4-di-O-isopropylidene-
a
-
-
D
-erythreo-hex-2-
-galactopyranose
¼þ29.7 (c 1.12 CHCl3,
1H NMR (400 MHz, CDCl3)
d 10.01 (s, 1H), 7.64 (s, 1H), 7.59 (d,
a
D
J¼7.5 Hz, 1H), 7.50 (t, J¼7.8 Hz, 1H), 7.39 (d, J¼8.0 Hz, 1H), 6.06 (dd,
J¼23.0, 10.3 Hz, 2H), 5.78 (s, 1H), 5.42 (d, J¼9.3 Hz, 1H), 4.33e4.21
(m, 2H), 4.15 (d, J¼11.1 Hz, 1H), 2.14 (s, 3H), 1.98 (s, 3H) ppm; 13C
10
(3d). White solid; mp¼131e132 ꢀC; [
a]
D
25
a:
b
¼88:12) {lit.:4b
[
a
]
¼þ16.8 (c 1.0, CHCl3,
a
only)}; 1H NMR
D
(400 MHz, CDCl3)
d
5.88e5.79 (m, 2H), 5.50 (d, J¼5.0 Hz, 1H), 5.30
NMR (101 MHz, CDCl3) d 191.81,170.69,170.23,157.61,137.88,130.58,
(d, J¼9.7 Hz, 1H), 5.07 (s, 1H), 4.61e4.57 (m, 1H), 4.32e4.29 (m, 1H),
4.27e4.21 (m, 2H), 4.16e4.07 (m, 2H), 3.97 (d, J¼7.7 Hz, 1H), 3.85
(dd, J¼10.2, 6.3 Hz, 1H), 3.73 (dd, J¼10.2, 7.0 Hz, 1H), 2.08 (s, 3H),
2.06 (s, 3H), 1.51 (s, 3H), 1.42 (s, 3H), 1.32 (s, 3H), 1.31 (s, 3H) ppm; IR
(film, cmꢂ1):2920, 2850, 1744, 1637, 1430, 1374, 1237, 1161, 783, 729,
671; MS(ESI) m/z: 495.1 ([MþNa]þ, 100).
130.17, 126.55, 124.31, 123.40, 117.08, 92.98, 68.00, 64.94, 62.60,
20.97, 20.66; IR (film, cmꢂ1): 2927, 2838, 1737, 1624, 1477, 1365,
1230, 1035, 780, 739; MS(ESI) m/z: 357.1 ([MþNa]þ, 25). HR-ESI:
C
17H18NaO7 [MþNa]þ calcd 357.0945, found. 357.0942.
4.2.7. 2-Naphenyl 4,6-di-O-acetyl-2,3-dideoxy-1-O-a-D-erythro-hex-
10
2-enopyranoside (3g). White solid; mp¼72e74 ꢀC; [
a
]
¼þ136.4 (c
D
25
4.2.5. 4-Methoxyphenyl
4,6-di-O-acetyl-2,3-dideoxy-1-O-
a
-
D
-er-
1.13, CHCl3,
a:
b
¼89:11) {lit.:5o
[
a]
¼þ153.9 (c 1.01, CHCl3,
D
ythro-hex-2-enopyrano side (3e). White solid; mp¼77e78 ꢀC,
a
only)}; 1H NMR (400 MHz, CDCl3)
d
8.58 (s, 1H), 7.81 (d, J¼8.1 Hz,
10
[
a
a
]
¼þ115.7 (c 1.08, CHCl3,
a
only) {lit.: ¼ þ139.1 (c 0.66, CHCl3,
1H), 7.76e7.68 (m, 2H), 7.51 (t, J¼7.7 Hz, 1H), 7.37 (t, J¼7.4 Hz, 1H),
7.13 (d, J¼8.9 Hz, 1H), 6.34 (s, 1H), 6.02 (d, J¼10.3 Hz, 1H), 5.92 (d,
J¼10.3 Hz, 1H), 5.69 (d, J¼8.9 Hz, 1H), 4.43e4.35 (m, 2H), 4.17e4.09
(m, 1H), 2.19 (s, 3H), 2.17 (s, 3H) ppm; IR (film, cmꢂ1): 3095,1740,
D
only)}; 1H NMR (400 MHz, CDCl3)
d
7.07 (d, J¼8.9 Hz, 2H), 6.86 (d,
J¼8.9 Hz, 2H), 6.03 (s, 2H), 5.59 (s, 1H), 5.40 (d, J¼9.2 Hz, 1H),
4.34e4.26 (m, 2H), 4.23e4.15 (m, 1H), 3.80 (s, 3H), 2.14 (s, 3H), 2.05
Please cite this article in press as: Chen, P.; Su, J., Tetrahedron (2015), http://dx.doi.org/10.1016/j.tet.2015.11.002

8
P. Chen, J. Su / Tetrahedron xxx (2015) 1e11
1617, 1388, 1220, 1036, 820, 795; MS (ESI) m/z: 357.0 ([MþH]þ,
a
:
b
¼85:15, no rotation value reported}; 1H NMR (400 MHz, CDCl3)
100).
d
6.02 (d, J¼10.1 Hz, 1H), 5.92e5.86 (m, 1H), 5.64e5.50 (m 2H), 5.26
(dd, J¼9.1, 1.7 Hz, 1H), 4.29 (dd, J¼12.1, 2.4 Hz, 1H), 4.16 (dd, J¼12.0,
6.6 Hz, 1H), 4.02e3.95 (m, 1H), 3.16 (s, 3H), 2.13 (s, 3H), 2.09 (s, 3H)
ppm; IR (film, cmꢂ1): 3284, 2919, 2833, 1740, 1445, 1132, 1040, 946;
MS(ESI) m/z: 329.9 ([MþNa]þ, 100).
4.2.8. Phenyl 4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-1-thio-hex-2-
10
enopyranoside (3h). White solid; mp¼56e57 ꢀC; [
a]
¼þ144.2 (c
D
25
1.17, CHCl3,
a
only) {lit.:4b
[a
]
¼þ28.2 (c 1.0, CHCl3,
a:b
¼12:1)}; 1H
D
NMR (400 MHz, CDCl3)
d
7.57 (d, J¼6.2 Hz, 2H), 7.39e7.25 (m, 3H),
6.09 (d, J¼9.2 Hz, 1H), 5.89 (d, J¼9.9 Hz, 1H), 5.78 (s, 1H), 5.41 (d,
J¼7.8 Hz, 1H), 4.55e4.43 (m, 1H), 4.38e4.16 (m, 2H), 2.13 (s, 3H),
2.10 (s, 3H) ppm; IR (film, cmꢂ1): 2945, 2880, 1738, 1640, 1520,
1433, 1232, 1076, 904, 746, 712; MS(ESI) m/z: 345.0 ([MþNa]þ, 100).
