Synthesis of 1-deoxyhept-2-ulosyl-glycono-1,5-lactone utilizing α-selective O-glycosidation of 2,6-anhydro-1-deoxy-d-hept-1-enitols

Article abstract of DOI:10.1016/j.tet.2006.07.032

A series of 1-deoxy-heptulo-2-pyranosyl-glycono-1,5-lactones were synthesized utilizing completely α-selective O-glycosidation of heptenitols. Anomeric configuration of the products was confirmed by ³J_C,H coupling measurement and X-ray crystal structural analysis. The benzyl-protected ketosyl saccharides were partly unstable, and glycosidic linkage was prone to cleave under the usual debenzylation conditions. To prevent this, we surveyed various additives for the Pd-catalyzed hydrogenation reaction and found that basic alumina was the most effective.

Full text of DOI:10.1016/j.tet.2006.07.032

Tetrahedron 62 (2006) 9183–9192
Synthesis of 1-deoxyhept-2-ulosyl-glycono-1,5-lactone
utilizing a-selective O-glycosidation of
2,6-anhydro-1-deoxy-D-hept-1-enitols
Rie Namme,a Takashi Mitsugi,a Hideyo Takahashi,a Moto Shirob and Shiro Ikegamia,
*
aSchool of Pharmaceutical Sciences, Teikyo University, Sagamiko, Sagamihara, Kanagawa 199-0195, Japan
bRigaku Corporation, 3-9-12 Matsubara, Akishima, Tokyo 196-0003, Japan
Received 13 June 2006; revised 6 July 2006; accepted 11 July 2006
Available online 7 August 2006
Abstract—A series of 1-deoxy-heptulo-2-pyranosyl-glycono-1,5-lactones were synthesized utilizing completely a-selective O-glycosidation
of heptenitols. Anomeric configuration of the products was confirmed by 3JC,H coupling measurement and X-ray crystal structural analysis.
The benzyl-protected ketosyl saccharides were partly unstable, and glycosidic linkage was prone to cleave under the usual debenzylation
conditions. To prevent this, we surveyed various additives for the Pd-catalyzed hydrogenation reaction and found that basic alumina was
the most effective.
Ó 2006 Elsevier Ltd. All rights reserved.
7
1
1. Introduction
O
O
O
2
6
BnO
BnO
BnO
BnO
BnO
Bioactive sugar chains containing ketoses such as fructose
and sialic acids are abundant in nature. The sialic acid family,
represented by N-acetylneuraminic acid (Neu5Ac), consists
of oligosaccharides or glycoconjugates in the form of a-keto-
sides. To take a notable example, 3-deoxy-D-manno-oct-2-
ulosonic acid is a constituent of glycolipids of Gram-negative
bacteria and is a-linked to lipid A. Since sialic acids are in-
volved in numerous biological processes, they are attractive
targets for drug discovery.1 It is also known that 1-deoxy-a-
D-gluco-heptulose 2-phosphate, which is a 1-C-methyl ana-
logue of D-glucose 1-phosphate, is a potent phosphorylase
inhibitor. The interaction of heptulose 2-phosphate with
enzymes has been examined thoroughly.2 It is expected that
heptulosyloligosaccharides can be utilized as a new class of
bioactive oligosaccharides. In the synthetic field, therefore,
stereoselective construction of ketosides3,4 as well as artifi-
cial ones5–8 has been enthusiastically investigated.
OBn
BnO
OBn
OBn
OBn
OBn
OBn
1a (Glc)
1b (Gal)
1c (Man)
Figure 1. 2,6-Anhydro-1-deoxyhept-1-enitols as glycosyl donors.
methyl a-D-glucopyranosides 2 and 3 afforded 1-deoxy-
hept-2-ulosylglucosides, i.e., the 10-C-methyl-substituted
analogue of naturally occurring aldoside (Scheme 1). This
glycosidation was promoted by various acids such as
TiCl4, SnCl4, trimethylsilyl trifluoromethanesulfonate
(TMSOTf), and trifluoromethanesulfonic acid (TfOH). The
best result was achieved using TfOH as a promoter at
ꢀ78 ꢁC. As far as we have examined, the glycosidation of
D-gluco-, D-galacto-, and D-manno-hept-1-enitols 1a–c
gave only a-ketoside, and the formation of b-ketoside was
not detected. The glycosidation of peracetylated heptenitols
with a 3-O-acetyl group also took place in an a-selective
manner.
For the synthesis of ketosyl saccharides, several methods
have been developed by our group.6,7 We have used exo-gly-
cals in the construction of artificial sugar chains and reported
the O-glycosidation of heptenitols,9–12 which are among the
simplest exo-glycals formed by Tebbe-type methylenation13
of glyconolactone. The acid-promoted O-glycosidation of
2,6-anhydro-1-deoxyhept-1-enitols 1a–c (Fig. 1) with
TfOH (cat.)
MS4A
BnO
BnO
BnO
BnO
BnO
O
O
+
ROH
BnO
CH2Cl2, –78 °C
71–98%
BnO
BnO
OR
donor
acceptor
1a-c
HO
BnO
BnO
O
O
HO
,
ROH =
BnO
BnO
Keywords: Ketoside; exo-Glycal; Heptenitol; Heptuloside; O-Glycosida-
tion; Basic alumina.
BnO
BnO
3
OMe
OMe
2
* Corresponding author. Tel.: +81 42 685 3730; fax: +81 42 685 3729;
e-mail: somc@pharm.teikyo-u.ac.jp
Scheme 1. Glycosidation of hept-1-enitols 1a–c.
0040–4020/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2006.07.032

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R. Namme et al. / Tetrahedron 62 (2006) 9183–9192
To investigate the generality of this a-selective glycosida-
tion, we planned to examine the O-glycosidation of hepteni-
tols using various glycosyl acceptors. We herein present
a new library of hept-2-ulosylsaccharides and their X-ray
crystallographic analyses.
hydroxyl groups, proceeded very slowly (3 h) to give disac-
charides in low yields (Table 1, entries 3 and 4). It is clear
that pyranoside with an axially oriented hydroxyl group is
reluctantly glycosylated. We next used the mannono-1,5-
lactone 7c as an acceptor because we were interested in its
conformational and electronic differentiation from 4C1
pyranoside. Surprisingly, the reaction with 7c proceeded
rapidly (15 min), and the corresponding disaccharide was
obtained in 86% yield with complete a-stereoselectivity. It
should be noted that the secondary alcohol 7c reacted
more rapidly than the primary alcohol 2. The rate of this
glycosidation with glycosyl acceptors increased roughly in
the following order:Axial secondary OH (5, 6)ꢂequatorial
secondary OH (4)zprimary OH (2)<secondary OH on
lactone ring (7c).
2. Results and discussion
2.1. Glycosidation of heptenitols
As the ketosyl saccharides have quaternary anomeric car-
bons, we suspected that the unreactive axial hydroxyl group
of the pyranose might not be glycosylated efficiently. We
first examined the O-glycosidation of heptenitol 1a with
pyranosides 2, 4, 5, and 6 (Table 1). The reaction was per-
formed in CH2Cl2 at ꢀ78 ꢁC in the presence of 10 mol %
of TfOH. After quenching the reaction with triethylamine,
the solvent was removed and the residue was subjected to
column chromatography to afford the desired disaccharide
in pure form. In the case of the primary alcohol 2, the cor-
responding disaccharide was obtained in 97% yield with
a-stereoselectivity.6a The glucopyranoside 4, which has an
equatorial secondary hydroxyl group, showed similar reac-
tivity (Table 1, entry 2). On the other hand, glycosidation
with mannopyranosides 5 and 6, which have axial secondary
Encouraged by the promising results obtained, we attempted
the synthesis of heptulosylsaccharide using glycono-1,5-
lactones as the most reactive glycosyl acceptors. The use
of lactones provides an additional advantage, enabling the
transformation of the resulting disaccharides by methylena-
tion,6b,13 reduction, or alkylation to afford a wide variety of
sugar-related compounds.
Thus, the glycosidation of a combination of heptenitols 1a–c
as glycosyl donors and sugar lactones 7–1014 derived from
D-glucose, D-galactose, and D-mannose as acceptors
(Fig. 2) was explored (Table 2).
Table 1. O-Glycosidation of 1a
TfOH (10 mol %)
BnO
BnO
BnO
BnO
BnO
BnO
O
MS4A
O
Hydroxyl groups at C-2 in glyconolactones were smoothly
glycosylated to afford heptulosyl-(2/2)-glyconolactones
11aa–cc in high yields (Table 2, entries 1–9). As we ex-
pected, C-2-OH in mannono-1,5-lactone reacted easily with
the heptenitol 1a, 1b, and 1c giving the corresponding di-
saccharides in high yield (Table 2, entries 3, 6, 9). Similarly,
C-3-OH and C-4-OH were efficiently glycosylated to afford
the corresponding heptulosyl-(2/3)-glyconolactones 12
and heptulosyl-(2/4)-glyconolactones 13, respectively
(Table 2, entries 10–27). Glycosidation with C-4-OH in gal-
actono-1,5-lactone 9b also proceeded well and yielded the
corresponding disaccharides (Table 2, entries 20, 23, 26).
