Substituent effects in endocyclic cleavage-recyclization anomerization reaction of pyranosides

Article abstract of DOI:10.1016/j.tet.2011.09.059

Pyranosides with 2,3-trans carbamate or 2,3-trans carbonate groups are anomerized under mild acidic conditions via endocyclic cleavage reaction. In order to understand the nature of the anomerization reaction via the endocyclic cleavage-recyclization proc

Full text of DOI:10.1016/j.tet.2011.09.059

Tetrahedron 67 (2011) 9966e9974
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Substituent effects in endocyclic cleavageerecyclization anomerization reaction
of pyranosides
,
a
,
,d,
*
Shino Manabe a , Kazuyuki Ishii b, Hiroko Satoh c, Yukishige Ito a
*
a RIKEN, Advanced Science Institute, Hirosawa Wako, Saitama 351-0198, Japan
b PRESTO, Japan Science and Technology Agency (JST), Kawaguchi, Saitama 332-1102, Japan
c National Institute of Informatics (NII), Chiyoda-ku, Tokyo 101-8430, Japan
d ERATO, Hirosawa Wako, Saitama 351-0198, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 1 August 2011
Received in revised form 14 September 2011
Accepted 15 September 2011
Available online 1 October 2011
Pyranosides with 2,3-trans carbamate or 2,3-trans carbonate groups are anomerized under mild acidic
conditions via endocyclic cleavage reaction. In order to understand the nature of the anomerization
reaction via the endocyclic cleavageerecyclization process, the substituent effects at various positions
were investigated.
Ó 2011 Elsevier Ltd. All rights reserved.
Keywords:
Anomerization
Carbohydrate
Endocyclic cleavage
Substituent effect
1. Introduction
a conformational change of the pyranoside ring is possible.1d,5 For
the
cannot depart easily because of lack of overlap with the electron
orbital of the ring oxygen. It is also discussed that the -pyranosides
b
-pyranosides in a 4C1 chair form, the exocyclic leaving group
The reaction mechanism of acetal hydrolysis with its stereo-
electronic aspects has received much attention as a fundamental
issue in organic chemistry.1 Since glycosides are acetals existing in
living systems, the issue on glycosidic cleavage is also important in
carbohydrate chemistry, biochemistry, and biotechnology. Since
pyranosides are asymmetric acetals, there are two possibilities for
their mode of CeO bond cleavage.2 One is exocyclic cleavage, where
the bond between the anomeric carbon and the exocyclic oxygen
breaks giving a cyclic oxocarbenium ion (Scheme 1, path A). The
cyclic oxocarbenium ion is assumed to be an important in-
termediate in glycosylation reactions, and a key species in carbo-
hydrate science.3 The other cleavage pattern is endocyclic cleavage,
where the bond between the ring oxygen and the anomeric carbon
is cleaved giving a linear cation (Scheme 1, path B). The endocyclic
cleavage is less common in carbohydrate chemistry compared to
the exocyclic cleavage. The mechanistic details of regioselectivity
on the cleavage site of pyranosides are discussed extensively in the
context of the stereoelectronic theory.4 According to this theory, it
b
has to adopt twist boat or flattened chair conformations to be
cleaved in an endocyclic manner. Thus, investigations into the
cleavage patterns of pyranosides will be interesting not only to
carbohydrate chemists but also to theoretical chemists studying
stereoelectronic issues.
Scheme 1. Endocyclic cleavage versus exocyclic cleavage reactions.
Haworth reported as early as 1941 that 3,6-anhydro-methyl
glucosides were hydrolyzed in the endocyclic cleavage mode.6 Post
and Karplus suggested the possibility of endocyclic cleavage in the
hydrolysis of an oligosaccharide in lysozyme with molecular dy-
namics simulations.7 These calculations were performed based on
the X-ray crystallographic studies of lysozyme with an oligosac-
charide substrate, wherein the conformation of N-acetylglucopyr-
anoside was restricted to a 4C1 chair form in the enzyme.8 Inspired
by the Post and Karplus hypothesis, several groups reported ex-
perimental evidence of conformationally locked sugar mimic
is explained that, for glucosides in a 4C1 chair form, the
preferentially proceed via an exocyclic pathway, whereas exocyclic
cleavage in the -anomers is energetically unfavorable unless
a-anomers
b
* Corresponding authors. Tel.: þ81 48 467 9432; fax: þ81 48 462 4680; e-mail
address: smanabe@riken.jp (S. Manabe).
0040-4020/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2011.09.059

S. Manabe et al. / Tetrahedron 67 (2011) 9966e9974
9967
compounds by capturing the cation generated in an endocyclic
cleavage mode. For example, Franck succeeded in capturing the
cation generated via endocyclic cleavage by an intramolecular aza-
with 2,3-trans cyclic protecting group, inner strain caused by the
fused rings distorting one ring by the force from the other is the
primary factor enhancing the endocleavage reaction.20b The effect
of the cyclic protecting group in restricting the pyranoside ring to
a 4C1 conformation is estimated to be a secondary factor.
In order to obtain further information aimed at the development
of this endocyclic cleavage reaction for synthetic utility, we in-
vestigated substituent effects at the anomeric center, the
5-position, and the 2-position in the anomerization reaction.
DielseAlder reaction during alkyl b
-acetal methanolysis.9 Fraser-
Reid demonstrated the presence of linear acetylium ions in acetic
acid during acetolysis in the presence of ferric chloride.10 Anslyn
used a pseudosymmetric deuterium scrambling test to show that
only a b-alkyl acetal locked in a cis-decalin type conformation un-
derwent endocyclic cleavage in MeOH, with a 30% maximum
ratio.11 Deslongchamps and Dory investigated reaction pathways of
the enzyme-catalyzed hydrolysis of glycosides based on quantum-
mechanical calculations as well as experimental studies, showing
endocyclic cleavage reactions.12 Recently, systematic analyses on
endocleavage of 6,1-anhydroglucopyranuronic acid were reported
by Murphy.13
2. Results and discussion
Reductive cleavage reaction of the benzylidene acetal group of
a pyranoside with a 2,3-trans carbamate group 1a was first carried
out. When the reaction was performed at 0 ꢀC for 30 min, ano-
During the development of a glycosyl donor for the 1,2-cis gly-
merized
in 14% and 72% yields, respectively (entry 1, Table 1). No pyranose
ring-opened diol 4a was observed. After 6 h, -glycoside 3a was
not obtained. Instead, -glycoside 2a (53%) and pyranoside-
opened alcohol 4a (11%) were obtained (entry 2). At room tem-
a-thioglycoside 2a and b-thioglycoside 3a were obtained
cosylation of 2-amino-2-deoxy sugar,14,15 we found that pyrano-
sides with
a 2,3-trans carbamate group were quite easily
b
anomerized under mild Lewis acidic conditions.16,17 Crich and
Oscarson also reported the same anomerization with 2,3-trans
carbamate-carrying pyranosides.18 We presented evidence that the
anomerization was caused by an endocyclic cleavage reaction and
subsequent recyclization of the pyranoside ring.19 The generated
linear cation was captured by intra- and inter-molecular Frie-
deleCrafts reactions, chloride addition, and reduction using Et3SiH
(Scheme 2). The anomerization reaction of pyranosides with 2,3-
trans carbamate occurs at lower temperatures and milder condi-
a
perature, both
(entry 3).
a- and b-glycosides were obtained within 30 min
When the N-substituent was replaced with an electron-
withdrawing o-nitrobenzyl group, the anomerization from the
b
-anomer to the
was obtained in 87% yield and only a trace amount of
2b was obtained at 0 ꢀC after 30 min (entry 4). Even when the
amount of BF3$OEt2 was increased to 4 equiv, the -glycoside was
increased only up to 3% yield (entry 5). Similar to the N-benzylated
substrate 1a, the yield of -glycoside 2b was increased when the
a
-anomer was suppressed. The
b
-thioglycoside 3b
a
-glycoside
tions compared to other reported examples. Even the
are anomerized to the
-anomers, although higher (0 ꢀC) temper-
ature is required. Complete anomerization from the - to the
a-anomers
a
b
b
a
a
-direction was observed in some cases.
reaction was carried out at room temperature (entries 6 and 7). The
α
β
Scheme 2. Experimental evidence of endocyclic cleavage reaction.
The endocyclic cleavage in this series of compounds was in-
electron-rich benzyl type NAP group21 enhanced the reduction
product. In the case of NAP-protected substrate 1c, only the ring
opened product 4c was obtained even at 0 ꢀC with 4 equiv of
BF3$OEt2 (entry 9) or at room temperature after 30 min (entry 10).
The non-substituted substrate 1d17a was submitted to the same
vestigated by density functional theory (DFT) calculations.20 Tran-
sition state (TS) search calculations demonstrated that pyranosides
carrying the cyclic protecting groups undergo endocyclic cleavage-
induced anomerization reaction more easily than typical pyr-
anosides.20a Further investigation concluded that, for glycosides
standard reaction conditions as entry 1, but only the
b-anomer

9968
S. Manabe et al. / Tetrahedron 67 (2011) 9966e9974
Table 1
Substituent effect on nitrogen of the carbamate group in endocyclic cleavage
Et3SiH (12 equiv.)