4.2.15. 4,6-Di-O-acetyl-2,3-dideoxy-
enopyranosyl-N-methyl-methanesulfonamide (3o). Colorless oil;
a-D -erythro-hex-2-
only) {lit.:7i
only)}; 1H NMR (400 MHz, CDCl3)
[a]
¼þ66.9 (c 1.10, CHCl3,
10
10
[a
]
¼þ73.4 (c 1.03, CHCl3,
a
D
D
a
d
5.97 (dt, J¼10.3, 2.0 Hz, 1H),
5.81e5.78 (m, 1H), 5.72 (dt, J¼10.4, 1.9 Hz, 1H), 5.26e5.20 (m, 1H),
4.2.9. 4-Methoxylphenyl 4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-1-
4.23 (dd, J¼12.1, 2.4 Hz, 1H), 4.10 (dd, J¼12.1, 6.2 Hz, 1H), 3.87e3.80
thio-hex-2-enopyranoside (3i). White solid; mp¼75e76 ꢀC;
(m, 1H), 2.91 (s, 3H), 2.74 (s, 3H), 2.06 (s, 3H), 2.03 (s, 3H) ppm; 13
C
10
[
a]
¼þ183.4 (c 1.09, CHCl3,
a
only) {lit.:4i, no rotation value re-
NMR (101 MHz, CDCl3) d 170.53, 170.18, 131.22, 128.44, 82.76, 73.88,
D
ported,
a
only}; 1H NMR (400 MHz, CDCl3)
d
7.52 (d, J¼8.6 Hz, 2H),
64.38, 62.75, 38.29, 29.14, 20.90, 20.71; IR (film, cmꢂ1): 2979,
2865,1743,1626,1316,1123, 904; MS(ESI) m/z: 344.1 ([MþNa]þ,100);
HR-ESI: C12H19NNaO7S [MþNa]þ, calcd 344.0774, found. 344.0762.
6.88 (d, J¼8.6 Hz, 2H), 6.08 (d, J¼10.1 Hz, 1H), 5.87 (d, J¼10.2 Hz,
1H), 5.62 (s, 1H), 5.39 (d, J¼9.5 Hz, 1H), 4.57e4.47 (m, 1H),
4.33e4.23 (m, 2H), 3.83 (s, 3H), 2.14 (s, 6H) ppm; IR (film, cmꢂ1):
2932, 2844,1740, 1628,1520, 1452,1233, 1064, 965, 812; MS(ESI) m/
z: 375.1 ([MþNa]þ, 100).
4.2.16. 4,6-Di-O-acetyl-2,3-dideoxy-
enopyranosyl-benzylcarbamate (3p). Colorless oil; [
0.94, CHCl3,
NMR (400 MHz, CHCl3)
5.87e5.82 (m, 1H), 5.81e5.71 (m, 1H), 5.63 (s, 1H), 5.31 (dd, J¼9.0,
1.8 Hz,1H), 5.17 (s, 2H), 4.27 (dd, J¼12.1, 5.0 Hz,1H), 4.17 (dd, J¼12.1,
2.4 Hz, 1H), 3.94e3.87 (m, 1H), 2.10 (s, 3H), 2.08 (s, 3H) ppm; IR
(film, cmꢂ1): 3328, 2934, 2865, 1740, 1638, 1520, 1431, 1209, 890,
765, 712; MS(ESI) m/z: 386.0 ([MþNa]þ, 100).
a-D -erythro-hex-2-
10
a
]
D
¼þ45.6 (c
25
a
only) {lit.:9d
[
a]
¼þ52 (c 0.5, CHCl3),
a
:b
¼3:1}; 1H
D
4.2.10. 2-Naphenyl 4,6-di-O-acetyl-2,3-dideoxy-
a
-
D
-erythro-hex-2-
d
7.44e7.32 (m, 5H), 5.98 (d, J¼10.2 Hz, 1H),
eno-1-thio-
a
-
D
-pyranoside (3j). White solid; mp¼97e98 ꢀC;
10
[
a]
¼133.8 (c 1.14,CHCl3,
a
only) {lit.:4i no rotation value reported,
D
a:
b
¼9:1}; 1H NMR (400 MHz, CDCl3)
d 8.07 (s, 1H), 7.87e7.77 (m,
3H), 7.64 (d, J¼8.6 Hz, 1H), 7.56e7.45 (m, 2H), 6.17e6.10 (m, 1H),
5.92 (d, J¼10.0 Hz, 2H), 5.43 (dd, J¼9.5, 1.6 Hz, 1H), 4.60e4.50 (m,
1H), 4.39e4.24 (m, 2H), 2.15 (s, 3H), 2.06 (s, 3H) ppm; IR (film,
cmꢂ1): 2925, 1740, 1624, 1520, 1428, 1231, 1036, 823; MS(ESI) m/z:
395.0 ([MþNa]þ, 100).
4.2.17. 2-(4,6-Di-O-acetyl-2,3-dideoxy-a-D-erythro-hex-2-
enopyranosyl) oxazolidinone (3q). White solid; mp¼80e82 ꢀC;
10
10
[a
]
¼þ96.4 (c 1.03, CHCl3,
a
only) {lit.:7i
[
d
a
]
D
¼þ111.6 (c 1.17, CHCl3,
D
4.2.11. 4,6-Di-O-acetyl-2,3-dideoxy-
enopyranosyl-phenylsulfonamide (3k). Colorless oil; [
a
-
D
-erythro-hex-2-
a:
b
¼10:1)}; 1H NMR (400 MHz, CDCl3)
6.01 (d, J¼10.2 Hz, 1H),
10
a
]
D
¼þ43.5 (c
5.86 (s, 1H), 5.75 (d, J¼10.3 Hz,1H), 5.28 (d, J¼9.1 Hz,1H), 4.43e4.30
(m, 2H), 4.19 (d, J¼4.1 Hz, 2H), 3.95e3.88 (m, 1H), 3.65 (q, J¼8.6 Hz,
1H), 3.50e3.42 (m, 1H), 2.09 (s, 3H), 2.08 (s, 3H) ppm; 13C NMR
0.96, CHCl3,
a
:
b
¼93:7) {lit.:9b
a
:
b
¼5:1}; 1H NMR (400 MHz, CDCl3)
d
7.97 (d, J¼7.4 Hz, 2H), 7.63 (t, J¼7.4 Hz, 1H), 7.55 (t, J¼7.5 Hz, 2H),
5.96 (d, J¼10.2 Hz, 1H), 5.85 (d, J¼10.1 Hz, 1H), 5.74e5.63 (m, 2H),
5.29 (d, J¼8.1 Hz, 1H), 3.93 (dd, J¼12.2, 3.4 Hz, 1H), 3.55 (dt, J¼9.2,
3.2 Hz, 1H), 3.36 (dd, J¼12.2, 2.3 Hz, 1H), 2.06 (s, 3H), 2.04 (s, 3H)
ppm; IR (film, cmꢂ1): 3267, 2940, 1741, 1638, 1580,1450, 1371, 1161,
1030, 746, 710; MS(ESI) m/z:391.9 ([MþNa]þ, 100).