No remarkable differences in reactivity were observed in the
glycosidation of gluco-, galacto-, and manno-heptenitols. In
addition, it is noteworthy that all heptulosides were obtained
as their respective single isomers.
+
ROH
CH2Cl2, –78 °C
BnO
BnO
OR
acceptor (1.0 eq)
donor (1.1 eq)
1a
Entry
1
Acceptor (ROH)
Time (min)
60
Yield (%)
97
HO
O
BnO
BnO
BnO
OMe
2
BnO
O
BnO
2
3
50
94
34
BnO
HO
OMe
4
OH
BnO
O
BnO
180
BnO
OMe
5
OH
BnO
The glycosidation of 1a–c with primary alcohols 10a–c was
performed in the same manner (Table 2, entries 28–38). In
entries 33 and 35 in Table 2, disaccharides were obtained in
excellent yields within 15 min. In other cases, a longer reac-
tion time was required for the completion of glycosidation.
In addition, a longer reaction time caused the decomposition
of heptenitols and heptulosides (Table 2, entries 30, 31, 37).
O
BnO
4
5
OMe
180
15
26
86
BnO
6
OH
O
BnO
BnO
BnO
O
7c
6
O
O
O
O
O
O
O
O
BnO
BnO
HO
BnO
BnO
BnO
HO
4
2
3
OBn
BnO
OH
OBn
OBn
OH
OBn
OBn
OBn
7a (Glc): 2-OH( ), 4-OBn( )
7b (Gal): 2-OH( ), 4-OBn( )
7c (Man): 2-OH( ), 4-OBn( )
8a (Glc): 2-OBn( ), 4-OBn( )
8b (Gal): 2-OBn( ), 4-OBn( )
8c (Man): 2-OBn( ), 4-OBn( )
9a (Glc): 2-OBn( ), 4-OH( )
9b (Gal): 2-OBn( ), 4-OH( )
9c (Man): 2-OBn( ), 4-OH( )
10a (Glc): 2-OBn( ), 4-OBn( )
10b (Gal): 2-OBn( ), 4-OBn( )
10c (Man): 2-OBn( ), 4-OBn( )
Figure 2. Glycono-1,5-lactones as glycosyl acceptors.

R. Namme et al. / Tetrahedron 62 (2006) 9183–9192
Table 2. O-Glycosidation of 1a–c with glycono-1,5-lactones
9185
TfOH (10 mol%)
MS4A
7a-c
8a-c
11
12
13
14
1a-c
+
9a-c
CH2Cl2, –78 °C
10a-c
donor (1.1 eq)
acceptor (1.0 eq)
Entry
Donor
Acceptor
Time (min)
Product
Yield (%)
1
2
3
4
5
6
7
8
9
1a
1a
1a
1b
1b
1b
1c
1c
1c
7a
7b
7c
7a
7b
7c
7a
7b
7c
40
30
15
15
17
17
17
15
12
11aa Glc-(2/2)-Glc
11ab Glc-(2/2)-Gal
11ac Glc-(2/2)-Man
11ba Gal-(2/2)-Glc
11bb Gal-(2/2)-Gal
11bc Gal-(2/2)-Man
11ca Man-(2/2)-Glc
11cb Man-(2/2)-Gal
11cc Man-(2/2)-Man
89
95
86
99
83
98
89
95
89
BnO
O
BnO
1'
2'
BnO
BnO
O
BnO
O
BnO
BnO
O
2
11
10
11
12
13
14
15
16
17
18
1a
1a
1a
1b
1b
1b
1c
1c
1c
8a
8b
8c
8a
8b
8c
8a
8b
8c
30
15
20
20
15
30
15
15
30
12aa Glc-(2/3)-Glc
12ab Glc-(2/3)-Gal
12ac Glc-(2/3)-Man
12ba Gal-(2/3)-Glc
12bb Gal-(2/3)-Gal
12bc Gal-(2/3)-Man
12ca Man-(2/3)-Glc
12cb Man-(2/3)-Gal
12cc Man-(2/3)-Man
93
91
81
88
89
77
84
88
84
BnO
BnO
1'
O
OBn
BnO
2'
BnO
O
O
O
OBn
BnO
12
3
19
20
21
22
23
24
25
26
27
1a
1a
1a
1b
1b
1b
1c
1c
1c
9a
9b
9c
9a
9b
9c
9a
9b
9c
30
30
20
22
20
20
16
15
30
13aa Glc-(2/4)-Glc
13ab Glc-(2/4)-Gal
13ac Glc-(2/4)-Man
13ba Gal-(2/4)-Glc
13bb Gal-(2/4)-Gal
13bc Gal-(2/4)-Man
13ca Man-(2/4)-Glc
13cb Man-(2/4)-Gal
13cc Man-(2/4)-Man
99
81
81
94
82
83
97
97
73
BnO
1'
4
O
OBn
O
BnO
BnO
2'
BnO
O
BnO
O
OBn
13
28
29a
30b
31
32a
33
34
35
36
37
38
1a
1a
1a
1a
1a
1b
1b
1b
1c
1c
1c
10a
10a
10b
10c
10c
10a
10b
10c
10a
10b
10c
50
10
210
120
15
14
60
10
90
14aa Glc-(2/6)-Glc
14aa Glc-(2/6)-Glc
14ab Glc-(2/6)-Gal
14ac Glc-(2/6)-Man
14ac Glc-(2/6)-Man
14ba Gal-(2/6)-Glc
14bb Gal-(2/6)-Gal
14bc Gal-(2/6)-Man
14ca Man-(2/6)-Glc
14cb Man-(2/6)-Gal
14cc Man-(2/6)-Man
72
67
77
74
82
96
75
97
69
70
79
BnO
BnO
O
2'
1'
BnO
6
BnO
O
O
BnO
BnO
O
OBn
14
60
40
a
The amount of TfOH was increased to 15 mol %.
After 200 min, 5 mol % of TfOH was added.
b
In particular, glycosidation of gluco-heptenitol 1a with
galactono-1,5-lactone 10b was quite slow, and therefore
another portion of TfOH was added for the completion
of the reaction (Table 2, entry 30). In entries 29 and 32 in
Table 2, although the amount of TfOH was increased to
15 mol % to complete the reaction in a shorter time, yields
were not increased.
of heptenitols 1a–c as glycosyl donors and 7–10 as acceptors.
All gluco-, galacto-, and manno-heptuloside products were
isolated as their respective single anomeric isomers.
2.2. Determination of the configurations at anomeric
position
The configurations at C-20 anomeric position of hept-2-
ulosides were determined by X-ray crystallographic analy-
ses and NMR study.
It was surprising that the primary alcohols 10a–c were
unreactive in some cases. The reactivity may depend on
the combination of a glycosyl donor and an acceptor. For
example, glycosidation of gluco-heptenitol 1a with manno-
nolactone 10c required 2 h (Table 2, entry 31), but otherwise
the reaction of galacto-heptenitol 1b with 10c was com-
pleted in 10 min (Table 2, entry 35). Although the reactivity
varied, heptulosyl-(2/6)-glyconolactones 14aa–cc were
obtained as their respective single isomers.
manno-Hept-2-uloside 14cc was obtained as colorless crys-
tals. The X-ray crystallographic structure of 14cc is shown in
Figure 3.15 Based on this X-ray crystallographic analysis, it
was elucidated that manno-heptuloside possessed a 5C2 chair
conformation and a-anomeric configuration. Additionally,
the mannonolactone part had a B2,5 boat conformation. As
only one isomer was formed in every case, it is suggested
that other manno-heptulosides also possess the a-anomeric
configuration.
We therefore achieved the synthesis of 36 examples of 1-de-
oxy-2-heptulopyranosyl-glycono-1,5-lactoneinacombination

9186
R. Namme et al. / Tetrahedron 62 (2006) 9183–9192
are oriented synclinally in a-ketoside and antiperiplanarly
in b-ketoside. By the measurement of the vicinal coupling
3
0
0
constant JC-1 ,H-3 of our products, which were approxi-
mately 1.8–2.0 Hz, it is obvious that newly formed glyco-
sidic bonds have the a-configuration. We can be fairly
certain that the O-glycosidation of gluco-, galacto-, and
manno-heptenitols gave a-glycosides.
O
C-1'
C-2'
C-6
OBn
O
BnO
BnO
BnO
1'
6
2.3. Deprotection
3'
2'
O
We then focused on the deprotection of protected hydroxyl
groups. In preliminary experiments, it was found that the re-
moval of benzyl groups by hydrogenolysis was accompanied
by the cleavage of ketoside bonds. Other reactions such as
Birch reduction, catalytic hydrogen transfer,17 the use of
lithium naphthalenide,18 and oxidation19–21 gave unsatisfac-
tory results.