BF3 OEt2
BnO
BnO
BnO
Ph
O
CH2Cl2
O
O
HO
O
O
OH
NR
HO
HO
SPh
+
SPh
+
O
SPh
SPh
O
O
O
O
N
R
NR
NR
O
O
O
1
2
3
4
Entry
R
BF3$OEt2 (equiv)
Temp (ꢀC)
Period (h)
Product
a
Yield (%)
a
Product
b
Yield (%)
b
Product alcohol
Yield alcohol (%)
1
2
3
4
5
6
7
8
1a
1a
1a
1b
1b
1b
1b
1c
1c
1c
1c
1d
Bn
Bn
Bn
2
2
2
2
4
2
2
2
4
2
2
2
0
0
rt
0
0.5
6
2a
2a
2a
2b
2b
2b
2b
2c
2c
2c
2c
2d
14
53
49
Trace
3
28
8
11
0
3a
3a
3a
3b
3b
3b
3b
3c
3c
3c
3c
3d
72
0
4a
4a
4a
4b
4b
4b
4b
4c
4c
4c
4c
4d
0
11
5
0
0
0
34
0
68
88
83
0
0.5
0.5
0.5
0.5
13
0.5
0.5
0.5
13
42
87
79
55
0
87
0
0
o-Nitrobenzyl
o-Nitrobenzyl
o-Nitrobenzyl
o-Nitrobenzyl
NAP
0
rt
rt
0
9
NAP
NAP
NAP
H
0
10
11
12
rt
rt
0
0
0
0
0
55
0.5
3d17a was obtained in 55% yield (entry 12). From the above results,
it was concluded that the N-substituent had a significant effect on
the degree of anomerization caused by endocyclic cleavage.
These results are explained as what follows: the cation gener-
ated by endocyclic cleavage under Lewis acidic conditions is cap-
tured by Et3SiH giving pyranoside ring opened alcohol 4 (Scheme 2).
It is clearly shown that the electron richness of the substituent on
the nitrogen of the carbamate group affects the endocyclic cleavage.
The electron-donating substituent increases the lifetime and pop-
ulation of the acyclic cation generated by endocyclic cleavage.
Next, the substituent effect at the sulfur of the thio group was
investigated in the same manner (Table 2). The reaction conditions
were chosen to be the same as in entry 1, Table 1. The 4-methox-
yphenyl thioglycoside derivative 5b more easily underwent
anomerization than 1a and 5a17i (entry 3). On the other hand,
thioglycoside 5c with the electron-withdrawing substituent
4-methoxycarbonyl phenyl did not anomerize under the same
conditions (entry 4). Similar to the substituent effect at the nitrogen
atom of the carbamate, electron density at the thio group also af-
fected the endocyclic cleavage reaction. The electronic properties at
the anomeric site are supposed to influence on the stability of the
acyclic cation, as well as on cyclic cation.
effect was observed for all of the Lewis acids, which worked as the
promoter for anomerization (entries 1e4, 7, and 8). Although FeCl3
has been known as a Lewis acid for anomerization of pyranosides,23
when FeCl3 was employed as a mediator for anomerization, the
yield of
a
-thioglycoside 1020a was reduced (entries 3 and 4). In
addition to 920a and 10, the chloride adduct of the endocyclic cation
11 was obtained in 34% yield in entry 3. Lewis acid Cu(OTf)2 was
recently reported as a useful Lewis acid for reductive benzylidene
ring opening reactions.24 However, in this reaction, Cu(OTf)2 did
not produce the a-anomer 10 in either CH2Cl2 or CH3CN. The strong
protic acid Tf2NH25 was also effective for anomerization, but the
yields of both anomers were low and the bis-trifluoroimide adduct
12 was obtained in 41% yield in CH2Cl2 (entry 7) and 40% yield in
CH3CN (entry 8). The possible discussion on the difference of the
reactivity is that the capability of the acid to the ring oxygen in
terms of acidity and steric hindrance factors.
Next, the effect at the 5-position on the anomerization reaction
was investigated. Substrates 14e16 were prepared from diol 13
(Scheme 3).19 Selective tosylation was carried out by TsCl in pyri-
dine and the tosylate was reduced by Bu3SnH under typical con-
ditions to generate the precursor to 14 in 85% yield. Subsequent
acetylation gave 6-deoxy compound 14. The selective trans-
Table 2
Substituent effect on the thio group in endocyclic cleavage
Et3SiH (12 equiv.)
BF3 OEt2 (2 equiv.)
BnO
BnO
BnO
Ph
O
CH2Cl2
O
O
N
Bn
2a, 6
O
O
OH
HO
HO
HO
R
+
+
R
R
O
O
0 °C, 0.5 h
O
O
O
NBn
NBn
NBn
R
O
O
O
1a, 5
3a, 7
4a, 8
Entry
R
Product
a
Yield (%)
a
Product
b
Yield (%)
b
Product alcohol
Yield (%) alcohol
1
2
3
4
1a
5a
5b
5c
SPh
STol
OMP
2a
6a
6b
6c
14
trace
25
3a
7a
7b
7c
72
66
37
65
4a
8a
8b
8c
0
14
15
0
4-SPhCO2Me
0
MP¼4-methoxyphenyl.
Next, the Lewis acid and protic acid effect in the endocyclic
cleavage reaction was investigated in CH2Cl2 and CH3CN (Table 3).
We previously reported that a CH3CN solvent enhances the
anomerization reaction.22 The same tendency about the solvent
formation of the primary alcohol of diol 13 to the sulfide was car-
ried out by the PhSSPheBu3P combination. Subsequent
methylation and acetylation gave compound 15 in 48% yield in
three steps. For 16, selective oxidation of the primary alcohol of 13

S. Manabe et al. / Tetrahedron 67 (2011) 9966e9974
9969
Table 3
Table 4
Lewis and protic acid effect in the anomerization reaction of pyranosides with 2,3-
Substitution effect at the 5-position on the anomerization reaction
trans carbamate
R
R
R
BF3 OEt2
-30 °C, 12 h
O
O
O
BnO
AcO
AcO
AcO
BnO
BnO
acid
SPh
SPh
+
O
O
O
O
O
O
AcO
AcO
AcO
-30 °C, 12 h
+
NBn
N
SPh
SPh
NBn
O
O
O
O
O
SPh
Bn
N
NBn
NBn
O
O
O
SPh
Bn
O
14-16,18
19-22
14-16,18
9
10
9
Entry
R
Solvent
Product
a
Yield
Product
b
Yield
(%) b
Entry
Lewis acid
Solvent
10 (%)
9 (%)
(%)
a
1
2
3
4
5
6
7
8
BF3ꢁOEt2
BF3ꢁOEt2
FeCl3
CH2Cl2
CH3CN
CH2Cl2
CH3CN
CH2Cl2
CH3CN
CH2Cl2
CH3CN
63
89
24
36
0
0
19
20
16
10
25
6
90
87
11
2
1
2
3
4
5
6
7
8
14
14
14
14
15
15
15
16
18
18
18
18
CH3
CH3
CH3
CH3
CH2SPh
CH2SPh
CH2SPh
CO2Me
CH2OAc
CH2OAc
CH2OAc
CH2OAc
CH3CN
CH2Cl2
Toluene
Et2O
CH2Cl2
Toluene
Et2O
CH2Cl2
CH3CN
CH2Cl2
Toluene
Et2O
19
19
19
19
20
20
20
21
22
22
22
22
69
88
32
<1
21
10
10
34
41
27
11
0
14
14
14
14
15
15
15
16
18
18
18
18
21
16
60
99
66
84
90
57
9
FeCl3
Cu(OTf)2
Cu(OTf)2
Tf2NH
Tf2NH
9a
10a
11a
12a
BnO
BnO
27
72
86
OH
OH
AcO
AcO
SPh
SPh
O
O
O
N
N
N
SO2CF3
Cl
Bn
11
a
O
Entries 9e12 are cited from Ref. 22 for comparison.
Bn
SO2CF3
12
a) 11 34%
b) 12 41%
c) 12 40%
Me
O
AcO
SPh
O
NBn
14
O
1) TsCl, pyridine
2) Bu3SnH, NaI, AIBN, DME
3) Ac2O, pyridine
1) PhSSPh
OH
SPh
O
PBu3
O
HO
AcO
SPh
SPh
toluene
O
O
NBn
NBn
2) Ac2O
pyridine
O
O
13
15
1) TEMPO, BAIB
CH2Cl2, H2O
2)TMSCHN2, MeOH, PhH
3) Ac2O, pyridine
O
H
R
MeO2C
AcO
MeO2C
AcO
O
O
HO
O
SPh
O
O
SPh
O
NBn
NBn
NBn
O
O
O
R = CH2OH or CO2Me
17
16
Scheme 3. Preparation of 5-position modified substrates.
was achieved by TEMPO-iodosobenzene diacetate in CH2Cl2/H2O.26
During the oxidation reaction, elimination of the sulfenyl group
occurred as a side reaction to give 17. The side reaction may have
occurred by sulfide oxidation and subsequent [2,3]-sigmatropic
rearrangement though the sulfoxide, although the intermediate
sulfoxide was not isolated.
14, the enhancement in CH3CN was not observed (entries 1e3). The
anomerization was slightly enhanced compared to the glucosamine
derivative 18. In Et2O, only a trace amount of anomerization
product was produced (entry 4). In the case of SPh-substituted
substrate 15, the anomerization tendency was reduced. These
phenomena are explained by the steric hindrance around O5 that
blocks the approach of the Lewis acids to O5 for the endocyclic
cleavage reaction.