(101 MHz, CDCl3) d 170.80, 170.28, 157.59, 131.26, 128.01, 78.53,
74.04, 64.46, 62.97, 62.42, 39.63, 20.93, 20.81. IR (film, cmꢂ1): 2930,
2842, 1740, 1623, 1425,1324, 1231, 1040, 966, 825; MS(ESI) m/z:
322.1 ([MþNa]þ,100). HR-ESI: C13H17NNaO7 [MþNa]þ, calcd
322.0897, found. 322.0890.
4.2.12. 4,6-Di-O-acetyl-2,3-dideoxy-
a
-
D
-erythro-hex-2-
4.2.18. 3-(40,60-Di-O-acetyl-20,30-dideoxy-
a
-
D
-erythro-hex-20-eno-
10
enopyranosyl-40-chloro-phenylsulfonamide
(3l). Colorless
oil;
pyranosyl)-1-propene (3r). Colorless oil; [
a
]
¼þ97.5 (c 1.05, CHCl3,
D
10
26
[
a
]
¼þ47.8 (c 0.89, CHCl3,a
:
b
¼93:7) {lit.:5r no rotation value re-
a
only) lit.:7g
[
a]
¼þ66.2 (c 1.0, CHCl3,
a
only)}; 1H NMR (400 MHz,
D
D
ported,
a:
b
¼85:15}; 1H NMR (400 MHz, CDCl3)
d
7.90 (d, J¼8.5 Hz,
CDCl3) d 5.98e5.92 (m, 1H), 5.92e5.78 (m, 2H), 5.19e5.10 (m, 3H),
2H), 7.52 (d, J¼8.5 Hz, 2H), 5.95 (t, J¼10.2 Hz, 2H), 5.84 (d, J¼10.2 Hz,
1H), 5.64 (d, J¼8.4 Hz, 1H), 5.27 (d, J¼8.8 Hz, 1H), 3.96 (dd, J¼12.8,
4.3 Hz, 1H), 3.64e3.55 (m, 2H), 2.06 (s, 3H), 2.04 (s, 3H) ppm; IR
(film, cmꢂ1): 3325, 2938, 1739, 1590, 1427, 1340, 1208, 1124, 1034,
902, 789; MS(ESI) m/z: 426.0 ([MþNa]þ, 100).
4.33e4.28 (m, 1H), 4.25 (dd, J¼11.9, 6.6 Hz, 1H), 4.17 (dd, J¼11.9,
3.5 Hz, 1H), 3.98 (td, J¼6.5, 3.5 Hz, 1H), 2.53e2.44 (m, 1H),
2.39e2.30 (m, 1H), 2.11 (s, 6H) ppm; IR (film, cmꢂ1): 2931, 2843,
1738, 1630, 1332, 1220, 1040, 920, 831; MS(ESI) m/z: 277.0
([MþNa]þ, 100).
4.2.13. 4,6-Di-O-acetyl-2,3-dideoxy-
a
-
D
-erythro-hex-2-
4.2.19. 2-(40,60-Di-O-acetyl-20,30-dideoxy-
a
-
D
-erythro-hex-20-eno-
10
enopyranosyl-benzylsulfonamide (3m). White solid; mp¼137e138
pyranosyl)-acetophenone (3s). Colorless oil; [
a
]
¼þ78.6 (c 0.92,
D
10
10
23
ꢀC; [
0.96, CHCl3,
a
]
¼þ40.5 (c 1.04,CHCl3,
a
:
b
¼90:10) {lit.:7i
[
d
a
]
¼þ44.9 (c
CHCl3,
a
only) {lit.:9a
a:b
¼8:2, [
a]
D
¼þ35.7 (c 0.99, CHCl3) for
D
D
a:b
¼10:1)}; 1H NMR (400 MHz, CDCl3)
7.51e7.45 (m,
a
anomer, [
a]
¼þ111.3 (c 0.574, CHCl3) for
b
anomer}; 1H NMR
23
D
2H), 7.44e7.39 (m, 3H), 6.00 (dt, J¼10.2, 1.9 Hz, 1H), 5.87e5.82 (m,
1H), 5.60 (d, J¼7.7 Hz, 1H), 5.35 (d, J¼8.8 Hz, 1H), 5.26 (dd, J¼8.9,
1.8 Hz, 1H), 4.56 (d, J¼13.7 Hz, 1H), 4.36e4.28 (m, 2H), 4.23 (dd,
J¼12.1, 6.4 Hz,1H), 4.05e3.99 (m, 1H), 2.13 (s, 3H), 2.04 (s, 3H) ppm;
IR (film, cmꢂ1): 3310, 2938, 1739, 1590,1427, 1340, 1208, 1124, 1034,
902, 789; MS(ESI) m/z: 406.0 ([MþNa]þ, 100).
(400 MHz, CDCl3) d 8.00e7.95 (m, 2H), 7.63e7.57 (m, 1H), 7.52e7.46
(m, 2H), 6.11e6.06 (m, 1H), 588e5.83 (m, 1H), 5.18e5.13 (m, 1H),
4.98e4.91 (m, 1H), 4.25 (dd, J¼11.9, 6.6 Hz, 1H), 4.14 (dd, J¼11.9,
3.6 Hz, 1H), 4.00 (td, J¼6.4, 3.7 Hz, 1H), 3.48 (dd, J¼16.4, 7.1 Hz, 1H),
3.15 (dd, J¼16.4, 6.6 Hz, 1H), 2.10 (s, 3H), 2.03 (s, 3H) ppm; IR
(film,cmꢂ1): 2930, 2838, 1741, 1590, 1325, 1224, 1030, 865, 710;
MS(ESI) m/z: 355.0 ([MþNa]þ, 100).