BnO
BnO
C-1
O
1
O
OBn
14cc Man-(2 6)-Man
We therefore returned to the use of Pd-catalyzed hydro-
genolysis. The deprotection of Man-(2/3)-Man 12cc was
examined in various solvents using Pd/C or Pd(OH)2/C as a
catalyst (Table 3). When the reaction proceeded in MeOH,
solvolysis occurred to afford 17 (Table 3, entry 1). Using
less nucleophilic trifluoroethanol (TFE) as a solvent, intra-
molecular cyclization followed by cleavage of the ketoside
bond gave the cyclized product 18 quantitatively (Table 3,
entry 2). It was speculated that the acidity of TFE caused
the cleavage of ketoside. Similarly, the use of THF as a
solvent resulted in the formation of 18 (Table 3, entry 3).
On the hypothesis that the formation of a hydrogen bond
would prevent intramolecular nucleophilic attack of the
anomeric center, hydrogenolysis was performed in mixed
solvents THF/H2O, and the desired product 15cc was
obtained in 44% yield (Table 3, entry 4).
Figure 3. X-ray crystal structure of 14cc. Hydrogen atoms are omitted for
clarity.
The anomeric configuration of gluco- and galacto- heptulo-
pyranosides was anticipated by analyzing the vicinal
3
C–H coupling constants JC,H in NMR spectra.10,16 It is
known that the magnitude of 3JC,H depends on the dihedral
angle between the C-1/C-2 bond and C-3/H-3 bond. As shown
in Figure 4, the C-10 exocyclic carbon and H-30 axial proton
H
H
O 2'
1'
O
Osugar
CH3
CH3
RO
RO
3'
3'
2'
RO
RO
Osugar
1'
-anomer
-anomer
11aa Glc-(2 2)-Glc 1.9 Hz
12ba Gal-(2 3)-Glc 2.0 Hz
13ab Glc-(2 4)-Gal 1.8 Hz
14bb Gal-(2 6)-Gal 1.9 Hz
Although the use of such mixedsolvents appeared promising,
unexpected solvolysis occurred in the case of Man-(2/2)-
Man 11cc (Table 3, entry 6). It was found that deprotected
disaccharides vary in stability. In order to prevent solvolysis,
slightly basic conditions were examined. In the presence of
Figure 4. Vicinal coupling constants 3JC-1 ,H-3
.
0
0
Table 3. Deprotection of 11cc and 12cc
OBn
BnO
OH
HO
HO
HO
O
O
O
BnO
Pd
H2
OBn
O
OH
OH
O
OH
O
BnO
HO
HO
HO
O
O
O
OBn
O
OH
O
OH
BnO
HO
15cc
17
OH 18
OMe
12cc
OBn
OH
O
BnO
HO
HO
HO
HO
HO
HO
O
Pd
BnO
OH
HO
HO
HO
BnO
BnO
H2
O
O
O
O
O
BnO
BnO
19
OH
O
O
16cc
11cc
Entry
Substrate
Pd
Cat. (wt %)
Solvent
Time (h)
Yield (%)
Other products
1
2
3
12cc
Pd/C
Pd(OH)2/C
Pd/C
Pd(OH)2/C
Pd(OH)2/C
20
25
50
20
50
MeOH
TFE
THF
THF/H2O
THF; MeOH
4
48
9
15
70
0
0
0
44
97
17
18
18
4
5a
6
11cc
Pd(OH)2/C
Pd(OH)2/C
50
50
THF/H2O
THF; MeOH
2
37
0
65
19
7a
a
Hydrogenation was performed in the presence of basic alumina (50 wt %).

R. Namme et al. / Tetrahedron 62 (2006) 9183–9192
9187
organic or inorganic bases such as pyridine, triethylamine,
3. Conclusion
sodium acetate, and potassium carbonate, hydrogenolysis
did not proceed smoothly.22 We finally found that basic
alumina was effective: it prevented undesired side reactions
and maintained the catalyst activity. In the presence of basic
alumina, the solubility of substrates in solvent markedly
affected the reaction rate. In the early stage of hydrogenoly-
sis, the reaction proceeds much faster in THF than in MeOH
or t-BuOH. Then, as debenzylation progresses, the solubility
in THF becomes low, requiring MeOH to be added. Under
these conditions, both 12cc and 11cc were debenzylated in
satisfactory yields (Table 3, entries 5 and 7).
We achieved the synthesis of disaccharides, hept-2-ulosyl-
glyconolactones, by acid-promoted O-glycosidation of 2,6-
anhydro-1-deoxyhept-1-enitols 1a–c. Under the reaction
conditions described here, O-glycosidation of heptenitols
1a–c proceeded with complete stereoselectivity, and each
disaccharide was isolated as a single anomeric isomer.
Their configurations at anomeric position were identified as
a-stereochemistry by X-ray crystallography and NMR
vicinal coupling constant 3JC-1 ,H-3 . Although the removal of
benzyl groups was problematic, we found that Pd-catalyzed
hydrogenolysis in the presence of basic alumina was effec-
tive in preventing cleavage of the ketoside bonds.
0
0
Thus, debenzylation of 36 heptulosides 11–14 was explored
using catalytic hydrogenation in the presence of Pd(OH)2/C
and basic alumina (Table 4). In many cases, debenzylation
afforded the desired deprotected disaccharides. However,
some substrates were quite unstable even under basic condi-
tions, and deprotected disaccharides could not be isolated.
Particularly, the removal of benzyl groups in heptulosyl-
(2/6)-glyconolactone was difficult. It appears that de-
protected heptulosides 21 are fairly unstable.23 Although
considerable effort was made, further improvement was not
achieved in these cases except for Gal-(2/6)-Gal 14b.
Ultimately, the 25 disaccharides shown in Table 4 were
obtained in a deprotected form.
4. Experimental
4.1. General methods
Melting points were measured on a YANACO Micro Melt-
ing Point Apparatus and were uncorrected. IR spectra were
recorded on a Jasco FT-IR-8000 Fourier-transform infrared
1
spectrometer. H and 13C NMR, and three-bond carbon–
3
proton coupling constants JC,H were measured on a JEOL
ECP 600 (600 MHz) NMR spectrometer in CDCl3, CD3OD,
Table 4. Deprotection
BnO
HO
O
Pd(OH)2/C, basic alumina
O
HO
BnO
H2
BnO
HO
O
O
BnO
HO
O
THF; MeOH
O
O
O
Entry
O-benzylated disaccharide
Product
Yield (%)
1
2
3
4
5
6
7
8
9
11aa Glc-(2/2)-Glc
11ab Glc-(2/2)-Gal
11ac Glc-(2/2)-Man
11ba Gal-(2/2)-Glc
11bb Gal-(2/2)-Gal
11bc Gal-(2/2)-Man
11ca Man-(2/2)-Glc
11cb Man-(2/2)-Gal
11cc Man-(2/2)-Man
16aa Glc-(2/2)-Glc
16ab Glc-(2/2)-Gal
16ac Glc-(2/2)-Man
16ba Gal-(2/2)-Glc
16bb Gal-(2/2)-Gal
16bc Gal-(2/2)-Man
16ca Man-(2/2)-Glc
16cb Man-(2/2)-Gal
16cc Man-(2/2)-Man
quant.
89
quant.
78
quant.
quant.
89
83
65
HO
HO
HO
O
HO
O
HO
HO
HO
O
O
16
10
11
12
13
14
15
16
12aa Glc-(2/3)-Glc
12ab Glc-(2/3)-Gal
12ba Gal-(2/3)-Glc
12bb Gal-(2/3)-Gal
12ca Man-(2/3)-Glc
12cb Man-(2/3)-Gal
12cc Man-(2/3)-Man
15aa Glc-(2/3)-Glc
15ab Glc-(2/3)-Gal
15ba Gal-(2/3)-Glc
15bb Gal-(2/3)-Gal
15ca Man-(2/3)-Glc
15cb Man-(2/3)-Gal
15cc Man-(2/3)-Man
quant.
99
97
quant.
98
83
HO
HO
HO
O
OH
HO
O
O
HO
O
O
OH
15
65
17
18
19
20
21
22
23
24
13aa Glc-(2/4)-Glc
13ab Glc-(2/4)-Gal
13ac Glc-(2/4)-Man
13ba Gal-(2/4)-Glc
13bb Gal-(2/4)-Gal
13bc Gal-(2/4)-Man
13cb Man-(2/4)-Gal
13cc Man-(2/4)-Man
20aa Glc-(2/4)-Glc
20ab Glc-(2/4)-Gal
20ac Glc-(2/4)-Man
20ba Gal-(2/4)-Glc
20bb Gal-(2/4)-Gal
20bc Gal-(2/4)-Man
20cb Man-(2/4)-Gal
20cc Man-(2/4)-Man
quant.
91
quant.
75
quant.
quant.
94
HO
HO
HO
O
OH
HO
O
O
HO
OH
20
quant.