Then, anomerization was then conducted with the prepared
compounds 14, 15, and 16 (Table 4). In the case of CH3-substituted

9970
S. Manabe et al. / Tetrahedron 67 (2011) 9966e9974
It is well known that aryl pyranosides are difficult to anomerize,
4. Experimental section
4.1. General
although the reason is not clear.1 In order to test the efficacy of 2,3-
trans carbamate and 2,3-trans carbonate groups for anomerization,
the anomerization reaction of aryl pyranosides with 2,3-trans car-
bamate and 2,3-trans carbonate groups was investigated. A re-
ported solvent effect for the anomerization reaction22 was
observed with thiophenyl glycoside 23 and O-methyl glycoside 24
(Table 5, entries 1e5). However, in the case of phenyl glycoside with
2,3-trans carbonate 25, no anomerization was observed in CH2Cl2
or CH3CN at ꢂ30 ꢀC after 12 h (entries 6 and 7), whereas at 0 ꢀC,
partial anomerization occurred in CH3CN (entry 8). More electron-
donating 4-methoxyphenyl glycosides 26e28 were also not ano-
1H and 13C NMR spectra were recorded at ambient temperature
(23e24 ꢀC) in CDCl3 using JEOL EX 400 MHz or JEOL JNM-ECP
500 MHz spectrometer. Chemical shifts are reported in parts per
million relative to internal tetramethylsilane (
d
¼0.00 ppm) for 1H
and CDCl3
(
d
¼77.00 ppm) for 13C NMR spectra. Optical rotations
were measured with a JASCO DIP-310 polarimeter. Melting points
(not corrected) were measured with a YANACO micro melting point
apparatus. Silica gel 60 N (spherical, neutral, Kanto Chemical Co.,
merized at ꢂ30 ꢀC (entries 9 and 10), but the
a
-anomer 32 was
Inc, Tokyo) was used for flash column (40e100
mm) and open col-
obtained in 56% yield at 0 ꢀC in the case of 2,3-trans carbonate
carrying pyranoside 26 (entry 11). Similarly, pyranosides with 2,3-
trans carbamates 27 and 28 were not anomerized at ꢂ30 ꢀC (entries
12 and 13). In these substrates and conditions, again, the anomeric
site considerably influences on the reactivity. These results suggest
that electronic properties at the anomeric site are essential to dis-
cuss the nature of the reactivity of anomerization.
umn (100e200 m) chromatography. Silica gel 60 F254 (E. Merck)
m
was used for analytical and preparative thin-layer chromatography.
4.2. Typical procedure for preparation of 1 and 5
4.2.1. Phenyl
bonyl-2-deoxy-1-thio-
N-benzyl-2-amino-4,6-O-benzylidene-2-N,3-O-car-
-glucopyranoside (1a)16,27. To an ice-cold
b-D
Table 5
Anomerization of aryl pyranosides with 2,3-trans carbamate and 2,3-trans carbonate group
BF3 OEt2
OBn
OBn
O
OBn
O
solvent
O
PO
PO
PO
-30 °C
+
X
X
O
O
O
Y
23-28
Y
23-28
Y
X
O
O
O
29-34
Entry
X
Y
P
Solvent
Temp (ꢀC)
Product
a
Yield (%)
a
Product
b
Yield (%) b
1a
2a
3a,b
4a,b
5a
6
7
8
9
10
11
12
13
23
23
24
24
24
25
25
25
26
26
26
27
28
SPh
SPh
O
O
O
O
O
O
O
O
O
O
O
NH
NBn
Ac
Ac
Ac
Ac
Ac
Ac
Ac
Ac
Bn
Bn
Bn
Ac
Ac
CH3CN
CH2Cl2
CH3CN
CH2Cl2
CH3CN
CH3CN
CH2Cl2
CH3CN
CH3CN
CH2Cl2
CH3CN
CH2Cl2
CH2Cl2
ꢂ30
ꢂ30
ꢂ30
ꢂ30
ꢂ30
ꢂ30
ꢂ30
0
29
29
30
30
30
31
31
31
32
32
32
33
34
62
46
71
33
86
0
0
23
0
23
23
24
24
24
25
25
25
26
26
26
27
28
10
14
5
47
0
96
90
77
71
75
33
98
94
OMe
OMe
OMe
OPh
OPh
OPh
OMP
OMP
OMP
OMP
OMP
ꢂ30
ꢂ30
0
0
56
0
ꢂ30
ꢂ30
0
MP¼4-methoxyphenyl.
a
Entries 9e12 are cited from Ref. 22 for comparison.
Reaction period 1.5 h.
b
3. Conclusion
mixture of phenyl N-trichloroethoxycarbonyl-2-amino-4,6-O-ben-
zylidene-2-deoxy-1-thio- -glucopyranoside (2.20 g, 4.11 mmol)
b-D
Here, we report the substituent effects at the nitrogen of the
carbamate group, at the 5-position of the pyranoside, and at the
anomeric position in the anomerization reaction via endocyclic
cleavage reaction. The present study suggests that electronic
properties of substituent at these sites, the acidity and the size of
the Lewis acid, and solvents influence the reactivity of the
anomerization reaction. These factors are supposed most likely to
contribute to increasing the inner strain and/or to stabilizing the
intermediate cation. The conformational distribution of the py-
ranoside ring is expected to be varied as the results of complex
interactions between these factors. The conformational properties
directly influence the stereoelectronic effect. Still, there is a possi-
bility that other factors influencing the reactivity of anomerization
exist. Further experimental and theoretical investigations on
propertyereactivity relationships will give better understanding of
the mechanistic details on the anomerization reaction. This
knowledge will enhance the synthetic utility of this endocyclic
cleavage-induced anomerization reaction.
and benzyl bromide (0.98 mL, 8.22 mmol) in DMF (40 mL) was
added NaH (0.2 g, 8.22 mmol). After stirring the mixture for 30 min
on the ice-water bath, the reaction mixture was warmed up to
room temperature and stirred for 30 min. The mixture was
quenched by addition of Et3N (1.5 mL), diluted with EtOAc, poured
into satd aqueous NH4Cl, and extracted with EtOAc. The combined
organic extracts were washed with water and brine, dried (Na2SO4),
filtered, and concentrated. The crystalline residue was crystallized
from EtOAc/hexane to give 1a (1.88 g, 96%) as a colorless crystal. 1H
NMR d: 7.47e7.26 (m, 15H, aromatic H), 5.59 (s, 1H, acetalePhCH),
4.85 (d, J1,2¼10.0 Hz, 1H, H-1), 4.83 and 4.78 (d, J¼15.5 Hz, 1H each,
NeCH2Ph), 4.32 (t, J2,3¼10.5 Hz, 1H, H-3), 4.32 (dd, J5,6a¼5.0 Hz,
J6a,6b¼10.5 Hz, 1H, H-6a), 4.04 (dd, J3,4¼10.0 Hz, J4,5¼8.5 Hz, 1H, H-
4), 3.90 (t, J5,6b¼10.0 Hz, 1H, H-6b), 3.57 (dddd, 1H, H-5), 3.52 (dd,
1H, H-2); 13C NMR
d 158.8 (oxazolidinone, C]O),136.4,136.3,132.6,
131.7, 129.3, 129.2, 128.7, 128.3, 128.0, 127.6 and 126.1 (aromatic C),
101.4 (acetaleCHPh), 87.7 (C-1), 78.9 (C-3), 78.4 (C-4), 72.8 (C-5),
68.2 (C-6), 61.5 (C-2), 47.7 (NeCH2Ph); mp 216e217 ꢀC; ½a D24
ꢂ72 (c
ꢃ

S. Manabe et al. / Tetrahedron 67 (2011) 9966e9974
9971
1.0, CHCl3); Anal. Calcd for C27H25NO5S: C, 68.19; H, 5.30; N, 2.95.
Found: C, 68.15; H, 5.17; N, 2.88.
4.3.1. Phenyl N-benzyl-2-amino-6-O-benzyl-2-N,3-O-carbonyl-2-
deoxy-1-thio- 7.50e7.24 (m,
-glucopyranoside (2a). 1H NMR
a-
D
d
15H, aromatic H), 5.37 (d, J¼4.5 Hz, 1H), 4.79 (d, J¼15.0 Hz, 1H
NeCH2Ph), 4.17 (d, J¼15.0 Hz, 1H), 4.60 (d, J¼12.0 Hz, 1H, CH2Ph),
4.50 (d, J¼12.0 Hz CH2Ph), 4.36 (dd, J¼12.0, J¼9.5 Hz, 1H), 4.14 (m, J
1H), 4.02 (ddd, J¼9.5, 9.5, 3.0 Hz, 1H), 3.78 (dd, J¼4.5, 10.5 Hz, 1H),
3.70 (dd, J¼10.5, 4.0 Hz, 1H), 3.50 (dd, J¼12.0, 4.5 Hz, 1H), 2.71 (d,
4.2.2. Phenyl N-o-nitrobenzyl-2-amino-4,6-O-benzylidene-2-N,3-O-
carbonyl-2-deoxy-1-thio-b-D d 8.10
-glucopyranoside (1b). 1H NMR
(d, J¼8.0 Hz, 1H), 7.59 (t, J¼7.2 Hz, 1H), 7.36e7.06 (m, 12H), 5.62 (s,
1H), 5.23 (d, J¼17.6 Hz, 1H), 5.00 (d, J¼17.6 Hz, 1H), 4.73 (d,
J¼10.0 Hz, 1H), 4.00 (t, J¼10.8 Hz, 1H), 4.35 (dd, J¼10.4, 4.8 Hz, 1H),
4.08 (t, J¼10.0 Hz, 1H), 3.92 (t, J¼10.0 Hz, 1H), 3.61 (m, 1H), 3.53 (t,
J¼3.0 Hz,1H); 13C NMR (125 MHz, CDCl3)
d 158.6, 137.5,134.4, 132.9,
131.9, 129.1, 129.0, 128.9, 128.5, 128.4, 127.9 and 127.7, 84.9, 78.4,
J¼10.0 Hz, 1H); 13C NMR
d
158.4, 147.9, 136.1, 133.6, 133.5, 132.1,
73.6, 73.0, 69.4, 68.7, 59.6, 47.8; mp 118e119 ꢀC; ½a D22
þ210 (c 1.0,
ꢃ
130.8, 129.2, 129.0, 128.6, 128.2, 128.0, 127.7, 126.0, 125.2, 101.4, 86.7,
CHCl3); Anal. Calcd for C27H27NO5S: C, 67.90; H, 5.70; N, 2.93.