4.2.14. 4,6-Di-O-acetyl-2,3-dideoxy-a-D -erythro-hex-2-
10
enopyranosyl-methanesulfonamide (3n). Colorless oil; [
a]
¼þ98.7
4.2.20. 4,6-Di-O-acetyl-2,3-dideoxy-a-D -erythro-hex-2-
enopyranosyl cyanide (3t). White solid; mp¼86e87 ꢀC;
D
25
(c 0.95, CHCl3,
a:b
¼95:5) {lit.:9e
[
a]
¼þ52 (c 0.5, CHCl3),
D
Please cite this article in press as: Chen, P.; Su, J., Tetrahedron (2015), http://dx.doi.org/10.1016/j.tet.2015.11.002

P. Chen, J. Su / Tetrahedron xxx (2015) 1e11
9
10
10
[
a
a
]
¼ꢂ15.6 (c 1.10, CHCl3, only) {lit.:7i
[a
]
¼ꢂ19.8 (c 0.98, CHCl3,
3.63e3.54 (m, 2H), 1.92e1.78 (m, 2H), 1.71e1.55 (m, 2H), 1.50e1.40
(m, 1H), 1.34e1.08 (m, 5H) ppm; IR (film, cmꢂ1): 3064, 2941, 2832,
1625, 1518, 1423, 1330, 1231, 1120, 836, 744; MS(ESI) m/z: 426.3
([MþNH4]þ, 100).
D
D
only)}; 1H NMR (400 MHz, CDCl3)
d
6.06 (dt, J¼10.2, 1.8 Hz, 1H),
5.92 (ddd, J¼10.2, 3.5, 1.9 Hz, 1H), 5.40e5.34 (m, 1H), 5.12e5.08 (m,
1H), 4.29 (d, J¼3.9 Hz, 2H), 4.10e4.04 (m, 1H), 2.15 (s, 3H), 2.14 (s,
3H) ppm; IR (film, cmꢂ1): 2935, 2840, 2212, 1741, 1565, 1350, 1221,
1032, 910, 721; MS(ESI) m/z: 261.9 ([MþNa]þ, 100).
4.2.27. Benzyl-4,6-di-O-benzyl-2,3-dideoxy-D-erythro-1-thio-hex-2-
10
enopyranoside (7b). Colorless oil; [
a
]
¼þ86.7 (c 1.28, CHCl3,
D
23
4.2.21. 30-Phenylpropyl
ythro-hex-2-enopyranoside (5a). Colorless oil; [
CHCl3,
only); 1H NMR (400 MHz, DMSO)
4-O-acetyl-6-deoxy-2,3-dideoxy-
a
-
D
-er-
a:b
¼88:12) {lit.:5v
[a
]
¼þ80.4 (c 1.4, CHCl3,
a:b
¼10:1)}; 1H NMR
D
10
a
]
¼ꢂ56.8 (c 0.95,
(400 MHz, CDCl3)
d
7.41e7.25 (m, 15H), 6.13 (d, J¼10.3 Hz, 1H), 5.83
D
a
d
7.31e7.25 (m, 2H),
(dt, J¼10.3, 2.3 Hz, 1H), 5.17 (s, 1H), 4.85 (d, J¼11.8 Hz, 1H), 4.69 (d,
J¼12.2 Hz, 1H), 4.66e4.61 (m, 2H), 4.55 (d, J¼12.2 Hz, 1H), 4.48 (d,
J¼11.5 Hz, 1H), 4.26e4.20 (m, 1H), 4.07e4.01 (m, 1H), 3.77 (dd,
J¼10.6, 4.1 Hz, 1H), 3.67 (dd, J¼10.6, 1.8 Hz, 1H) ppm; IR (film,
cmꢂ1): 2937, 1623, 1486, 1392, 1223, 1141, 1056, 809. MS(ESI) m/z:
434.2 ([MþNH4]þ, 100).
7.23e7.14 (m, 3H), 5.83 (q, J¼10.4 Hz, 2H), 4.96 (s, 1H), 4.92 (d,
J¼9.2 Hz, 1H), 3.88e3.79 (m, 1H), 3.69e3.61 (m, 1H), 3.49e3.40 (m,
1H), 2.70e2.57 (m, 2H), 2.06 (s, 3H), 1.87e1.78 (m, 2H), 1.12 (d,
J¼6.3 Hz, 3H) ppm; 13C NMR (101 MHz, DMSO)
d 170.53, 142.07,
129.33, 128.91, 128.76, 128.75, 126.20, 94.16, 70.61, 67.52, 64.79,
32.18, 31.49, 21.29, 18.23; IR (film, cmꢂ1): 2924, 1739, 1630, 1542,
1430, 1342, 1235, 1037, 923, 730; MS(ESI) m/z: 313.1 ([MþNa]þ,
100). HR-ESI: C17H22NaO4 [MþNa]þ, calcd 313.1410, found. 313.1417.
4.2.28. Benzyl 4,6-di-O-benzyl-2,3-dideoxy-a-D-erythro-hex-2-eno-
10
1-thio-
CHCl3,
a
-
D
-pyranoside (7c). Colorless oil;
[
a
d
]
D
¼þ76.5 (c 1.02,
a
:
b
¼93:7); 1H NMR (400 MHz, CDCl3)
7.44e7.23 (m, 15H),
4.2.22. Cyclohexanethiol
ythro-hex-2-enopyranoside (5b). Colorless oil; [
CHCl3,
(400 MHz, CDCl3)
5.61 (s, 1H), 5.12 (d, J¼9.0 Hz, 1H), 4.23e4.14 (m, 1H), 2.96e2.86 (m,
1H), 2.10 (s, 3H), 2.08e1.99 (m, 2H), 1.82e1.73 (m, 2H), 1.64e1.57
(m, 1H), 1.46e1.29 (m, 5H), 1.24 (d, J¼6.3 Hz, 3H) ppm; IR (film,
cmꢂ1): 2932, 1741, 1630, 1423, 1235, 1042, 924, 833; MS(ESI) m/z:
293.0 ([MþNa]þ, 100).
4-O-acetyl-6-deoxy-2,3-dideoxy-
a
-
D
-er-
6.00 (d, J¼10.2 Hz, 1H), 5.84e5.79 (m, 1H), 5.47 (s, 1H), 4.73e4.46
(m, 4H), 4.31e4.20 (m, 2H), 3.96 (d, J¼13.4 Hz, 1H), 3.83e3.76 (m,
2H), 3.66 (dd, J¼10.7, 1.6 Hz, 1H) ppm; 13C NMR (101 MHz, CDCl3)
10
a
]
¼ꢂ117.5 (c 1.08,
D
25
a
only) {lit.:5v
[
a]
¼ꢂ156.9 (c 1.0, CHCl3,
a
only)}; 1H NMR
D
d
5.91 (d, J¼10.1 Hz, 1H), 5.74 (d, J¼10.1 Hz, 1H),
d 138.49, 138.24, 138.08, 129.04, 128.78, 128.49, 128.41, 128.39,
127.91, 127.89, 127.79, 127.66, 127.44, 126.93, 79.28, 73.37, 71.14,
70.37, 69.26, 68.88, 35.68; IR (film, cmꢂ1): 3043, 2936, 2845, 1621,
1486, 1378, 1236, 1120, 1035, 912, 823, 755, 708; MS(ESI) m/z: 450.2
([MþNH4]þ, 100). HR-ESI: C27H29O3S [MþH]þ, calcd 433.1837,
found. 433.1840.