OH
O
HO
HO
HO
25
14bb Gal-(2/6)-Gal
21bb Gal-(2/6)-Gal
59
O
HO
O
HO
O
OH
21

9188
R. Namme et al. / Tetrahedron 62 (2006) 9183–9192
or D2O solutions. Mass spectra (MS) and high-resolution
mass spectra (HRMS) were recorded with a JEOL JMS-
SX102A mass spectrometer with FAB using 3-nitrobenzyl
alcohol (NBA) as the matrix. Optical rotations were mea-
sured with a Jasco DIP-370 digital polarimeter. X-ray crys-
tallographic measurements were performed with a Rigaku
RAXIS-RAPID Imaging Plate Diffractometer with graphite
monochromated MoKa radiation at 123 K. TLC was per-
formed on precoated plates (Merck TLC Aluminum sheets
silica 60 F254) with detection by UV light or with phospho-
molybdic acid in EtOH/H2O followed by heating. Column
chromatography was performed using SiO2 (Silica Gel 60
N, spherical, neutral, Kanto).
IR (neat): 3031, 2915, 2867, 1775, 1455, 1096, 1059, 737,
698 cmꢀ1
HRMS (FAB): calcd for C62H64O11K
1023.4086, found 1023.4061.
;
4.2.7. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-manno-hept-
2-ulosyl-(2/2)-3,4,6-tri-O-benzyl-D-glucono-1,5-lactone
(11ca). Colorless syrup; [a]2D7 +49.1 (c 1.06, CHCl3); IR
(neat): 3031, 2911, 2869, 1763, 1455, 1098, 1078, 737,
698 cmꢀ1; HRMS (FAB): calcd for C62H64O11K 1023.4086,
found 1023.4086.
4.2.8. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-manno-hept-
2-ulosyl-(2/2)-3,4,6-tri-O-benzyl-D-galactono-1,5-lac-
tone (11cb). Colorless syrup; [a]2D6 +57.7 (c 1.13, CHCl3); IR
(neat): 3031, 2915, 2867, 1758, 1455, 1096, 737, 698 cmꢀ1
;
4.2. General procedure 1: glycosidation of heptenitols
with alcohols
HRMS (FAB): calcd for C62H64O11K 1023.4086, found
1023.4105.
To a stirred mixture of hept-1-enitol 1a (237.0 mg,
0.44 mmol), hydroxylactone 7a (180.0 mg, 0.40 mmol), and
molecular sieves 4 A (400.0 mg) in CH2Cl2 (8.0 mL) was
4.2.9. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-manno-hept-
2-ulosyl-(2/2)-3,4,6-tri-O-benzyl-D-mannono-1,5-lac-
tone (11cc). Colorless syrup; [a]2D5 +65.5 (c 1.01, CHCl3); IR
˚
added TfOH (3.5 mL, 0.04 mmol) at ꢀ78 ꢁC. The reaction
mixture was stirred at ꢀ78 ꢁC and then quenched with tri-
ethylamine. After the removal of the solvent, the residue was
purified by column chromatography (silica gel, neutral, hexane/
ethyl acetate 3:1) to give disaccharide 11aa (350.0 mg).24
(neat): 3031, 2923, 2867, 1777, 1455, 1073, 739, 698 cmꢀ1
;
HRMS (FAB): calcd for C62H64O11K 1023.4086, found
1023.4084.
4.2.10. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-gluco-hept-2-
ulosyl-(2/3)-2,4,6-tri-O-benzyl-D-glucono-1,5-lactone
(12aa). Colorless syrup; [a]2D6 +98.8 (c 1.14, CHCl3); IR
4.2.1. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-gluco-hept-2-
ulosyl-(2/2)-3,4,6-tri-O-benzyl-D-glucono-1,5-lactone
(11aa). Colorless syrup; [a]2D6 +64.9 (c 1.16, CHCl3); IR
(neat): 3031, 2913, 2869, 1763, 1105, 1082, 1028, 1029,
739, 700 cmꢀ1; HRMS (FAB): calcd for C62H64O11K
1023.4086, found 1023.4096.
(neat): 3031, 2927, 2863, 1754, 1455, 1073, 737, 698 cmꢀ1
;
HRMS (FAB): calcd for C62H64O11Na 1007.4346, found
1007.4355.
4.2.11. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-gluco-hept-2-
ulosyl-(2/3)-2,4,6-tri-O-benzyl-D-galactono-1,5-lactone
(12ab). Colorless syrup; [a]3D0 +90.9 (c 1.04, CHCl3); IR
(neat): 3032, 2921, 2867, 1750, 1455, 1096, 737,
4.2.2. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-gluco-hept-2-
ulosyl-(2/2)-3,4,6-tri-O-benzyl-D-galactono-1,5-lactone
(11ab). Colorless needle; mp 81–83 ꢁC; [a]D25 +70.6 (c 0.5,
CHCl3); IR (KBr): 3031, 2913, 2869, 1761, 1497, 1455,
1362, 735, 698 cmꢀ1; HRMS (FAB): calcd for C62H64O11K
1023.4086, found 1023.4096.
698 cmꢀ1
;
1023.4086, found 1023.4075.
HRMS (FAB): calcd for C62H64O11K
4.2.12. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-gluco-hept-2-
ulosyl-(2/3)-2,4,6-tri-O-benzyl-D-mannono-1,5-lactone
(12ac). Colorless syrup; [a]2D7 +35.3 (c 1.08, CHCl3); IR
(neat): 3031, 2924, 2869, 1765, 1455, 1125, 1088, 739,
698 cmꢀ1; HRMS (FAB): calcd for C62H64O11K 1023.4086,
found 1023.4085.
4.2.3. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-gluco-hept-2-
ulosyl-(2/2)-3,4,6-tri-O-benzyl-D-mannono-1,5-lactone
(11ac). Colorless syrup; [a]2D7 +47.6 (c 1.15, CHCl3); IR
(neat): 3031, 2928, 2867, 1775, 1455, 1127, 1082, 1065,
1028, 737, 698 cmꢀ1; HRMS (FAB): calcd for C62H64O11K
1023.4086, found 1023.4076.
4.2.13. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-galacto-hept-
2-ulosyl-(2/3)-2,4,6-tri-O-benzyl-D-glucono-1,5-lactone
(12ba). Colorless syrup; [a]2D6 +101.7 (c 1.08, CHCl3); IR
(neat): 3031, 2924, 2870, 1754, 1455, 1096, 1069, 737,
4.2.4. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-galacto-hept-
2-ulosyl-(2/2)-3,4,6-tri-O-benzyl-D-glucono-1,5-lactone
(11ba). Colorless syrup; [a]2D9 +59.4 (c 1.21, CHCl3); IR
698 cmꢀ1
;
1007.4346, found 1007.4354.
HRMS (FAB): calcd for C62H64O11Na
(neat): 3031, 2917, 2869, 1763, 1455, 1100, 737, 700 cmꢀ1
;
HRMS (FAB): calcd for C62H64O11K 1023.4086, found
1023.4096.
4.2.14. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-galacto-hept-
2-ulosyl-(2/3)-2,4,6-tri-O-benzyl-D-galactono-1,5-lac-
tone (12bb). Colorless needle; mp 127–128 ꢁC; [a]D24 +101.0
(c 1.0, CHCl3); IR (KBr): 3031, 2867, 1732, 1497, 1098, 735,
696 cmꢀ1; HRMS (FAB): calcd for C62H64O11K 1023.4086,
found 1023.4094.
4.2.5. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-galacto-hept-
2-ulosyl-(2/2)-3,4,6-tri-O-benzyl-D-galactono-1,5-lac-
tone (11bb). Colorless syrup; [a]2D6 +52.5 (c 1.05, CHCl3); IR
(neat): 3031, 2923, 2874, 1763, 1455, 1101, 739, 700 cmꢀ1
;
HRMS (FAB): calcd for C62H64O11K 1023.4086, found
1023.4084.
4.2.15. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-galacto-hept-
2-ulosyl-(2/3)-2,4,6-tri-O-benzyl-D-mannono-1,5-lac-
tone (12bc). Colorless syrup; [a]2D8 +44.2 (c 1.28, CHCl3);
IR (neat): 3031, 2915, 2869, 1765, 1455, 1098, 737,
4.2.6. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-galacto-hept-
2-ulosyl-(2/2)-3,4,6-tri-O-benzyl-D-mannono-1,5-lac-
tone (11bc). Colorless syrup; [a]2D7 +48.9 (c 1.03, CHCl3);

R. Namme et al. / Tetrahedron 62 (2006) 9183–9192
9189
698 cmꢀ1; HRMS (FAB): calcd for C62H64O11K 1023.4086,
found 1023.4082.
4.2.25. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-manno-hept-
2-ulosyl-(2/4)-2,3,6-tri-O-benzyl-D-glucono-1,5-lactone
(13ca). Colorless syrup; [a]2D7 +36.9 (c 1.06, CHCl3); IR
(neat): 3031, 2915, 2867, 1786, 1455, 1100, 1084, 745,
700 cmꢀ1; HRMS (FAB): calcd for C62H64O11K 1023.4086,
found 1023.4087.