Found: C, 67.96; H, 5.64; N, 2.85.
70.0, 78.2, 77.2, 72.8, 68.3, 62.4, 46.3; ½a Drt
ꢂ7.5 (c 0.40, CHCl3);
ꢃ
HRMS calcd for [C27H24N2O7SþNa]þ 543.1202, found 543.1175.
4.3.2. Phenyl N-benzyl-2-amino-6-O-benzyl-2-N,3-O-carbonyl-2-
4.2.3. Phenyl
bonyl-2-deoxy-1-thio-
N-naphtyl-2-amino-4,6-O-benzylidene-2-N,3-O-car-
-glucopyranoside (1c). 1H NMR
7.83e7.78
deoxy-1-thio-b-D d: 7.40e7.22 (m),
-glucopyranoside (3a). 1H NMR
b-D
d
4.77 (d, J¼9.0 Hz, 1H, H-1), 4.74 (s, 2H), 4.58 (d, J¼11.5 Hz, 1H), 4.55
(d, J¼11.5 Hz, 1H), 4.07 (t, J¼10.5 Hz, 1H), 4.01 (dddd, J¼10.5 Hz,
10.3, J¼8.0, 2.5 Hz, 1H), 3.79 (dd, J¼5.0 Hz, J¼10.0 Hz, 1H), 3.76 (dd,
J¼10.0, 5.0, 1H), 3.56 (m, 1H), 3.41 (dd, J¼10.5, 9.0 Hz, 1H, H-2),
(m, 4H), 7.50e7.15 (m, 5H), 7.25e7.15 (m, 8H), 5.57 (s, 1H), 4.98 (d,
J¼15.6 Hz, 1H), 4.92 (d, J¼15.6 Hz, 1H), 4.85 (d, J¼9.6 Hz, 1H), 4.35 (t,
J¼10.8 Hz, 1H), 4.29 (dd, J¼4.8, 10.4 Hz, 1H), 4.02 (t, J¼8.8 Hz, 1H),
3.86 (t, J¼10.4 Hz, 1H), 3.83e3.51 (m, 2H); 13C NMR
d
158.7, 136.2,
2.97 (d, J¼2.5 Hz, 1H, 4-OH); 13C NMR (125 MHz, CDCl3)
d 159.3,
133.6, 133.2, 132.7, 132.4, 131.5, 129.1, 129.0, 128.6, 128.5, 128.2, 127.7,
127.5, 126.9, 126.2, 126.0, 125.8, 101.4, 87.8, 79.0, 78.4, 72.8, 68.3, 61.6,
137.5, 136.2, 132.4, 132.3, 129.1, 128.6, 128.5, 128.4, 128.2, 127.9,
127.7 and 127.6, 86.7, 82.4, 79.6, 73.7, 69.7, 69.1, 60.1, 47.6; mp
48.0; ½a 2D4
ꢃ
ꢂ38.4 (c 0.5, CHCl3); HRMS calcd for [C31H27NO5SþNa]þ
125e126 ꢀC; ½a 2D2
ꢂ77 (c 1.0, CHCl3); Anal. Calcd for C27H27NO5S:
ꢃ
548.1508, found 548.1498.
C, 67.90; H, 5.70; N, 2.93. Found: C, 67.89; H, 5.56; N, 2.84.
4.2.4. Tolyl N-benzyl-2-amino-4,6-O-benzylidene-2-N,3-O-carbonyl-
4.3.3. Phenyl N-o-nitrobenzyl-2-amino-6-O-benzyl-2-N,3-O-carbonyl-
2-deoxy-1-thio-
b-D
-glucopyranoside (5a)17i
.
1H NMR
d
7.44e7.29
2-deoxy-1-thio-
a
-
D
-glucopyranoside (2b). 1H NMR
d
7.86 (d, J¼8.0 Hz,
(m, 10H), 7.15 (d, J¼8.0 Hz, 2H), 7.09 (d, J¼8.0 Hz, 2H), 5.57 (s, 1H),
4.84e4.74 (m, 3H), 4.32e4.27 (m, 2H), 4.01 (t, J¼8.4 Hz, 1H), 3.87 (t,
J¼10.4 Hz, 1H), 3.53 (m, 1H), 3.52 (d, J¼10.8 Hz, 1H), 3.48 (d,
1H), 7.61 (d, J¼7.6 Hz, 1H), 7.50 (t, J¼6.8 Hz, 1H), 7.35e7.15 (m, 11H),
5.34 (d, J¼4.4 Hz, 1H), 4.95 (d, J¼16.0 Hz, 1H), 4.58 (d, J¼16.0 Hz, 1H),
4.54 (d, J¼12.4 Hz, 1H), 4.45 (d, J¼12.0 Hz, 1H), 4.34 (t, J¼9.6 Hz, 1H),
4.08e4.02 (m, 2H), 3.78e3.64 (m, 3H), 2.85 (br s, 1H); 13C NMR
J¼10.8 Hz, 1H), 2.33 (s, 3H); 13C NMR
d 158.7, 139.0, 136.2, 133.0.
129.8, 129.1, 128.6, 128.1, 127.9, 127.7, 127.5, 125.9, 101.3, 88.0, 78.9,
d 158.7, 148.5, 137.3, 133.3, 132.3, 131.6, 131.3, 130.4, 128.9, 128.8,
78.4, 77.2, 72.8, 68.3, 61.6, 47.8, 21.3; ½a D24
ꢃ
ꢂ54.8 (c 1.22, CHCl3);
128.4, 127.8, 127.8, 127.6, 124.8, 85.1, 78.6, 73.7, 72.9, 69.8, 61.7, 45.0;
HRMS calcd for [C28H27NO5SþNa]þ 512.1502, found 512.1501.
½
a rDt
ꢃ
þ88.3 (c 0.5, CHCl3); HRMS calcd for [C27H26N2O7SþNa]þ
545.1353, found 545.1347.
4.2.5. 4-Methoxylphenyl N-benzyl-2-amino-4,6-O-benzylidene-2-N,
3-O-carbonyl-2-deoxy-1-thio-
b
-
D
-glucopyranoside (5b). 1H NMR
4.3.4. Phenyl
N-o-nitrobenzyl-2-amino-6-O-benzyl-2-N,3-O-car-
d
7.44e7.26 (m, 10H), 7.17 (d, J¼8.8 Hz, 2H), 6.78 (d, J¼8.8 Hz, 2H),
bonyl-2-deoxy-1-thio-b-D d 8.09 (d,
-glucopyranoside (3b). 1H NMR
5.56 (s, 1H), 4.84 (d, J¼15.6 Hz, 1H), 4.76 (d, J¼15.6 Hz, 1H), 4.69 (d,
J¼10.0 Hz, 1H), 4.31e4.26 (m, 2H), 4.00 (t, J¼8.8 Hz, 1H), 3.87 (t,
J¼8.0 Hz, 1H), 7.58e7.09 (m, 13H), 5.19 (d, J¼17.2 Hz, 1H), 4.92 (d,
J¼17. 2 Hz, 1H), 4.64 (d, J¼9.6 Hz, 1H), 4.60 (d, J¼12.0 Hz, 1H), 4.56
(d, J¼12.0 Hz, 1H), 4.18e4.07 (m, 2H), 3.85e3.75 (m, 2H), 3.59 (m,
J¼10.4 Hz, 1H), 3.79 (s, 3H), 3.49e3.44 (m, 2H); 13C NMR
d 160.4,
158.8, 136.4, 136.3, 135.5, 129.2, 128.6, 128.2, 127.9, 127.5, 126.0,
1H), 3.44 (t, J¼10.4 Hz, 1H); 13C NMR
d 159.0, 147.8, 137.4, 133.6,
121.5, 114.6, 101.3, 88.2, 78.9, 78.4, 72.7, 68.3, 61.6, 55.4, 47.8; ½a D24
ꢃ
133.5, 131.8, 131.4, 129.1, 128.9, 128.3, 128.2, 127.8, 127.8, 127.7, 127.6,
ꢂ60.5 (c 0.58, CHCl3); Anal. Calcd for C28H27NO6S: C, 66.52; H, 5.56;
125.0, 85.6, 82.6, 79.8, 73.7, 69.5, 68.6, 61.0, 46.0; ½a Drt
ꢃ ꢂ30.3 (c 0.57,
N, 2.85. Found C, 66.26; H, 5.56, N, 2.85.
CHCl3); HRMS calcd for [C27H26N2O7SþNa]þ 545.1358, found
545.1384.