4.2.23. 4-Methylphenyl
4-O-acetyl-6-deoxy-2,3-dideoxy-
a
-
D
-er-
4.2.29. 40-Methoxylphenyl 4,6-di-O-benzyl-2,3-dideoxy-
a-D-erythro-
10
ythro-hex-2-enopyranoside (5c). Colorless oil; [
a
]
¼ꢂ118.6 (c 1.03,
1-thio-hex-2-enopyranoside (7d). White solid; mp¼46e48 ꢀC;
D
10
CHCl3,
a
only); {lit.:9c
a
:
b
¼9:1, no rotation value reported}. 1H NMR
[
d
a
]
¼þ117.6 (c 0.92, CHCl3,
a:
b
¼92:8); 1H NMR (400 MHz, CDCl3)
D
(400 MHz, CDCl3)
d
7.84 (d, J¼8.3 Hz, 2H), 7.33 (d, J¼8.1 Hz, 2H), 5.90
7.52 (d, J¼8.6 Hz, 2H), 7.40e7.30 (m, 10H), 6.77 (d, J¼8.7 Hz, 2H),
(d, J¼10.1 Hz, 1H), 5.83e5.78 (m, 1H), 5.66 (d, J¼9.1 Hz, 1H),
5.58e5.52 (m, 1H), 4.95e4.90 (m, 1H), 3.46e3.37 (m, 1H), 2.45 (s,
3H), 2.06 (s, 3H), 0.73 (d, J¼6.2 Hz, 3H) ppm; IR (film, cmꢂ1): 3324,
2931, 2837, 1742, 1640, 1431, 1355, 1228, 1030, 910, 824, 732;
MS(ESI) m/z: 343.1 ([MþNH4]þ, 100).
6.08e5.99 (m, 2H), 5.63 (s, 1H), 4.71e4.64 (m, 2H), 4.58e4.49 (m,
2H), 4.47e4.41 (m, 1H), 4.23 (d, J¼9.2 Hz, 1H), 3.85e3.81 (m, 2H),
3.79 (s, 3H) ppm; 13C NMR (101 MHz, CDCl3)
d 159.63, 138.26,
138.02, 135.02, 128.77, 128.46, 128.35, 127.93, 127.90, 127.86, 127.60,
127.56, 125.49, 114.40, 84.85, 73.35, 71.10, 70.50, 69.36, 69.31, 55.32;
IR (film, cmꢂ1): 2932, 2820, 1531, 1423, 1332, 1041, 945, 817;
MS(ESI) m/z: 466.2 ([MþNH4]þ, 100). HR-ESI: C27H32O4NS
[MþNH4]þ, calcd 466.2047, found. 466.2040.
4.2.24. 4-O-acetyl-6-deoxy-2,3-dideoxy-
enopyranosyl-N-methyl-methanesulfonamide (5d). Colorless oil;
a-D-erythro-hex-2-
10
[
d
a
]
¼ꢂ106.5 (c 1.17, CHCl3,
a
only); 1H NMR (400 MHz, CDCl3)
D
5.93 (d, J¼10.3 Hz,1H), 5.74 (s, 1H), 5.66 (d, J¼10.3 Hz, 1H), 5.00 (d,
4.2.30. 40-Trifluoromethoxylphenyl 4,6-di-O-benzyl-2,3-dideoxy-
a-D-
J¼7.1 Hz, 1H), 3.73e3.64 (m, 1H), 2.91 (s, 3H), 2.74 (s, 3H), 2.05 (s,
erythro-1-thio-hex-2-enopyranoside (7e). White solid; mp¼74e76
10
3H), 1.19 (d, J¼6.2 Hz, 3H) ppm; 13C NMR (101 MHz, CDCl3)
d
170.37,
ꢀC; [
CDCl3)
a
]
¼þ121.5 (c 0.98, CHCl3,
a
:
b
¼96:4); 1H NMR (400 MHz,
D
131.73, 128.34, 82.68, 71.99, 69.71, 38.32, 29.13, 20.98, 18.00; IR
(film, cmꢂ1): 3078, 2920, 2853, 1740, 1641, 1336, 1223, 1040, 915,
816; MS(ESI) m/z: 286.1 ([MþNa]þ, 100). HR-ESI: C10H17NNaO5S
[MþNa]þ, calcd 286.0720, found. 286.0714.
d
7.66 (d, J¼8.1 Hz, 2H), 7.48 (d, J¼8.2 Hz, 2H), 7.41e7.29 (m,
10H), 6.12 (d, J¼10.2 Hz, 1H), 6.00 (d, J¼10.2 Hz,1H), 5.88 (s, 1H), 4.66
(d, J¼12.5 Hz, 2H), 4.55e4.49 (m, 2H), 4.36e4.25 (m, 2H), 3.84e3.75
(m, 2H) ppm; 13C NMR (101 MHz, CDCl3)
d 137.98, 137.82, 130.44,
129.86, 128.49, 128.38, 127.96, 127.91, 127.75, 126.61, 125.58 (q,
4.2.25. 2-(40-O-acetyl-60-deoxy-20,30-dideoxy-
a
-
]
D
-erythro-hex-20-
¼ꢂ110.7 (c 1.09,
J¼4.0 Hz, 1C), 83.23, 73.36, 71.38, 70.15, 69.88, 68.91; 19F NMR
10
enopyranosyl) acetophenone (5e). Colorless oil; [
a
(377 MHz, CDCl3)
d
ꢂ62.56(s); IR (film, cmꢂ1): 2936, 2841,1623,1512,
D
10
CHCl3,
(400 MHz, CDCl3)
a
:
b
¼97:3) {lit.:7i[
a
]
¼ꢂ110.7 (c 1.09, CHCl3 a only)}; 1H NMR
1421, 1320, 1226, 1037, 915, 816; MS(ESI) m/z: 487.2 ([MþH]þ, 100).
D
d 8.01e7.97 (m, 2H), 7.63e7.57 (m, 1H), 7.53e7.46
HR-ESI: C27H26O3F3S [MþH]þ, calcd 487.1549, found 487.1541.