4.2.16. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-manno-hept-
2-ulosyl-(2/3)-2,4,6-tri-O-benzyl-D-glucono-1,5-lactone
(12ca). Colorless syrup; [a]2D7 +68.3 (c 1.18, CHCl3);
IR (neat): 3031, 2911, 2867, 1757, 1455, 1092, 1073,
745, 702 cmꢀ1; HRMS (FAB): calcd for C62H64O11K
1023.4086, found 1023.4093.
4.2.26. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-manno-hept-
2-ulosyl-(2/4)-2,3,6-tri-O-benzyl-D-galactono-1,5-lac-
tone (13cb). Colorless syrup; [a]2D7 ꢀ0.43 (c 1.07, CHCl3); IR
(neat): 3031, 2907, 2869, 1788, 1455, 1111, 739, 700 cmꢀ1
;
4.2.17. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-manno-hept-
2-ulosyl-(2/3)-2,4,6-tri-O-benzyl-D-galactono-1,5-lac-
tone (12cb). Colorless syrup; [a]2D6 +77.9 (c 1.10, CHCl3);
IR (neat): 3031, 2919, 2869, 1750, 1455, 1119, 1071, 752,
735, 696 cmꢀ1; HRMS (FAB): calcd for C62H64O11K
1023.4086, found 1023.4064.
HRMS (FAB): calcd for C62H64O11K 1023.4086, found
1023.4074.
4.2.27. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-manno-hept-
2-ulosyl-(2/4)-2,3,6-tri-O-benzyl-D-mannono-1,5-lac-
tone (13cc). Colorless syrup; [a]3D0 +9.8 (c 1.05, CHCl3); IR
(neat): 3031, 2924, 2870, 1767, 1455, 1109, 748, 737,
698 cmꢀ1; HRMS (FAB): calcd for C62H64O11K 1023.4086,
found 1023.4080.
4.2.18. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-manno-hept-
2-ulosyl-(2/3)-2,4,6-tri-O-benzyl-D-mannono-1,5-lac-
tone (12cc). Colorless syrup; [a]3D0 +39.7 (c 1.16, CHCl3); IR
(neat): 3031, 2915, 2867, 1773, 1455, 1113, 739, 698 cmꢀ1
;
HRMS (FAB): calcd for C62H64O11K 1023.4086, found
1023.4083.
4.2.28. 3,4,5,7-Tetra-O-benzyl-1-deoxy-D-gluco-hept-2-
ulosyl-(2/6)-2,3,4-tri-O-benzyl-D-glucono-1,5-lactone
(14aa). Colorless syrup; mp 79–81 ꢁC; [a]D25 +70.3 (c 1.00,
CHCl3); IR (KBr): 3031, 2867, 1759, 1455, 1123, 1071,
739, 696 cmꢀ1; HRMS (FAB): calcd for C62H64O11K
1023.4086, found 1023.4102.
4.2.19. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-gluco-hept-2-
ulosyl-(2/4)-2,3,6-tri-O-benzyl-D-glucono-1,5-lactone
(13aa). Colorless syrup; [a]2D8 +47.6 (c 1.09, CHCl3); IR
(neat): 3031, 2924, 2869, 1792, 1455, 1088, 735, 698 cmꢀ1
;
HRMS (FAB): calcd for C62H64O11K 1007.4346, found
1007.4331.
4.2.29. 3,4,5,7-Tetra-O-benzyl-1-deoxy-D-gluco-hept-2-
ulosyl-(2/6)-2,3,4-tri-O-benzyl-D-galactono-1,5-lactone
(14ab). Colorlesssyrup;[a]2D5 +78.8 (c1.17, CHCl3); IR (neat):
3031, 2921, 2869, 1752, 1455, 1067, 735, 698 cmꢀ1; HRMS
(FAB): calcd for C62H64O11Na 1007.4346, found 1007.4333.
4.2.20. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-gluco-hept-2-
ulosyl-(2/4)-2,3,6-tri-O-benzyl-D-galactono-1,5-lactone
(13ab). Colorless syrup; [a]2D7 +29.8 (c 1.13, CHCl3); IR
(neat): 3031, 2924, 2867, 1791, 1455, 1090, 7367,
698 cmꢀ1; HRMS (FAB): calcd for C62H64O11K 1023.4086,
found 1023.4074.
4.2.30. 3,4,5,7-Tetra-O-benzyl-1-deoxy-D-gluco-hept-2-
ulosyl-(2/6)-2,3,4-tri-O-benzyl-D-mannono-1,5-lactone
(14ac). Colorlesssyrup;[a]2D9 +19.8(c1.07, CHCl3);IR(neat):
3031, 2928, 2870, 1775, 1455, 1096, 739, 698 cmꢀ1; HRMS
(FAB): calcd for C62H64O11K 1023.4088, found 1023.4066.
4.2.21. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-gluco-hept-2-
ulosyl-(2/4)-2,3,6-tri-O-benzyl-D-mannono-1,5-lactone
(13ac). Colorless syrup; [a]2D7 +26.8 (c 1.06, CHCl3); IR
(neat): 3031, 2924, 2869, 1769, 750, 739, 698 cmꢀ1; HRMS
(FAB): calcd for C62H64O11K 1023.4086, found 1023.4111.
4.2.31. 3,4,5,7-Tetra-O-benzyl-1-deoxy-D-galacto-hept-2-
ulosyl-(2/6)-2,3,4-tri-O-benzyl-D-glucono-1,5-lactone
(14ba). Colorlesssyrup;[a]2D7 +66.6 (c1.12, CHCl3); IR (neat):
3031, 2919, 2874, 1757, 1455, 1096, 739, 698 cmꢀ1; HRMS
(FAB): calcd for C62H64O11K 1023.4086, found 1023.4086.
4.2.22. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-galacto-hept-
2-ulosyl-(2/4)-2,3,6-tri-O-benzyl-D-glucono-1,5-lactone
(13ba). Colorless syrup; [a]3D0 +60.6 (c 0.83, CHCl3); IR
(neat): 3031, 2921, 2870, 1790, 1455, 1098, 737, 698 cmꢀ1
;
4.2.32. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-galacto-hept-
2-ulosyl-(2/6)-2,3,4-tri-O-benzyl-D-galactono-1,5-lac-
tone (14bb). Colorless syrup; [a]2D7 +75.8 (c 1.19, CHCl3); IR
(neat): 3031, 2917, 2869, 1750, 1455, 1109, 1057, 745, 737,
745, 698 cmꢀ1; HRMS (FAB): calcd for C62H64O11Na
1007.4346, found 1007.4362.
HRMS (FAB): calcd for C62H64O11K 1023.4086, found
1023.4082.
4.2.23. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-galacto-hept-
2-ulosyl-(2/4)-2,3,6-tri-O-benzyl-D-galactono-1,5-lac-
tone (13bb). Colorless syrup; [a]3D0 +27.4 (c 0.85, CHCl3); IR
(neat): 3031, 2923, 2870, 1788, 1455, 1100, 737, 698 cmꢀ1
;
4.2.33. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-galacto-hept-
2-ulosyl-(2/6)-2,3,4-tri-O-benzyl-D-mannono-1,5-lac-
tone (14bc). Colorless syrup; [a]2D6 +23.1 (c 1.14, CHCl3);
IR (neat): 3031, 2917, 2870, 1775, 1455, 1113, 1098, 735,
HRMS (FAB): calcd for C62H64O11K 1023.4086, found
1023.4083.
4.2.24. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-galacto-hept-
2-ulosyl-(2/4)-2,3,6-tri-O-benzyl-D-mannono-1,5-lac-
tone (13bc). Colorless syrup; [a]2D7 +28.6 (c 1.02, CHCl3);
IR (neat): 3031, 2923, 2872, 1769, 1455, 1101, 1082, 735,
698 cmꢀ1; HRMS (FAB): calcd for C62H64O11K 1023.4086,
found 1023.4081.
698 cmꢀ1
;
1023.4086, found 1023.4099.
HRMS (FAB): calcd for C62H64O11K
4.2.34. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-manno-hept-
2-ulosyl-(2/6)-2,3,4-tri-O-benzyl-D-glucono-1,5-lactone
(14ca). Colorless syrup; [a]2D7 +57.2 (c 1.32, CHCl3); IR

9190
R. Namme et al. / Tetrahedron 62 (2006) 9183–9192
(neat): 3031, 2921, 2867, 1757, 1455, 1094, 1078, 735,
698 cmꢀ1; HRMS (FAB): calcd for C62H64O11K 1023.4086,
found 1023.4081.
NMR (600 MHz, CD3OD): d 4.52–4.47 (m, 2H), 4.39 (dd,
J¼4.7, 5.0 Hz, 1H), 3.91 (m, 1H), 3.80 (m, 2H), 3.70–3.66
(m, 2H), 3.63–3.55 (m, 3H), 3.49 (d, J¼10.2 Hz, 1H,
H-30), 1.46 (s, 3H, H-10).