4.2.6. 4-Methoxycarbonylphenyl N-benzyl-2-amino-4,6-O-benzyli-
dene-2-N,3-O-carbonyl-2-deoxy-1-thio-
b
-
D
-glucopyranoside
4.3.5. 5-[(1R,2R)-1,2-Dihydroxy-3-(phenylmethoxy)propyl]-3-(phe-
(5c). 1H NMR
d
7.92 (d, J¼8.4 Hz, 2H), 7.45e7.26 (m, 12H), 5.58 (s,
nylmethyl)-4-[(phenylthio)methyl]-2-oxazolidinone (4a). 1H NMR
1H), 4.93 (d, J¼9.6 Hz, 1H), 4.78 (d, J¼15.6 Hz, 1H), 4.73 (d,
J¼15.6 Hz, 1H), 4.37e4.30 (m, 2H), 4.05 (t, J¼8.8 Hz, 1H), 3.91 (s,
3H), 3.91e3.86 (m, 2H), 3.56 (m, 1H), 3.54 (t, J¼10.0 Hz, 1H); 13C
d 7.34e7.20 (m, 15H), 4.71e4.62 (m, 2H), 4.55 (s, 2H), 4.02 (s, 2H),
4.02 (d, J¼15.2 Hz, 1H), 3.85e3.80 (m, 2H), 3.70e3.69 (m, 2H), 3.52
(t, J¼8.0 Hz, 1H), 3.15 (d, J¼12.4 Hz, 1H), 2.89 (dd, J¼8.4, 14.4 Hz,
NMR
d
166.0, 158.5, 137.8, 136.1, 135.9, 130.6, 130.1, 129.7, 129.2,
1H), 2.56 (d, J¼8.4 Hz, 1H), 2.47 (d, J¼8.4 Hz, 1H); 13C NMR
d 157.4,
128.6, 128.2, 127.8, 127.6, 125.9, 101.4, 86.7, 78.6, 78.3, 73.0, 68.2,
137.3, 135.0, 134.1, 130.0, 129.1, 128.7, 128.4, 128.0, 127.9, 127.8, 127.7,
52.4, 47.9; ½a 2D4
ꢃ
ꢂ48.1 (c 0.59, CHCl3); Anal. Calcd for C29H27NO7S; C,
126.9, 77.6, 77.2, 73.6, 73.4, 71.3, 70.0, 55.5, 46.5, 36.3; ½a D24
ꢂ21.2 (c
ꢃ
65.28; H, 5.10; N, 2.62. Found C, 65.30; H, 5.21; N, 2.73.
0.5, CHCl3); HRMS calcd for [C27H29NO5SþNa]þ 502.1659, found
502.1670.
4.3. General procedure for anomerization reaction of 1 and 5
(Tables 1 and 2)
4.3.6. Tolyl N-benzyl-2-amino-6-O-benzyl-2-N,3-O-carbonyl-2-
deoxy-1-thio-a-D d 7.33e7.25 (m,
-glucopyranoside (6a). 1H NMR
To a solution of 1 or 5 (1 equiv) and Et3SiH (12 equiv) in CH2Cl2
(0.077 M), BF3$OEt2 (2 equiv) was added at 0 ꢀC or room temper-
ature. After certain reaction period, the reaction was quenched with
satd NaHCO3 and the mixture was extracted with EtOAc. The
combined layers were washed with brine and dried over Na2SO4.
After concentration, the residue was purified by preparative TLC.
12H), 7.09 (d, J¼8.0 Hz, 2H), 5.31 (d, J¼4.8 Hz, 1H), 4.79 (d,
J¼14.8 Hz, 1H), 4.59 (d, J¼12.0 Hz, 1H), 4.49 (d, J¼12.0 Hz, 1H), 4.35
(t, J¼12.0 Hz, 1H), 4.18e4.14 (m, 2H), 4.00 (t, J¼9.2 Hz, 1H), 3.77 (dd,
J¼10.0, 4.4 Hz, 1H), 3.70 (dd, J¼10.4, 3.6 Hz, 1H), 3.48 (dd, J¼10.4,
4.4 Hz,1H), 2.80 (br s,1H), 2.34 (s, 3H); 13C NMR
d 158.3,138.1,137.3,
134.3, 132.4, 129.8, 128.9, 128.8, 128.0, 128.4, 128.3, 127.8, 127.6,

9972
S. Manabe et al. / Tetrahedron 67 (2011) 9966e9974
85.3, 78.4, 77.2, 73.6, 72.9, 69.6, 68.8, 59.5, 47.8, 21.3; ½a D24
ꢃ
þ30.5
1H), 3.77 (dd, J¼10.4, 4.0 Hz, 1H); 13C NMR
d 170.0, 156.1, 137.0,
134.9, 131.2, 131.4, 129.8, 128.7, 128.5, 128.4, 128.0, 127.9, 127.9,
126.9, 126.5, 77.2, 76.8, 73.8, 72.0, 71.9, 69.1, 57.3, 50.7, 42.8, 21.2.
(c 1.0, CHCl3); HRMS calcd for [C28H29NO5SþNa]þ 502.1117, found
502.1113.
4.3.7. Tolyl N-benzyl-2-amino-6-O-benzyl-2-N,3-O-carbonyl-2-
4.4.2. Phenyl N-benzyl-2-amino-4-O-acetyl-2-N,3-O-carbonyl-2,6-
O-dideoxy-1-thio-b-D-glucopyranoside (14). To a solution of diol 13
deoxy-1-thio-
b
-D
-glucopyranoside (7a). 1H NMR
d
7.39e7.21 (m,
12H), 7.02 (d, J¼7.6 Hz, 1H), 4.73 (s, 2H), 4.69 (d, J¼9.2 Hz, 1H),
4.57 (d, J¼12.0 Hz, 1H), 4.53 (d, J¼12.0 Hz, 1H), 4.04 (t, J¼10.4 Hz,
1H), 3.98 (m, 1H), 3.76 (m, 2H), 3.52 (m, 1H), 3.37 (t, J¼10.8 Hz,
(1.83 g, 4.72 mmol) in pyridine (20 mL), TsCl (1.17 g, 6.14 mmol) was
added at 0 ꢀC. The mixture was stirred at room temperature over-
night. After evaporation of the solvent, the residue was partitioned
between EtOAc and satd NaHCO3. The aqueous layer was extracted
with EtOAc. The combined layers were washed with brine. After
drying the extract over Na2SO4, the solvent was evaporated. The
residue was purified by silica gel column chromatography to give
the 6-tosylate (2.03 g, 80%). To the suspension of tosylate (0.64 g,
1.18 mmol) and NaI (355 mg, 2.37 mmol) in DME (10 mL), Bu3SnH
(0.53 mL, 1.95 mmol) was added. Then, AIBN (20 mg) was added.
The mixture was refluxed for 4 h under N2 atmosphere. After
cooling the mixture to room temperature, aqueous 10% KF was
added. After filtration the mixture through Celite, the aqueous layer
was extracted with EtOAc. The combined layers were washed with
brine. After drying the mixture over Na2SO4, the solvent was
evaporated. The residue was dissolved in pyridine (10 mL) and Ac2O
(3 mL) was added. After 1 h, the mixture was concentrated. The
residue was purified by silica gel column chromatography (hexane/
EtOAc 7:3) to give the product 14 (0.40 g, 91%).
1H), 3.17 (br s, 1H), 2.31 (s, 3H); 13C NMR
d 159.1, 138.6, 137.3,
136.1, 132.8, 129.7, 128.5, 128.3, 128.3, 128.0, 127.3, 127.6, 127.4,
87.0, 82.4, 79.5, 77.2, 73.7, 69.8, 69.2, 60.2, 47.6, 21.3; ½a D24
ꢂ66.7
ꢃ
(c 0.81, CHCl3); HRMS calcd for [C28H29NO5SþNa]þ 514.1659,
found 514.1662.
4.3.8. 4-Methoxyphenyl
carbonyl-2-deoxy-1-thio-
N-benzyl-2-amino-6-O-benzyl-2-N,3-O-
-glucopyranoside (6b). 1H NMR
7.34e
a-D
d
7.25 (m, 12H), 6.78 (d, J¼8.4 Hz, 2H), 5.22 (d, J¼4.4 Hz, 1H), 4.78 (d,
J¼14.8 Hz, 1H), 4.58 (d, J¼11.6 Hz, 1H), 4.50 (d, J¼11.6 Hz, 1H), 4.37
(t, J¼11.2 Hz, 1H), 4.21e4.17 (m, 2H), 3.97 (m, 1H), 3.78 (s, 3H),
3.77e3.76 (m, 2H), 3.47 (dd, J¼11.6, 4.4 Hz, 1H), 3.04 (br s, 1H); 13C
NMR
d 159.8, 158.4, 137.4, 134.8, 134.4, 128.8, 128.3, 128.2, 127.7,
127.6, 122.6, 114.6, 85.7, 78.4, 77.2, 73.6, 72.9, 69.6, 68.9, 59.6, 55.4,
47.9; ½a 2D4
þ17.7 (c 0.90, CHCl3); Anal. Calcd for C28H29NO6S; C,
ꢃ
66.25; H, 5.76; N, 2.76. Found C, 66.31; H, 5.82; N, 2.89.
1H NMR
d
7.34e7.12 (m, 10H), 4.95 (t, J¼8.8 Hz, 1H), 4.69e4.67
4.3.9. 4-Methoxyphenyl
carbonyl-2-deoxy-1-thio-
N-benzyl-2-amino-6-O-benzyl-2-N,3-O-
-glucopyranoside NMR
(7b). 1H
(m, 3H), 4.06 (t, J¼10.8 Hz, 1H), 3.53 (m, 1H), 3.44 (t, J¼7.2 Hz, 1H),
b-
D
2.05 (s, 3H), 1.23 (d, J¼6.0 Hz, 3H); 13C NMR
d 169.2, 158.6, 135.8,
d
7.40e7.25 (m, 10H), 7.23 (d, J¼8.8 Hz, 2H), 6.73 (d, J¼8.8 Hz, 2H),
132.4, 131.9, 129.0, 128.9, 128.6, 128.4, 128.0, 127.5, 86.5, 80.0, 75.8,
4.77 (d, J¼15.6 Hz, 1H), 4.72 (d, J¼15.6 Hz, 1H), 4.62 (d, J¼9.2 Hz,
1H), 4.57 (d, J¼12.0 Hz, 1H), 4.54 (d, J¼12.0 Hz, 1H), 4.04 (t,
J¼10.4 Hz, 1H), 3.98 (m, 1H), 3.76 (s, 5H), 3.50 (m, 1H), 3.35 (t,
71.9, 60.1, 47.6, 20.9, 17.8; ½a D24
ꢂ54.5 (c 1.39, CHCl3); HRMS calcd for
ꢃ
[C22H23NO5þNa]þ 436.1189 found 436.1191.