(m, 2H), 6.09 (ddd, J¼10.3, 2.1, 1.2 Hz, 1H), 5.85 (ddd, J¼10.4, 3.6,
2.0 Hz, 1H), 4.95e4.85 (m, 2H), 4.01e3.92 (m, 1H), 3.47 (dd, J¼16.5,
6.8 Hz,1H), 3.16 (dd, J¼16.5, 6.7 Hz,1H), 2.11 (s, 3H),1.27 (d, J¼6.6 Hz,
3H) ppm; IR (film, cmꢂ1):2933, 2842, 1738, 1645, 1564, 1437, 1346,
1230, 1125, 1041, 814, 725; MS(ESI) m/z: 292.2 ([MþNH4]þ, 24).
4.2.31. 4,6-Di-O-benzyl-2,3-dideoxy-a-D -erythro-hex-2-
enopyranosyl-40-methoxyl-phenylsulfonamide (7f). Colorless oil;
10
[
d
a
]
¼þ121.5 (c 1.12, CHCl3,
a:
b
¼80:20); 1H NMR (400 MHz, CDCl3)
D
7.85 (d, J¼8.9 Hz, 2H), 7.41e7.25 (m, 10H), 6.82 (d, J¼8.9 Hz, 2H),
6.11 (d, J¼10.2 Hz, 1H), 5.79e5.73 (m, 1H), 5.67e5.61 (m, 1H),
5.58e5.51 (m, 1H), 4.57 (d, J¼11.3 Hz, 1H), 4.51e4.35 (m, 3H), 4.19
(dd, J¼9.1, 1.7 Hz, 1H), 3.79 (s, 3H), 3.44 (dd, J¼10.7, 2.9 Hz, 1H), 3.30
(dt, J¼9.0, 2.3 Hz, 1H), 2.80 (dd, J¼10.7, 2.0 Hz, 1H) ppm; 13C NMR
4.2.26. Cyclohexyl-4,6-di-O-benzyl-2,3-dideoxy-D-erythro-1-thio-
10
hex-2-enopyranoside (7a). Colorless oil; [
a]
¼þ68.7 (c 1.06, CHCl3,
D
25
a
only) {lit.:5v
(400 MHz, DMSO)
[a
]
¼þ53.6 (c 1.0 CHCl3,
a:b
¼10:1)}; 1H NMR
D
d
7.38e7.24 (m, 10H), 6.09 (d, J¼10.3 Hz,1H), 5.74
(101 MHz, CDCl3) d 162.77, 138.07, 137.62, 133.54, 131.97, 130.97,
(d, J¼10.3 Hz, 1H), 5.11 (s, 1H), 4.65 (d, J¼11.7 Hz, 1H), 4.56e4.43 (m,
3H), 3.92 (d, J¼9.6 Hz,1H), 3.89e3.82 (m,1H), 3.66 (d, J¼9.7 Hz,1H),
129.63, 129.41, 128.46, 128.42, 127.99, 127.95, 127.74, 127.71, 125.51,
113.91, 79.39, 73.34, 71.83, 69.48, 69.26, 67.65, 55.59; IR (film,
Please cite this article in press as: Chen, P.; Su, J., Tetrahedron (2015), http://dx.doi.org/10.1016/j.tet.2015.11.002

10
P. Chen, J. Su / Tetrahedron xxx (2015) 1e11
cmꢂ1):3341, 3076, 2964, 1634, 1517, 1418, 1334, 1225, 1078, 934,
817; MS(ESI) m/z: 513.2 ([MþNH4]þ, 100). HR-ESI: C27H33N2O6S
[MþNH4]þ, calcd 513.2054, found. 513.2047.
128.33, 128.21, 127.96, 127.81, 127.77, 127.58, 125.86, 73.43, 72.15,
71.11, 69.85, 69.18, 69.16, 42.38; IR (film, cmꢂ1): 2925, 2852, 1731,
1524, 1413, 1332, 1210, 1128, 1058, 755, 687; MS(ESI) m/z: 446.2
([MþNH4]þ, 100). HR-ESI: C28H29O4 [MþH]þ, calcd 429.2066, found
429.2060.
4.2.32. 4,6-Di-O-benzyl-2,3-dideoxy-a-D-erythro-hex-2-
10
enopyranosyl-methanesulfonamide (7g). Colorless oil; [
a
]
¼þ94.6
D
25
(c 1.15, CHCl3,
a:b
¼85:15) {lit.:9d
[a]
¼þ54 (c 0.7, CHCl3,
a:b
¼3:1)};
4.2.38. 4,6-Di-O-benzyl-2,3-dideoxy-
a
-
D
10
-erythro-hex-2-enopyr-
D
1H NMR (400 MHz, CDCl3)
d
7.41e7.26 (m, 10H), 6.16 (dt, J¼10.2,
anosyl cyanide (7m). Colorless oil; [
a
]
¼þ72.8 (c 0.98, CHCl3,
D
25
1.7 Hz, 1H), 5.80 (ddd, J¼10.2, 3.0, 1.8 Hz, 1H), 5.58e5.53 (m, 1H),
5.39 (d, J¼9.2 Hz, 1H), 4.68e4.46 (m, 4H), 4.00e3.95 (m, 1H),
3.85e3.79 (m, 1H), 3.75 (dd, J¼10.3, 2.0 Hz, 1H), 3.64 (dd, J¼10.3,
6.2 Hz,1H), 3.06 (s, 3H) ppm; IR (film, cmꢂ1): 3289, 3035, 2921, 2857,
1372, 1233, 1020, 952, 724; MS(ESI) m/z: 421.2 ([MþNH4]þ, 100).
a:b
¼80:20) {lit.:5x
[
a
]
D
¼þ44.737 (c 3.8, CHCl3,
a:
b
¼60:40)}; 1H
NMR (400 MHz, CDCl3)
d
7.40e7.24 (m, 10H), 6.19 (d, J¼10.2 Hz, 1H),
5.83e5.77 (m, 1H), 5.10e5.04 (m, 1H), 4.64 (dd, J¼11.7, 6.7 Hz, 2H),
4.56e4.47 (m, 2H), 4.27 (dd, J¼8.9, 1.8 Hz, 1H), 3.88 (dt, J¼8.9,
2.7 Hz, 1H), 3.83e3.74 (m, 2H) ppm; IR (film, cmꢂ1): 3067, 2942,
2835, 2210, 1621, 1530, 1425, 1337, 1252, 1135, 1058, 945, 844, 753;
MS(ESI) m/z: 453.2 ([MþNH4]þ, 80).