4.2.35. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-manno-hept-
2-ulosyl-(2/6)-2,3,4-tri-O-benzyl-D-galactono-1,5-lac-
tone (14cb). Colorless syrup; [a]2D7 +56.8 (c 1.28, CHCl3); IR
4.3.5. 1-Deoxy-a-D-galacto-hept-2-ulosyl-(2/2)-D-galac-
tono-1,5-lactone (16bb). Colorless amorphous solid; [a]D28
+60.2 (c 1.01, CH3OH); 1H NMR (600 MHz, CD3OD):
d 4.68 (d, J¼8.8 Hz, 1H, H-2), 4.35 (dd, J¼8.5, 8.5 Hz,
1H), 4.16 (dd, J¼2.2, 8.8 Hz, 1H, H-3), 4.04 (m, 1H), 3.81
(m, 1H), 3.71–3.65 (m, 3H), 3.61–3.51 (m, 4H), 1.49
(s, 3H, H-10); 13C NMR (150 MHz, CD3OD): d 175.0,
103.6, 81.2, 75.7, 74.7, 73.4, 73.0, 71.7, 71.2, 70.4, 63.5,
62.9, 22.7.
(neat): 3031, 2921, 2869, 1750, 1455, 1104, 737, 698 cmꢀ1
;
HRMS (FAB): calcd for C62H64O11K 1023.4086, found
1023.4101.
4.2.36. 3,4,5,7-Tetra-O-benzyl-1-deoxy-a-D-manno-hept-
2-ulosyl-(2/6)-2,3,4-tri-O-benzyl-D-mannono-1,5-lac-
tone (14cc). Colorless block; mp 111 ꢁC; [a]D27 +22.7
(c 0.92, CHCl3); IR (KBr): 3032, 2936, 2346, 1775, 1499,
1456, 1109, 739, 700 cmꢀ1; HRMS (FAB): calcd for
C62H64O11K 1023.4086, found 1023.4168.
4.3.6. 1-Deoxy-a-D-galacto-hept-2-ulosyl-(2/2)-D-man-
nono-1,5-lactone (16bc). Colorless amorphous solid; H
1
NMR (600 MHz, CD3OD): d 4.91 (d, J¼2.5 Hz, 1H, H-2),
4.16 (ddd, J¼8.3, 2.5, 5.8 Hz, 1H, H-5), 4.12 (ddd, J¼1.4,
4.1, 7.7 Hz, 1H, H-60), 4.00 (dd, J¼2.5, 0.8 Hz, 1H, H-3),
3.95 (dd, J¼9.9, 3.3 Hz, 1H, H-40), 3.85 (dd, J¼3.3,
1.4 Hz, 1H, H-50), 3.79 (dd, J¼2.5, 12.4 Hz, 1H, H-6),
3.75 (dd, J¼0.8, 8.3 Hz, 1H, H-4), 3.69 (dd, J¼5.8,
12.4 Hz, 1H, H-6), 3.67 (dd, J¼7.7, 11.5 Hz, 1H, H-70),
3.57 (d, J¼9.9 Hz, 1H, H-30), 3.56 (dd, J¼4.1, 11.5 Hz,
1H, H-70), 1.45 (s, 3H, H-10); 13C NMR (150 MHz,
CD3OD): d 172.8, 103.4, 82.2, 77.3, 74.8, 74.2, 71.6, 71.6,
70.8, 69.8, 63.3, 62.8, 22.6.
4.3. General procedure 2: deprotection
To a solution of 11aa (73.0 mg, 0.07 mmol) in THF (2.5 mL)
were added basic alumina (18.0 mg) and 20% Pd(OH)2/C
(37.0 mg) under an argon atmosphere, and the mixture was
stirred under a hydrogen atmosphere (balloon) at room tem-
perature. After 20 h, to the mixture was added MeOH
(0.3 mL) and stirred for 28 h. The reaction mixture was fil-
tered through filter paper, and the filtrate was evaporated
and dried to give 16aa (28.0 mg).
4.3.1. 1-Deoxy-D-gluco-hept-2-ulosyl-(2/2)-D-glucono-
1,5-lactone (16aa). Colorless amorphous solid; [a]D23
+96.2 (c 1.24, CH3OH); 1H NMR (600 MHz, CD3OD):
d 4.61 (m, 1H), 4.52 (m, 1H), 4.48 (m, 1H), 3.99 (m, 1H),
3.86–3.58 (m, 8H), 1.53 (s, 3H, H-10); 13C NMR
(150 MHz, CD3OD): d 176.0, 103.5, 81.5, 77.8, 75.2, 75.1,
74.0, 73.8, 71.8, 71.4, 64.4, 62.8, 23.2.
4.3.7. 1-Deoxy-a-D-manno-hept-2-ulosyl-(2/2)-D-glu-
cono-1,5-lactone (16ca). Colorless amorphous solid; 1H
NMR (600 MHz, CD3OD): d 4.46 (m, 1H), 4.38 (m, 1H),
3.90 (m, 1H), 3.77 (dd, J¼1.7, 11.8 Hz, 1H), 3.72 (dd,
J¼3.3, 9.1 Hz, 1H, H-40), 3.68 (dd, J¼3.9, 11.8 Hz, 1H),
3.63–3.59 (m, 3H), 3.55 (d, J¼3.3 Hz, 1H, H-30), 3.51 (dd,
J¼1.9, 6.1 Hz, 1H), 3.47 (dd, J¼9.1, 9.4 Hz, 1H, H-50),
1.41 (s, 3H, H-10); 13C NMR (150 MHz, CD3OD):
d 176.0, 104.6, 81.4, 76.0, 74.4, 73.8, 73.7, 72.5, 71.2,
67.9, 64.3, 63.0, 22.3.
4.3.2. 1-Deoxy-a-D-gluco-hept-2-ulosyl-(2/2)-D-galac-
tono-1,5-lactone (16ab). Colorless amorphous solid; [a]D27
+60.8 (c 0.23, CH3OH); 1H NMR (600 MHz, CD3OD):
d 4.67 (d, J¼8.8 Hz, 1H, H-2), 4.36 (dd, J¼8.3, 8.8 Hz,
1H), 4.15 (dd, J¼2.2, 8.8 Hz, 1H, H-3), 3.82 (ddd, J¼2.2,
5.8, 10.2 Hz, 1H), 3.74 (dd, J¼2.5, 11.6 Hz, 1H), 3.70 (m,
1H), 3.58–3.52 (m, 4H), 3.23 (m, 1H), 3.09 (d, J¼9.9 Hz,
1H, H-30), 1.47 (s, 3H, H-10); 13C NMR (150 MHz,
CD3OD): d 175.0, 103.3, 81.2, 78.1, 75.7, 75.1, 74.4, 73.4,
71.7, 70.3, 63.5, 62.5, 22.8.
4.3.8. 1-Deoxy-a-D-manno-hept-2-ulosyl-(2/2)-D-galac-
tono-1,5-lactone (16cb). Colorless amorphous solid; 1H
NMR (600 MHz, CD3OD): d 4.69 (d, J¼8.8 Hz, 1H, H-2),
4.32 (dd, J¼8.5, 8.5 Hz, 1H, H-6), 4.14 (dd, J¼2.5,
8.8 Hz, 1H, H-3), 3.82 (ddd, J¼2.2, 5.8, 9.9 Hz, 1H, H-60),
3.78 (dd, J¼3.3, 9.6 Hz, 1H, H-40), 3.73 (dd, J¼2.2,
11.6 Hz, 1H, H-70), 3.69 (m, 1H, H-5), 3.64 (d, J¼3.3 Hz,
1H, H-30), 3.59 (dd, J¼5.8, 11.6 Hz, 1H, H-70), 3.56 (m,
1H, H-4), 3.55 (dd, J¼6.6, 8.5 Hz, 1H, H-6), 3.53 (dd,
J¼9.6, 9.9 Hz, 1H, H-50) 1.39 (s, 3H, H-10); 13C NMR
(150 MHz, CD3OD): d 174.8, 104.4, 81.2, 75.3, 75.1, 74.5,
73.5, 72.6, 70.3, 67.8, 63.6, 62.8, 21.9.
4.3.3. 1-Deoxy-a-D-gluco-hept-2-ulosyl-(2/2)-D-man-
nono-1,5-lactone (16ac). Colorless amorphous solid;
[a]2D4 +118.6 (c 0.5, CH3OH); 1H NMR (600 MHz,
CD3OD): d 4.86 (d, J¼2.8 Hz, 1H, H-2), 4.12 (ddd, J¼8.3,
5.8, 2.5 Hz, 1H, H-5), 3.95 (dd, J¼1.1, 2.8 Hz, 1H, H-3),
3.87 (ddd, J¼9.9, 2.2, 6.6 Hz, 1H, H-60), 3.78 (dd, J¼9.1,
9.6 Hz, 1H, H-40), 3.75 (dd, J¼2.5, 12.4 Hz, 1H, H-6),
3.71 (dd, J¼2.2, 11.8 Hz, 1H, H-70), 3.7 (dd, J¼1.1,
8.3 Hz, 1H, H-4), 3.64 (dd, J¼6.6, 11.8 Hz, 1H, H-70),
3.49 (dd, J¼5.8, 12.4 Hz, 1H, H-6), 3.13 (dd, J¼9.9,
9.1 Hz, 1H, H-50), 3.11 (d, J¼9.6 Hz, 1H, H-30), 1.45 (s,
3H, –CH3); 13C NMR (150 MHz, CD3OD): d 172.5, 103.1,
82.2, 78.3, 77.2, 75.3, 74.9, 72.1, 70.8, 69.9, 63.0, 62.8, 22.7.