J¼10.4 Hz, 1H), 3.06 (br s, 1H); 13C NMR
d
160.0, 159.1, 137.3,
4.4.3. Phenyl N-benzyl-2-amino-4-O-acetyl-2-N,3-O-carbonyl-2,6-
dideoxy-6-phenylthio-1-thio-b-D-glucopyranoside (15). To a solu-
126.2, 135.3, 128.5, 128.4, 128.0, 127.8, 127.6, 127.4, 122.0, 114.5,
87.3, 82.4, 70.3, 77.2, 73.7, 69.9, 69.3, 60.2, 55.4, 47.6; ½a D24
ꢃ
ꢂ68.7
tion of diol 13 (361.5 mg, 0.934 mmol) in toluene (5 mL), PBu3
(0.47 mmol, 1.88 mmol), and PhSSPh (408 mg, 1.88 mmol) were
added at room temperature. After overnight, the mixture was
evaporated and the residue was purified by silica gel column
chromatography (hexane/EtOAc 7:3) to give the sulfide (445 mg,
quant.). The sulfide (445 mg, 0.934 mmol) was dissolved in pyri-
dine (2 mL), and Ac2O (1 mL) was added. After stirring the mixture
for 2 h, the volatile materials were removed in vacuo. The residue
was purified by silica gel column chromatography (hexane/EtOAc
4:1) to give the product 15 (233 mg, 48%, two steps); 1H NMR
(c 1.21, CHCl3); HRMS calcd for [C28H29NO6SþNa]þ 530.1608,
found 530.1611.
4.3.10. 4-Methoxycarbonylphenyl N-benzyl-2-amino-6-O-benzyl-2-
N,3-O-carbonyl-2-deoxy-1-thio-b-D
-glucopyranoside (7c). 1H NMR
d
7.86 (d, J¼8.8 Hz, 2H), 7.36e7.24 (m, 12H), 4.85 (d, J¼9.6 Hz, 1H),
4.69 (s, 2H), 4.57 (d, J¼11.6 Hz, 1H), 4.53 (d, J¼11.6 Hz, 1H), 4.09 (t,
J¼10.0 Hz, 1H), 4.02 (m, 1H), 3.90 (s, 3H), 3.76 (d, J¼4.4 Hz, 2H), 3.60
(m, 1H), 3.43 (t, J¼10.8 Hz, 1H); 13C NMR
d 166.2, 159.0, 138.6, 135.8,
130.3, 130.0, 129.3, 128.6, 128.4, 128.0, 127.9, 127.6, 127.6, 85.6, 82.4,
d
7.40e7.18 (m, 15H), 5.20 (t, J¼8.8 Hz, 1H), 4.75 (s, 2H), 4.73 (d,
79.9, 77.2, 73.7, 69.5, 69.0, 60.1, 52.3, 47.7; ½a D24
ꢃ
ꢂ76.9 (c 0.42,
J¼10.0 Hz,1H), 4.10 (t, J¼10.8 Hz,1H), 3.64 (m,1H), 3.52 (t, J¼9.6 Hz,
1H), 3.15 (dd, J¼14.0, 2.8 Hz, 1H), 3.08 (dd, J¼14.0, 8.0 Hz, 1H), 2.03
CHCl3); Anal. Calcd for C29H29NO7S; C, 65.03; H, 5.46; N, 2.62. Found
C, 65.09; H, 5.50, N; 2.77.
(s, 3H); 13C NMR
d 169.1, 158.4, 153.7, 135.6, 132.7, 132.1, 131.8, 129.6,
129.5, 129.1, 128.9, 128.9, 128.8, 128.6, 128.5, 128.1, 127.6, 126.4, 87.1,
4.4. General procedure for anomeization of 9 with various
acids (Table 3)
79.7, 78.3, 70.3, 60.5, 60.4, 47.7, 36.1, 20.8; ½a D24
ꢃ
3.3 (c 0.90, CHCl3);
Anal. Calcd for C28H27NO5S2: C, 64.47, H, 5.22, N, 2.69. Found C,
64.33, H, 5.26, N, 2.63.
To a solution of 9 (1 equiv) in CH2Cl2 (0.077 M), an acid
(2 equiv) was added at ꢂ30 ꢀC. After 12 h, the reaction was
quenched with satd NaHCO3. The aqueous layer was extracted
with EtOAc. The combined layers were washed with brine and
dried over Na2SO4. After concentration, the residue was purified
by preparative TLC.
4.4.4. Phenyl N-benzyl-2-amino-4-O-acetyl-6-carbomethoxy-2-N,3-
O-carbonyl-2,6-dideoxy-1-thio-b-D-glucopyranoside (16). To a sus-
pension of diol 13 (0.60 g, 1.69 mmol) in CH2Cl2 (2.5 mL) and H2O
(0.5 mL), iodosobenzene diacetate (BAIB) (1.40 g, 4.23 mmol) and
TEMPO (100 mg, 0.64 mmol) was added at room temperature. After
30 min, the mixture was diluted with CHCl3 and 1 M HCl. The
aqueous layer was extracted with CHCl3. The combined layers were
washed with brine and dried over Na2SO4. After filtration, the
solvent was removed in vacuo. The residue was roughly purified by
silica gel column chromatography (CHCl3/EtOAc 4:1 to CHCl3/
MeOH 9:1). The residue was dissolved in PhH (5 mL) and MeOH
(5 mL), TMSCHN2 (4.0 M in hexane) was added until the color of
reaction mixture became yellow. After evaporation, the residue was
4.4.1. (1R)-1-((4R,5R)-3-Benzyl-2-oxo-4-((R)-phenylthio(1,1,1-
trifluoro-N-(trifluoromethylsulfonyl)methylsulfonamido)methyl)ox-
azolidin-5-yl)-3-(benzyloxy)-2-hydroxypropyl acetate (12). 1H NMR
d
7.34e7.08 (m, 14H), 6.99 (d, J¼7.6 Hz, 1H), 5.12 (dd, J¼5.2, 2.8 Hz,
1H), 5.02 (m, 1H), 4.59 (d, J¼11.6 Hz, 1H), 4.54 (d, J¼11.6 Hz, 1H),
4.28 (m, 1H), 4.24 (d, J¼2.8 Hz, 1H), 4.22 (d, J¼18.8 Hz, 1H), 4.10 (d,
J¼18.8 Hz, 1H), 3.96 (dd, J¼5.6, 2.4 Hz, 1H), 3.89 (dd, J¼10.4, 2.4 Hz,

S. Manabe et al. / Tetrahedron 67 (2011) 9966e9974
9973
dissolved in pyridine (5 mL) and Ac2O (3 mL) was added. After 1 h,
volatile material was evaporated. The crude was purified by pre-
parative TLC (toluene/EtOAc 4:1) to give product 16 (432 mg, 56%,
three steps) together with glycal 17 (170 mg, 26%, three steps) 1H
was suspended in CH2Cl2 (30 mL) and Et3SiH (6 mL) was added.
BF3$OEt2 (1.36 mL, 11.1 mmol) was added at 0 ꢀC. After 1 h, the re-
action was quenched with satd NaHCO3 and extracted with CHCl3.
The combined layers were washed with brine and concentrated.
The residue was dissolved in pyridine (10 mL) and Ac2O (5 mL) was
added. After stirring the mixture for 1 h, the volatile reagents were
evaporated in vacuo. The residue was purified by silica gel column
chromatography (CHCl3/EtOAc 4:1) to give the product 25 (1.89 mg,
46%, three steps).
NMR
d
7.32e7.22 (m, 10H), 5.42 (dd, J¼10.0, 6.4 Hz, 1H), 4.86 (d,
J¼9.6 Hz, 1H), 4.74 (d, J¼15.6 Hz, 1H), 4.59 (d, J¼15.6 Hz, 1H), 4.19 (t,
J¼11.6 Hz, 1H), 4.09 (m, 2H), 3.74 (s, 3H), 3.63 (m, 1H), 2.05 (s, 3H);
13C NMR
d 169.31, 169.41, 158.25, 135.93, 132.73, 131.50, 129.08,
128.68, 128.65, 127.94, 127.68, 87.45, 77.63, 69.42, 59.62, 53.08,
47.81, 20.56;
½
a 2D4
ꢃ
ꢂ136.0 (c 2.0, CHCl3); HRMS calcd for
1H NMR
d 7.25e7.24 (m, 7H), 7.07e7.03 (m, 3H), 5.40 (d,
[C23H23NO7SþNa]þ 480.1087, found 480.1096. glycal 17; 1H NMR
J¼7.2 Hz, 1H), 5.35 (t, J¼9.2 Hz, 1H), 4.52 (d, J¼11.6 Hz, 1H),
d
7.34e7.22 (m, 5H), 5.90 (d, J¼2.8 Hz, 1H), 5.33 (t, J¼9.6 Hz, 1H),
4.46e4.32 (m, 3H), 3.44 (m, 1H), 3.63 (m, 2H), 2.00 (s, 3H); 13C NMR
4.73 (d, J¼14.8 Hz,1H), 4.65 (t, J¼10.4 Hz,1H), 4.27 (d, J¼9.2 Hz,1H),
4.07 (d, J¼14.8 Hz, 1H), 4.06 (m, 1H), 3.68 (s, 3H), 3.55 (dd, J¼11.2,
d 169.0, 155.9, 152.6, 137.3, 129.6, 128.3, 127.8, 127.7,123.5, 117.1, 97.7,
79.5, 77.3, 73.6, 68.7, 68.4, 20.6; ½a D24
ꢂ64 (c 1.0, CHCl3); HRMS calcd
ꢃ
2.8 Hz, 1H), 2.06 (s, 3H), 13C NMR
d
168.85, 166.18, 157.14, 133.42,
for [C22H22O8þNa]þ 447.1207, found 437.1209.