4.2.33. 4,6-Di-O-benzyl-2,3-dideoxy-
a-D-erythro-hex-2-
enopyranosyl-N-methyl-methanesulfonamide (7h). Colorless oil;
10
[
d
a
]
¼þ68.6 (c 1.10, CHCl3,
a
only); 1H NMR (400 MHz, CDCl3)
D
Acknowledgements
7.41e7.29 (m, 10H), 6.21 (dt, J¼10.3,1.9 Hz,1H), 5.82e5.79 (m, 1H),
5.70 (dt, J¼10.3, 1.8 Hz, 1H), 4.67 (d, J¼11.5 Hz, 1H), 4.61e4.51 (m,
3H), 4.13e4.07 (m, 1H), 3.80e3.74 (m, 1H), 3.73e3.68 (m, 2H), 2.97
This work is financially supported by a grant of the National
Natural Science Foundation of China (NSFC, Grant No. 21272305).
(s, 3H), 2.81 (s, 3H) ppm; 13C NMR (101 MHz, CDCl3)
d 138.18,137.71,
132.57, 128.51, 128.41, 127.99, 127.96, 127.72, 127.59, 127.21, 83.01,
76.53, 73.26, 71.57, 69.56, 69.33, 38.36, 29.29. IR (film,cmꢂ1): 3056,
2931, 2846, 1513, 1382, 1217, 1040, 843, 722; MS(ESI) m/z: 440.2
([MþNa]þ, 100). HR-ESI: C22H27NNaO5S [MþNa]þ, calcd 440.1502,
found. 440.1502.
Supplementary data
Supplementary data (1H and 13C NMR spectra) associated with
this article can be found, in the online version, at http://dx.doi.org/
10.1016/j.tet.2015.11.002.
4.2.34. 4,6-Di-O-benzyl-2,3-dideoxy-a-D-erythro-hex-2-
References and notes
10
enopyranosyl-benzylcarbamate (7i). Colorless oil; [
a
]
a
¼þ104.5 (c
D
25
1.11, CHCl3,
a:b
¼89:11) {lit.:9d
[a]
¼þ29 (c 2.0, CHCl3,
:b
¼7:3)}; 1H
D
1. For recent examples, see (a) Durham, T. B.; Miller, M. J. Org. Lett. 2002, 4, 135; (b)
Williams, D. R.; Heidebrecht, R. W., Jr. J. Am. Chem. Soc. 2003, 125, 1843; (c)
Domon, D.; Fujiwara, K.; Ohtaniuchi, Y.; Takezawa, A.; Takeda, S.; Kawasaki, H.;
Murai, A.; Kawai, H.; Suzuki, T. Tetrahedron Lett. 2005, 46, 8279; (d) Panarese, J.
D.; Waters, S. P. Org. Lett. 2009, 11, 5086; (e) Rusin, A.; Zawisza-Puchalka, J.;
Kujawa, K.; Gogler-Piglowska, A.; Wietrzyk, J.; Switalska, M.; Glowala-Kosinska,
M.; Gruca, A.; Szeja, W.; Krawczyk, Z.; Grynkiewicz, G. Bioorg. Med. Chem. 2011,
19, 295.
NMR (400 MHz, CDCl3)
d
7.40e7.23 (m, 15H), 6.09 (dt, J¼10.1, 1.9 Hz,
1H), 5.76 (d, J¼9.4 Hz 1H), 5.71(d, J¼10.2 Hz 1H), 5.40e5.31 (m, 1H),
5.22e5.07 (m, 2H), 4.70e4.41 (m, 4H), 4.27e4.19 (m, 1H), 3.80e3.67
(m, 3H) ppm; IR (film, cmꢂ1): 3048, 2940, 2841, 1520, 1410, 1221,
1032, 942, 825, 732; MS(ESI) m/z: 477.2 ([MþNH4]þ, 100).
2. For example, see Bozell, J. J.; Tice, N. C.; Sanyal, N.; Thompson, D.; Kim, J.-M.;
Vidal, S. J. Org. Chem. 2008, 73, 8763.
4.2.35. 2-(4,6-Di-O-benzyl-2,3-dideoxy-a-D-erythro-hex-2-
enopyranosyl) oxazolidinone (7j). White solid; mp¼54e56 ꢀC;
3. (a) Ferrier, R. J. Top. Curr. Chem. 2001, 215, 153; (b) Ferrier, R. J. Org. React. 2003,
ꢀ
61, 174; (c) Ferrier, R. J.; Zubkov, O. A. Org. React. 2004, 62, 569; (d) Gomez, A. M.;
10
[
d
a
]
¼þ86.4 (c 0.96, CHCl3,
a
only); 1H NMR (400 MHz, CDCl3)
D
ꢀ
ꢀ
Lobo, F.; Uriel, C.; Cristobal Lopez, J. Eur. J. Org. Chem. 2013, 7221.
7.41e7.25 (m, 10H), 6.20 (d, J¼10.3 Hz, 1H), 5.85 (s, 1H), 5.68 (d,
4. For recent examples, see, (a) Agarwal, A.; Rani, S.; Vankar, Y. D. J. Org. Chem.
2004, 69, 6137; (b) Misra, A. K.; Tiwari, P.; Agnihotri, G. Synthesis 2005, 260; (c)
Tiwari, P.; Agnihotri, G.; Misra, A. K. Carbohydr. Res. 2005, 340, 749; (d) Yadav, J.
S.; Satyanarayana, M.; Balanarsaiah, E.; Raghavendra, S. Tetrahedron Lett. 2006,
47, 6095; (e) Gorityala, B. K.; Cai, S.; Lorpitthaya, R.; Ma, J.; Pasunooti, K. K.; Liu,
X.-W. Tetrahedron Lett. 2009, 50, 676; (f) Zhou, J.; Zhang, B.; Yang, G.; Chen, X.;
Wang, Q.; Wang, Z.; Zhang, J.; Tang, J. Synlett 2010, 893; (g) Chen, P.; Wang, S.
Tetrahedron 2013, 69, 583; (h) Zhang, J.; Zhang, B.; Zhou, J.; Chen, H.; Li, J.; Yang,
G.; Wang, Z.; Tang, J. J. Carbohydr. Chem. 2013, 32, 380; (i) Goutam Guchhait, G.;
Misra, A. K. Catal. Lett. 2011, 141, 925.
5. For recent examples, see (a) Yadav, J. S.; Subba Reddy, B. V.; Chand, P. K. Tet-
rahedron Lett. 2001, 42, 4057; (b) Swamy, N. R.; Venkateswarlu, Y. Synthesis
2002, 598; (c) Bettadaiah, B. K.; Srinivas, P. Tetrahedron Lett. 2003, 44, 7257; (d)
Kim, H.; Men, H.; Lee, C. J. Am. Chem. Soc. 2004, 126, 1336; (e) Swamy, N. R.;
Srinivasulu, M.; Reddy, T. S.; Goud, T. V.; Venkateswarlu, Y. J. Carbohydr. Chem.