4.3.9. 1-Deoxy-a-D-manno-hept-2-ulosyl-(2/2)-D-man-
nono-1,5-lactone (16cc). Colorless amorphous solid; H
1
NMR (600 MHz, CD3OD): d 4.79 (d, J¼4.4 Hz, 1H, H-2),
4.43 (dd, J¼4.4, 2.8 Hz, 1H, H-3), 4.24 (dd, J¼2.8, 9.1 Hz,
1H, H-4), 3.96 (dd, J¼3.3, 9.6 Hz, 1H, H-40), 3.89–3.85
(m, 2H, H-5, H-60), 3.74 (dd, J¼2.2, 11.6 Hz, 1H, H-70),
3.71 (d, J¼3.3 Hz, 1H, H-30), 3.7 (dd, J¼2.6, 11.6 Hz, 1H,
H-6), 3.57 (dd, J¼6.6, 11.6 Hz, 1H, H-70), 3.56 (dd, J¼5.2,
11.6 Hz, 1H, H-6), 3.47 (dd, J¼9.6, 9.6 Hz, 1H, H-50), 1.39
(s, 3H, H-10); 13C NMR (150 MHz, CD3OD): d 176.0,
4.3.4. 1-Deoxy-a-D-galacto-hept-2-ulosyl-(2/2)-D-glu-
cono-1,5-lactone (16ba). Colorless amorphous solid; 1H

R. Namme et al. / Tetrahedron 62 (2006) 9183–9192
9191
103.9, 79.7, 75.6, 74.2, 72.5, 71.4, 70.9, 69.5, 68.1, 64.3,
63.1, 21.9.
4.3.16. 1-Deoxy-a-D-manno-hept-2-ulosyl-(2/3)-D-man-
nono-1,5-lactone (15cc). Colorless amorphous solid; [a]D28
+76.4 (c 0.99, CH3OH); 1H NMR (600 MHz, CD3OD):
d 4.61 (dd, J¼3.3 Hz, 1H, H-2), 4.18 (dd, J¼3.3, 0.6 Hz,
1H, H-3), 4.15 (ddd, J¼2.5, 5.0, 9.9 Hz, 1H, H-60), 4.03
(ddd, J¼2.5, 5.2, 8.0 Hz, 1H, H-5), 3.82 (m, 1H, H-4),
3.75 (dd, J¼2.5, 12.7 Hz, 1H, H-6), 3.72 (dd, J¼3.3,
9.6 Hz, 1H, H-40), 3.67 (dd, J¼2.5, 11.8 Hz, 1H, H-70),
3.62 (dd, J¼5.0, 12.7 Hz, 1H, H-6), 3.60 (dd, J¼5.2,
11.8 Hz, 1H, H-70), 3.48 (d, J¼3.3 Hz, 1H, H-30), 3.46 (dd,
J¼9.6, 9.9 Hz, 1H, H-50), 1.41 (s, 3H, H-10); 13C NMR
(150 MHz, CD3OD): d 175.0, 103.3, 82.6, 76.5, 75.2, 74.4,
72.4, 70.2, 68.8, 68.0, 62.9, 62.4, 22.4.
4.3.10. 1-Deoxy-a-D-gluco-hept-2-ulosyl-(2/3)-D-glu-
cono-1,5-lactone (15aa). Colorless amorphous solid; [a]D28
+87.7 (c 1.02, CH3OH); 1H NMR (600 MHz, CD3OD):
d 4.57 (dd, J¼6.9, 6.9 Hz, 1H, H-3), 4.49 (d, J¼6.9 Hz,
1H, H-2), 4.43 (dd, J¼6.9, 8.0 Hz, 1H, H-4), 3.89 (m, 1H,
H-5), 3.72–3.66 (m, 3H, H-6, H-50, H-60), 3.62–3.53 (m,
3H, H-6, H-40, H-70), 3.29 (m, 1H, H-70), 3.14 (d,
J¼9.4 Hz, 1H, H-30), 1.46 (s, 3H, H-10); 13C NMR
(150 MHz, CD3OD): d 176.1, 102.9, 78.8, 77.7, 76.1, 75.3,
74.5, 72.1, 71.4, 71.2, 64.0, 62.2, 21.9.
4.3.11. 1-Deoxy-a-D-gluco-hept-2-ulosyl-(2/3)-D-galac-
tono-1,5-lactone (15ab). Colorless amorphous solid; [a]D25
+44.4 (c 1.02, CH3OH); 1H NMR (600 MHz, CD3OD):
d 4.52–4.48 (m, 2H), 4.28 (m, 1H), 3.80 (m, 1H), 3.72–
3.69 (m, 2H), 3.60–3.50 (m, 4H), 3.17 (dd, J¼9.4, 9.6 Hz,
1H), 3.10 (dd, J¼9.6 Hz, 1H, H-2), 1.45 (s, 3H, H-10); 13C
NMR (150 MHz, CD3OD): d 175.9, 102.8, 80.1, 78.2,
76.0, 75.1, 75.1, 74.6, 72.1, 70.5, 63.7, 62.7, 22.1.
4.3.17. 1-Deoxy-a-D-gluco-hept-2-ulosyl-(2/4)-D-glu-
cono-1,5-lactone (20aa). Colorless amorphous solid; [a]D25
+93.0 (c 0.96, CH3OH); H NMR (600 MHz, D2O): d 4.65
(m, 1H), 4.41 (m, 1H), 4.15 (m, 1H), 3.74–3.62 (m, 5H),
3.57–3.51 (m, 2H), 3.19 (m, 1H), 3.12 (m, 1H), 1.28
(s, 3H, H-10); 13C NMR (150 MHz, D2O): d 178.0,
102.9, 80.1, 77.0, 74.1, 74.0, 73.8, 73.7, 73.4, 70.7, 62.3,
61.4, 21.4.
1
4.3.12. 1-Deoxy-a-D-galacto-hept-2-ulosyl-(2/3)-D-glu-
cono-1,5-lactone (15ba). Colorless amorphous solid; 1H
NMR (600 MHz, CD3OD): d 4.58 (dd, J¼6.9, 7.2 Hz, 1H,
H-3), 4.51 (d, J¼7.2 Hz, 1H, H-2), 4.43 (dd, J¼6.9,
7.7 Hz, 1H, H-4), 3.95 (m, 1H), 3.87 (m, 1H, H-5), 3.82
(m, 1H), 3.68–3.65 (m, 2H), 3.63–3.52 (m, 4H), 1.46 (s,
3H, H-10); 13C NMR (150 MHz, CD3OD): d 176.1, 103.2,
78.7, 76.0, 74.4, 73.1, 72.1, 71.9, 71.6, 71.0, 64.0, 62.6, 21.9.
4.3.18. 1-Deoxy-a-D-gluco-hept-2-ulosyl-(2/4)-D-galac-
tono-1,5-lactone (20ab). Colorless amorphous solid; [a]D25
+135.2 (c 0.6, H2O); H NMR (600 MHz, D2O): d 4.46
(m, 2H), 4.40 (m, 1H), 4.04 (m, 1H), 3.84 (m, 1H), 3.70
(m, 1H), 3.66–3.58 (m, 3H), 3.54 (m, 1H), 3.24 (m, 1H),
3.19 (m, 1H), 1.28 (s, 3H, H-10); 13C NMR (150 MHz,
D2O): d 177.0, 102.0, 81.0, 77.0, 74.6, 73.6, 73.3, 73.3,
71.4, 70.3, 61.0, 60.5, 21.4.
1
4.3.13. 1-Deoxy-D-galacto-hept-2-ulosyl-(2/3)-D-galac-
tono-1,5-lactone (15bb). Colorless amorphous solid; 1H
NMR (600 MHz, CD3OD): d 4.53 (d, J¼8.0 Hz, 1H, H-2),
4.48 (dd, J¼8.0, 8.0 Hz, 1H), 4.27 (dd, J¼2.5, 8.0 Hz, 1H,
H-3), 3.93 (m, 1H), 3.79 (m, 1H, H-4), 3.71–3.69 (m, 2H),
3.66 (dd, J¼3.0, 10.2 Hz, 1H, H-40), 3.60–3.54 (m, 3H),
3.50 (dd, J¼10.2 Hz, 1H, H-30), 1.48 (s, 3H, H-10); 13C
NMR (150 MHz, CD3OD): d 176.0, 103.1, 80.0, 76.0,
74.9, 74.5, 73.7, 71.7, 71.4, 70.6, 63.7, 63.1, 21.9.