129.16, 128.77, 128.65, 87.21, 72.82, 72.41, 68.12, 60.75, 53.29, 48.12,
20.59; ½a 2D4
ꢃ
þ15.0 (c 1.0, CHCl3).
4.5.5. Phenyl
4-O-acetyl-6-O-benzyl-2-O,3-O-carbonyl-
a
-
D
-gluco-
pyranoside (31). 1H NMR
d 7.33e7.26 (m, 7H), 7.12e7.08 (m, 3H),
4.5. General procedure for anomerization of 14e16 and 18
(Table 4)
5.86 (d, J¼2.8 Hz, 1H), 5.54 (t, J¼9.6 Hz, 1H), 4.99 (t, J¼11.2 Hz, 1H),
4.59 (d, J¼12.0 Hz, 1H), 4.44 (d, J¼12.0 Hz, 1H), 4.43 (t, J¼9.6 Hz,
1H), 3.97 (m, 1H), 3.61e3.52 (m, 2H); 13C NMR
d 169.6, 155.6, 152.6,
To a solution of
b
-anomer (1 equiv) in solvent (0.077 M), BF3$OEt2
137.1,129.7,128.3,127.8,127.8123.7,116.9, 93.5, 77.2, 76.6, 73.6, 72.0,
(2 equiv) was added at ꢂ30 ꢀC. After 12 h, the reactionwas quenched
with satd NaHCO3. The aqueous layer was extracted with EtOAc. The
combined layers were washed with brine and dried over Na2SO4.
After concentration, the residue was purified by preparative TLC.
68.2, 67.1, 20.7;
½
a 2D4
67.4 (c 0.65 CHCl3); HRMS calcd for
ꢃ
[C22H22O8þNa]þ 447.1207, found 447.1212.
4.5.6. 4-Methoxyphenyl 2-O,3-O-carbonyl-4,6-O-dibenzyl-b-D-glu-
copyranoside (26). To
a solution of 4-methoxyphenyl 4,6-O-
4.5.1. Phenyl N-benzyl-2-amino-4-O-acetyl-2-N,3-O-carbonyl-2,6-O-
dibenzyl-
b-D
-glucopyranoside29 (2.00 g, 4.29 mmol) in Et3N (2 mL)
dideoxy-1-thio-
a
-
D
-glucopyranoside (19). 1H NMR
d
7.41e7.21 (m,
and CH2Cl2 (20 mL), triphosgene (450 mg, 1.52 mol) was added in
some portion at ꢂ20 ꢀC. After 2 h, the reaction was quenched with
satd NaHCO3 and the aqueous layer was extracted with CHCl3. The
combined layers were washed with brine and dried over Na2SO4.
After concentration, the residue was purified by silica gel column
chromatography (CHCl3/EtOAc 4:1e1:1) to give the pyranoside
with 2,3-trans carbonate 26 (1.59 g, 75%).
10H), 5.31 (d, J¼4.8 Hz, 1H), 4.95 (t, J¼9.2 Hz, 1H), 4.80 (d,
J¼14.8 Hz, 1H), 4.39 (dd, J¼12.0, 10.4 Hz, 1H), 4.19 (m, 1H), 4.13 (d,
J¼14.8 Hz, 1H), 3.56 (dd, J¼12.0, 4.4 Hz, 1H), 2.11 (s, 3H), 13C NMR
d
169.2, 157.9, 134.0, 132.7, 131.6, 129.1, 128.9, 128.7, 128.3, 127.9,
84.6, 75.8, 72.9, 68.8, 60.1, 47.9, 20.9, 17.0; ½a D24
þ172.8 (c 1.13,
ꢃ
CHCl3); Anal. Calcd for C22H23NO5: C, 63.90, H, 5.61, N, 3.39. Found
C, 63.84, H, 5.62, N, 3.34.
1H NMR
d
7.34e7.25 (m, 10H), 7.02 (d, J¼8.8 Hz, 2H), 6.80 (d,
J¼8.8 Hz, 2H), 5.23 (d, J¼7.6 Hz, 1H), 4.80 (d, J¼11.2 Hz, 1H), 4.56 (t,
J¼12.8 Hz, 1H), 4.50 (d, J¼11.2 Hz, 1H), 4.37 (dd, J¼11.6, 8.8 Hz, 1H),
4.26 (dd, J¼11.2, 7.2 Hz, 1H), 4.02 (t, J¼9.2 Hz , 1H), 3.75 (s, 3H),
4.5.2. Phenyl N-benzyl-2-amino-4-O-acetyl-2-N,3-O-carbonyl-2,6-
dideoxy-6-phenylthio-1-thio-a-D
-glucopyranoside (20). 1H NMR
d
7.47e7.17 (m, 15H), 5.34 (d, J¼4.8 Hz, 1H), 5.16 (t, J¼9.2 Hz, 1H),
3.78e3.71 (m, 4H); 13C NMR
d 169.2, 158.5, 149.0,135.8,135.6, 132.8,
4.79 (d, J¼14.8 Hz, 1H), 4.37 (t, J¼10.0 Hz, 1H), 4.32 (m, 1H), 4.15 (d,
J¼15.8 Hz, 1H), 3.58 (dd, J¼12.0, 4.4 Hz, 1H), 3.16 (dd, J¼14.0, 2.8 Hz,
129.6, 129.0, 128.9, 128.6, 128.5, 128.1, 127.6, 126.5, 87.0, 79.7, 78.2,
70.2, 60.4, 47.6, 36.0, 20.7; ½a D24
ꢂ11.5 (c 0.92, CHCl3); HRMS calcd
ꢃ
1H), 3.09 (dd, J¼14. 0, 8.0 Hz, 1H), 2.08 (s, 3H); 13C NMR
d
169.0,
for [C28H28O8þNa]þ515.1676, found 515.1680.
157.8, 137.3, 134.4, 132.2, 129.0, 128.8, 128.7, 128.2, 128.2, 127.9,
127.7, 127.6, 85.8, 74.2, 73.5, 70.1, 68.3, 66.1, 56.1, 48.2, 20.8; ½a D24
ꢃ
4.5.7. 4-Methoxyphenyl-2-amino-4-O-acetyl 6-O-benzyl-2-N,3-O-
þ255.3 (c 1.0 CHCl3); Anal. Calcd for C28H27NO5S2: C, 64.47, H, 5.22,
carbonyl-2-deoxy-1-thio-
xyphenyl-2-amino-4,6-O-benzylidene-2-N,3-O-carbonyl-2-deoxy-
1-thio-
-glucopyranoside,30 27 was prepared by a similar pro-
cedure as 25.
1H NMR
b-D-glucopyranoside (27). From 4-metho-
N, 2.69. Found C, 64.11, H, 5.32, N, 2.63.
b-D
4.5.3. Phenyl N-benzyl-2-amino-4-O-acetyl-6-carbometoxy-2-N,3-
O-carbonyl-2,6-dideoxy-1-thio-
a-
D
-glucopyranoside (21). 1H NMR
d
7.30e7.26 (m, 5H), 6.99 (d, J¼9.2 Hz, 2H), 6.80 (d,
d
7.32e7.18 (m, 10H), 5.40 (d, J¼4.4 Hz, 1H), 5.30 (t, J¼9.2 Hz, 1H),
J¼9.2 Hz, 2H), 5.35 (dd, J¼10.0, 8.4 Hz, 1H), 5.24 (s, 1H), 5.09 (d,
J¼8.0 Hz, 1H), 4.55 (d, J¼12.0 Hz, 1H), 4.49 (d, J¼12.0 Hz, 1H), 4.24
(t, J¼12.0 Hz, 1H), 3.84e3.79 (m, 2H), 3.76 (s, 3H), 3.67e3.63 (m,
4.75 (d, J¼14.8 Hz,1H), 4.60 (d, J¼9.6 Hz,1H), 4.41 (t, J¼12.0 Hz,1H),
4.12 (d, J¼14.8 Hz, 1H), 3.67 (s, 3H), 3.61 (dd, J¼12.0, 4.8 Hz, 1H),
2.05 (s, 3H); 13C NMR
d
169.1, 167.2, 157.6, 131.8129.3, 129.2, 128.8,
2H); 2.02 (s, 3H); 13C NMR
d 169.1, 158.1, 155.6, 149.9, 137.4, 128.3,
128.7, 128.6, 128. 3, 85.5, 74.8, 70.8, 69.5, 59.5, 53.1, 48.0, 20.6.