2004, 23, 435; (f) Ghosh, R.; Chakraborty, A.; Maiti, S. ARKIVOC 2004, IV, 1; (g)
Babu, J. L.; Khare, A.; Vankar, Y. D. Molecules 2005, 10, 884; (h) Naik, P. U.; Nara,
J. S.; Harjani, J. R.; Salunkhe, M. M. J. Mol. Catal. A: Chem. 2005, 234, 35; (i)
Procopio, A.; Dalpozzo, R.; Nino, A. D.; Maiuolo, L.; Nardi, M.; Oliverio, M.;
Russo, B. Carbohydr. Res. 2007, 342, 2125; (j) Zhang, G.; Shi, L.; Liu, Q.; Wang, J.;
Li, L.; Liu, X. Tetrahedron 2007, 63, 9705; (k) Zhang, G.; Liu, Q. Synth. Commun.
2007, 37, 3485; (l) Tayama, E.; Otoyama, S.; Isaka, W. Chem. Commun. 2008,
4216; (m) Zhang, G.-S.; Liu, Q.-F.; Shi, L.; Wang, J.-X. Tetrahedron 2008, 64, 339;
(n) Rodriguez, O. M.; Colinas, P. A.; Bravo, R. D. Synlett 2009, 1154; (o) Gorityala,
B. K.; Lorpitthaya, R.; Bai, Y.; Liu, X.-W. Tetrahedron 2009, 65, 5844; (p) Nagaraj,
P.; Ramesh, N. G. Tetrahedron Lett. 2009, 50, 3970; (q) Balamurugan, R.; Kop-
polu, S. R. Tetrahedron 2009, 65, 8139; (r) Ding, F.; William, R.; Gorityala, B. K.;
Ma, J.; Wang, S.; Liu, X.-W. Tetrahedron Lett. 2010, 51, 3146; (s) Chen, P.-R.;
Wang, S.-S. Tetrahedron 2012, 68, 5356; (t) Chen, P.-R.; Lin, L. Tetrahedron 2013,
69, 4524; (u) Chen, P.-R.; Lin, L. Tetrahedron 2013, 69, 10045; (v) Chen, P.-R.; Li,
S. Tetrahedron Lett. 2014, 55, 5813; (w) Narasimha, G.; Srinivas, B.; Krishna, P. R.;
Kashyap, S. Synlett 2014, 523; (x) Srinivas, B.; Reddy, T. R.; Kashyap, S. Carbo-
hydr. Res. 2015, 406, 86; (y) Reddy, T. R.; Rao, D. S.; Kashyap, S. RSC Adv. 2015, 5,
28338; (z) Battina, S. K.; Reddy, T. R.; Palakodety Radha Krishna, P. R.; Kashyap,
S. Tetrahedron Lett. 2015, 56, 1798.
J¼10.3 Hz, 1H), 4.68e4.60 (m, 2H), 4.56e4.49 (m, 2H), 4.42e4.29
(m, 2H), 4.20 (d, J¼6.9 Hz, 1H), 3.83e3.73 (m, 3H), 3.71e3.63 (m,
1H), 3.50e3.42 (m, 1H) ppm; 13C NMR (101 MHz, CDCl3)
d 157.69,
138.20, 137.78, 132.66, 128.47, 128.36, 127.94, 127.81, 127.65, 126.57,
78.77, 76.99, 73.48, 71.70, 69.45, 68.91, 62.37, 39.78; IR (film, cmꢂ1):
2934, 2841, 1702, 1615, 1391, 1234, 1026, 840, 752; MS(ESI) m/z:
413.2 ([MþNH4]þ, 100). HR-ESI: C23H29O5N2 [MþNH4]þ, calcd 413.
2071, found. 413.2065.
4.2.36. 3-(40,60-Di-O-benzyl-20,30-dideoxy-
a
-
D
-erythro-hex-20-eno-
10
pyranosyl)-1-propene (7k). Colorless oil; [
a]
¼þ88.4 (c 0.92, CHCl3,
D
25
a
only) {lit.:5x
(400 MHz, CDCl3)
[
a
d
]
¼þ73.529 (c 3.4, CHCl3,
a
only)}; 1H NMR
D
7.39e7.24 (m,10H), 5.97e5.82 (m, 3H), 5.17e5.06
(m, 2H), 4.66e4.46 (m, 4H), 4.30e4.23 (m, 1H), 4.04e3.98 (m, 1H),
3.87e3.81 (m, 1H), 3.74e3.64 (m, 2H), 2.55e2.45 (m, 1H), 2.38e2.28
(m, 1H) ppm; IR (film, cmꢂ1): 3058, 2921, 2853, 1642, 1372, 1233,
1040, 912, 732; MS(ESI) m/z:373.0 ([MþNa]þ, 100).
4.2.37. 2-(40,60-Di-O-benzyl-20,30-dideoxy-
pyranosyl)-acetophenone (7l). Colorless oil; [
CHCl3,
only); 1H NMR (400 MHz, CDCl3)
a
-
D
-erythro-hex-20-eno-
10
a]
¼þ112.6 (c 0.97,
D
a
d
7.97 (d, J¼7.5 Hz, 2H),
7.62e7.56 (m, 1H), 7.52e7.44 (m, 2H), 7.36e7.27 (m, 10H), 6.00 (s,
2H), 4.94 (t, J¼6.8 Hz, 1H), 4.67e4.48 (m, 4H), 4.03 (d, J¼6.9 Hz, 1H),
3.91e3.85 (m, 1H), 3.73e3.61 (m, 2H), 3.51 (dd, J¼16.3, 6.6 Hz, 1H),
3.19 (dd, J¼16.3, 7.0 Hz, 1H) ppm; 13C NMR (101 MHz, CDCl3)
d
197.78, 138.18, 138.09, 136.99, 133.24, 131.08, 128.62, 128.41,
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P. Chen, J. Su / Tetrahedron xxx (2015) 1e11
11
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2000, 1450; (b) Takhi, M.; Abdel-Rahman, A. A.-H.; Schmidt, R. R. Synlett 2001,
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Reddy, Ch R.; Chandrashekar, G. Tetrahedron Lett. 2004, 45, 6481; (c) Abhishek
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Please cite this article in press as: Chen, P.; Su, J., Tetrahedron (2015), http://dx.doi.org/10.1016/j.tet.2015.11.002