127.7, 118.4, 114.6, 100.3, 79.2, 77.2, 76.7, 73.6, 68.8, 68.3, 59.2, 55.7,
20.8; ½a rDt
ꢃ
ꢂ50 (c 1.4, CHCl3); HRMS calcd for [C23H25NO8þNa]þ
4.5.4. Phenyl 4-O-acetyl-6-O-benzyl-2-O,3-O-carbonyl-4-
b-
D-gluco-
466.1478, found 466.1472.
pyranoside (25). To a solution of phenyl 4,6-O-benzylidene-
b-D-
glucopyranoside28 (3.44 g, 10.0 mmol) in Et3N (6 mL) and CH2Cl2
(20 mL), triphosgene (1.48 g, 5.00 mol) was added in some portion
at ꢂ20 ꢀC. After 2 h, the reaction was quenched with satd NaHCO3
and the aqueous layer was extracted with CHCl3. The combined
layers were washed with brine and dried over Na2SO4. After con-
centration, the residue was purified by silica gel column chroma-
tography (CHCl3/EtOAc 4:1e1:1) to give the pyranoside with 2,3-
trans carbonate. Then, the benzylidene product (2.05 g, 5.54 mmol)
4.5.8. 4-Methoxyphenyl-N-benzyl-2-amino-4-O-acetyl-6-O-benzyl-
2-N,3-O-carbonyl-2-deoxy-1-thio-b-D -glucopyranoside
(28). Compound 28 was prepared in a similar manner as 1a and 25
from 4-methoxyphenyl N-trichloroethoxycarbonyl-2-amino-4,6-
O-benzylidene-2-deoxy-
b-D-glucopyranoside.
1H NMR
d
7.41e7.22 (m, 10H), 6.86 (d, J¼8.8 Hz, 2H), 6.76 (d,
J¼8.8 Hz, 2H), 5.25 (dd, J¼10.0, 8.0 Hz, 1H), 5.09 (d, J¼7.2 Hz, 1H),
4.61 (d, J¼15.2 Hz, 1H), 4.51 (d, J¼10.8 Hz, 1H), 4.50e4.43 (m, 3H),

9974
S. Manabe et al. / Tetrahedron 67 (2011) 9966e9974
4. (a) Deslongchamps, P. Pure Appl. Chem. 1993, 65, 1161e1178; (b) Deslong-
champs, P. Stereoelectronic Effects in Organic Chemistry; Pergamon: Oxford,
1983; (c) Kirby, A. J. Stereoelectronic Effects; Oxford University: USA, 1996.
5. (a) Gorenstein, D. G.; Findlay, J. B.; Luxon, B. A.; Kar, D. J. Am. Chem. Soc. 1977, 99,
3473e3479; (b) Hosie, L.; Marshall, P. J.; Sinnott, M. L. J. Chem. Soc., Perkin Trans.
2 1984, 1121e1131.
6. Haworth, W. N.; Owen, L. N.; Smith, F. J. Chem. Soc. 1941, 88e102.
7. Post, C. B.; Karplus, M. J. Am. Chem. Soc. 1986, 108, 1317e1319.
8. Later, half-chair conformation of pyranoside in hen egg-white lysozyme by
high-resolution crystallographic analyses were reported, see; (a) Chipman,
D. M.; Sharon, N. Science 1969, 165, 454e465; (b) Ford, L. O.; Johnson, L. N.;
Machin, P. A.; Phillips, D. C.; Tjian, R. J. Mol. Biol. 1974, 88, 349e371; (c)
Strynadka, N. C. J.; James, M. N. G. J. Mol. Biol. 1991, 220, 401e424; (d)
Hadfield, A. T.; Harvey, D. J.; Archer, D. B.; MacKenzie, D. A.; Jeenes, D. J.;
Radford, S. E.; Lowe, G.; Dobson, C. M.; Johnson, L. N. J. Mol. Biol. 1994, 243,
856e872.
4.16 (t, J¼2.0 Hz, 1H), 3.79 (m, 1H), 3.76 (s, 3H), 3.70e3.59 (m, 3H),
2.01 (s, 3H); 13C NMR
169.1, 158.2, 155.6, 149.8, 137.4, 135.5, 128.6,
d
128.6, 128.2, 127.6, 118.4, 114.5, 100.6, 77.2, 76.9, 76.8, 73.6, 68.9,
68.5, 60.5, 55.7, 48.3, 20.8; ½a D24
ꢂ38.8 (c 0.84, CHCl3); HRMS calcd
ꢃ
for [C30H31NO8þNa]þ 556.1947, found 556.1957.
4.5.9. Phenyl
4-O-acetyl-6-O-benzyl-2-O,3-O-carbonyl-
a-D-gluco-
pyranoside (31). 1H NMR
d
7.33e7.26 (m, 7H), 7.12e7.08 (m, 3H),
5.86 (d, J¼2.8 Hz, 1H), 5.54 (t, J¼9.6 Hz, 1H), 4.99 (t, J¼11.2 Hz, 1H),
4.59 (d, J¼12.0 Hz, 1H), 4.44 (d, J¼12.0 Hz, 1H), 4.43 (t, J¼9.6 Hz,
1H), 3.97 (m, 1H), 3.61e3.52 (m, 2H); 13C NMR
d 169.6, 155.6, 152.6,
137.1, 129.7, 128.3, 127.8, 127.8, 123.7, 116.9, 93.5, 77.2, 76.6, 73.6,
72.0, 68.2, 67.1, 20.7; ½a D24
þ30.5 (c 1.0, CHCl3), 67.4 (c 0.65, CHCl3);
ꢃ
9. Gupta, R. B.; Franck, R. W. J. Am. Chem. Soc. 1987, 109, 6554e6556.
10. McPhail, D. R.; Lee, J. R.; Fraser-Reid, B. J. Am. Chem. Soc. 1992, 113, 1905e1906.
11. (a) Liras, J. L.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2645e2646; (b) Liras, J. L.;
Lynch, V. M.; Anslyn, E. V. J. Am. Chem. Soc. 1997, 119, 8191e8200.
12. Deslongchamps, P.; Li, S.; Dory, Y. L. Org. Lett. 2004, 6, 505e508.
HRMS calcd for [C22H22O8þNa]þ 447.1207, found 447.1212.
4.5.10. 4-Methoxyphenyl-2-O,3-O-carbonyl-4,6-O-dibenzyl-
a
-
D
-glu-
copyranoside (32). 1H NMR
d
7.24e7.18 (m, 10H), 6.96 (d, J¼9.2 Hz,
ꢀ
ꢀ
13. O’Brien, C.; Polakova, M.; Pitt, N.; Tosin, M.; Murphy, P. V. Chem.dEur. J. 2007, 13,
902e909.
2H), 6.75 (d, J¼9.2 Hz, 2H), 5.66 (d, J¼2.0 Hz, 1H), 4.97 (t, J¼11.6 Hz,
1H); 4.76 (d, J¼10.8 Hz, 1H), 4.53 (d, J¼12.0 Hz, 1H), 4.46 (d,
J¼11.2 Hz, 1H), 4.39 (d, J¼12.4 Hz, 1H), 4.24 (dd, J¼11.6, 2 Hz, 1H),
4.07 (d, J¼9.2 Hz, 1H), 3.86 (m, 1H), 3.70 (s, 3H), 3.72e3.60 (m, 4H);
14. For reviews of 1,2-cis glycosylation; (a) Demchenko, A. V. Curr. Org. Chem. 2003,
7, 35e79; (b) Demchenko, A. V. Synlett 2003, 1225e1240; (c) Fairbanks, A. J.
Synlett 2003, 1945e1958.
15. Other examples of 1,2-cis amino glycoside preparation; (a) Kochetkov, N. K.;
Klimov, E. M.; Malysheva, N. N.; Demchenko, A. V. Carbohydr. Res. 1993, 242,
C7eC10; (b) Winterfeld, G. A.; Schmidt, R. R. Angew. Chem., Int. Ed. 2001, 40,
2654e2657; (c) Imamura, A.; Ando, H.; Korogi, S.; Tanabe, G.; Muraoka, O.;
Ishida, H.; Kiso, M. Tetrahedron Lett. 2003, 44, 6725e6728; (d) Bongat, A. F. G.;
Demchenko, A. V. Carbohydr. Res. 2007, 342, 374e406; (e) Park, J.; Kawatkar,
S.; Kim, J.-H.; Boons, G.-J. Org. Lett. 2007, 9, 1959e1962; (f) Koshiba, M.; Su-
zuki, N.; Arihara, R.; Tsuda, T.; Nambu, H.; Nakamura, S.; Hashimoto, S. Chem.
dAsian J. 2008, 3, 1664e1677; (g) Ryan, D. A.; Gin, D. Y. J. Am. Chem. Soc. 2008,
130, 15228e15229; (h) Wei, G.; Lv, X.; Du, Y. Carbohydr. Res. 2008, 343,
3096e3099; (i) Ajayi, K.; Thakur, V. V.; Lapo, R. C.; Knapp, S. Org. Lett. 2010, 12,
2630e2633.
13C NMR
d 155.7, 153.4, 129.7, 137.5, 136.8, 128.4, 128.4, 128.1, 128.0,
127.8, 118.3, 115.7, 94.3, 80.2, 76.9, 74.4, 73.5, 73.0, 72.9, 67.4, 55.6;
½
a 2D4
ꢃ
þ30.5 (c 1.0, CHCl3), 124 (c 1.05, CHCl3); HRMS calcd for
[C21H21O7þNa]þ 408.1180, found 408.1178.
Acknowledgements
S.M. was supported by a Grant-in-Aid for Scientific Research (C)
(Grant Nos. 21590036) from the Japan Society for the Promotion of
Science and an Incentive Research Grant from RIKEN. We thank Ms.
Keiko Yamada for elemental analyses and Dr. Kaori Otsuki and
Dr. Masaya Usui at the Research Resource Center of RIKEN’s Brain
Science Center, and Dr. Yayoi Hongo at the Advanced Technology
Support Division, RIKEN Advanced Science Institute for high-
resolution MS measurements, and Instrumental Analysis Division,
Equipment Management Center, Creative Research Institution,
Hokkaido University. We also thank Ms. Akemi Takahashi for her
technical assistance.
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