4.3.19. 1-Deoxy-a-D-gluco-hept-2-ulosyl-(2/4)-D-man-
nono-1,5-lactone (20ac). Colorless amorphous solid; [a]D25
+135.2 (c 0.6, H2O); 1H NMR (600 MHz, D2O): d 4.65 (d,
J¼2.8 Hz, 1H, H-2), 4.29 (m, 1H, H-5), 4.03 (m, 1H, H-
3), 3.93 (m, 1H, H-4), 3.71 (dd, J¼2.2, 12.4 Hz, 1H, H-70),
3.63–3.59 (m, 2H, H-6, H-6), 3.55 (dd, J¼5.0, 12.4 Hz,
1H, H-70), 3.46 (dd, J¼9.4, 9.6 Hz, 1H), 3.37 (ddd, J¼2.2,
5.0, 9.9 Hz, 1H, H-60), 3.21 (dd, J¼9.6, 9.6 Hz, 1H), 3.10
(d, J¼9.9 Hz, 1H, H-30), 1.37 (s, 3H, H-10); 13C NMR
(150 MHz, D2O): d 175.2, 102.7, 81.3, 76.4, 73.9, 73.8,
73.4, 70.3, 70.1, 68.9, 61.9, 61.1, 22.1.
4.3.14. 1-Deoxy-a-D-manno-hept-2-ulosyl-(2/3)-D-glu-
cono-1,5-lactone (15ca). Colorless amorphous solid; [a]D26
+59.6 (c 0.69, CH3OH); 1H NMR (600 MHz, CD3OD):
d 4.63 (d, J¼7.2 Hz, 1H, H-2), 4.59 (dd, J¼6.9, 7.2 Hz,
1H, H-3), 4.53 (dd, J¼4.4, 6.9 Hz, 1H, H-4), 3.87 (m, 1H),
3.78 (dd, J¼3.3, 9.6 Hz, 1H, H-40), 3.72–3.69 (m, 2H),
3.64–3.58 (m, 3H), 3.59 (d, J¼3.3 Hz, 1H, H-30), 3.52 (dd,
J¼9.6, 9.6 Hz, 1H, H-50), 1.42 (s, 3H, H-10); 13C NMR
(150 MHz, CD3OD): d 176.8, 104.1, 80.1, 76.2, 75.2, 74.7,
73.0, 72.7, 72.3, 67.9, 64.2, 62.6, 20.8.
4.3.20. 1-Deoxy-a-D-galacto-hept-2-ulosyl-(2/4)-D-glu-
cono-1,5-lactone (20ba). Colorless amorphous solid; 1H
NMR (600 MHz, CD3OD): d 4.62 (dd, J¼4.9, 7.1 Hz, 1H,
H-4), 4.24 (dd, J¼3.6, 4.9 Hz, 1H, H-3), 4.21 (d, J¼3.6 Hz,
1H, H-2), 4.07 (ddd, J¼1.1, 4.1, 8.2 Hz, 1H, H-60), 4.05
(ddd, J¼7.1, 3.3, 3.6 Hz, 1H, H-5), 3.88 (dd, J¼3.3,
12.7 Hz, 1H, H-6), 3.76 (dd, J¼3.3, 1.1 Hz, 1H, H-50), 3.67–
3.64 (m, 3H, H-6, H-40, H-70), 3.56 (dd, J¼4.1, 11.3 Hz, 1H,
H-70), 3.48 (d, J¼9.9 Hz, 1H, H-30), 1.44 (s, 3H, H-10).
4.3.15. 1-Deoxy-a-D-manno-hept-2-ulosyl-(2/3)-D-gal-
actono-1,5-lactone (15cb). Colorless amorphous solid;
[a]2D5 +7.39 (c 0.57, CH3OH); 1H NMR (600 MHz,
CD3OD): d 4.61 (dd, J¼7.7, 8.0 Hz, 1H, H-50), 4.51 (d,
J¼8.0 Hz, 1H, H-2), 4.23 (dd, J¼1.7, 8.0 Hz, 1H, H-3),
3.80 (dd, J¼2.2, 11.3 Hz, 1H, H-6), 3.75 (dd, J¼3.3,
9.6 Hz, 1H, H-70), 3.67 (dd, J¼2.2, 7.7 Hz, 1H, H-40), 3.67
(m, 1H, H-5), 3.57–3.52 (m, 4H, H-4, H-6, H-30, H-60),
3.47 (dd, J¼9.6, 9.9 Hz, 1H, H-70), 1.44 (s, 3H, H-10); 13C
NMR (150 MHz, CD3OD): d 175.9, 104.0, 80.0, 79.6,
75.9, 75.6, 75.0, 74.7, 72.6, 69.7, 68.0, 63.5, 20.8.
4.3.21. 1-Deoxy-a-D-galacto-hept-2-ulosyl-(2/4)-D-gal-
actono-1,5-lactone (20bb). Colorless amorphous solid;
1H NMR (600 MHz, CD3OD): d 4.99 (dd, J¼2.2, 5.8 Hz,
1H, H-4), 4.33 (dd, J¼5.8, 6.3 Hz, 1H, H-3), 4.17 (d,
J¼6.3 Hz, 1H, H-2), 3.96–3.90 (m, 2H), 3.78–3.76 (m,
2H), 3.62–3.55 (m, 4H), 3.46 (d, J¼9.9 Hz, 1H), 1.46
(s, 3H, H-10); 13C NMR (150 MHz, CD3OD): d 177.1,
102.9, 83.0, 76.3, 75.4, 75.3, 73.4, 73.2, 71.3, 71.1, 62.7,
61.5, 21.6.

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R. Namme et al. / Tetrahedron 62 (2006) 9183–9192
4. Krog-Jensen, C.; Oscarson, S. J. Org. Chem. 1998, 63, 1780–1784.
5. Dondoni, A. Pure Appl. Chem. 2000, 72, 1577–1588 and refer-
ences cited therein.
6. (a) Li, X. L.; Ohtake, H.; Takahashi, H.; Ikegami, S.
Tetrahedron 2001, 57, 4283–4295; (b) Li, X. L.; Ohtake, H.;
Takahashi, H.; Ikegami, S. Synlett 2001, 1885–1888; (c)
Namme, R.; Mitsugi, T.; Takahashi, H.; Ikegami, S.
Tetrahedron Lett. 2005, 46, 3033–3036.
7. (a) Li, X. L.; Ohtake, H.; Takahashi, H.; Ikegami, S.
Tetrahedron 2001, 57, 4297–4309; (b) Li, X. L.; Takahashi,
H.; Ohtake, H.; Shiro, M.; Ikegami, S. Tetrahedron 2001, 57,
8053–8066.
8. Yamanoi, T.; Oda, Y.; Yamazaki, I.; Shinbara, M.; Morimoto,
K.; Matsuda, S. Lett. Org. Chem. 2005, 2, 242–246.
9. Other groups also investigated the O-glycosidation of exo-
glycals: (a) Chang, C.-F.; Yang, W.-B.; Chang, C.-C.; Lin,
C.-H. Tetrahedron Lett. 2002, 43, 6515–6519; (b) Lin, H.-C.;
Yang, W.-B.; Gu, Y.-F.; Chen, C.-Y.; Wu, C.-Y.; Lin, C.-H.
Org. Lett. 2003, 5, 1087–1089; (c) Colinas, P. A.;
Lieberknecht, A.; Bravo, R. D. Tetrahedron Lett. 2002, 43,
9065–9068; (d) Colinas, P. A.; Ponzinibbio, A.; Lieberknecht,
A.; Bravo, R. D. Tetrahedron Lett. 2003, 44, 7985–7988.
10. Enzymatic O-glycosidation of heptenitols: Schlesselmann, P.;
Fritz, H.; Lehmann, J.; Uchiyama, T.; Brewer, C. F.; Hehre,
E. J. Biochemistry 1982, 21, 6606–6614.
11. O-Glycosidation of heptenitols promoted by iodonium ion, see:
Noort, D.; Veeneman, G. H.; Boons, G.-J. P. H.; van der Marel,
G. A.; Mulder, G. J.; van Boom, J. H. Synlett 1990, 205–206.
12. For reviews of exo-glycal chemistry, see: (a) Taillefumier, C.;
Chapleur, Y. Chem. Rev. 2004, 104, 263–292; (b) Lin, C.-H.;
Lin, H.-C.; Yang, W.-B. Curr. Top. Med. Chem. 2005, 5,
1431–1457.
4.3.22. 1-Deoxy-a-D-galacto-hept-2-ulosyl-(2/4)-D-
mannono-1,5-lactone (20bc). Colorless amorphous solid;
13C NMR (150 MHz, CD3OD): d 174.8, 103.5, 82.9, 74.7,
74.6, 73.7, 71.6, 71.1, 70.8, 69.6, 63.2, 62.8, 22.9.
4.3.23. 1-Deoxy-a-D-manno-hept-2-ulosyl-(2/4)-D-gal-
actono-1,5-lactone (20cb). Colorless amorphous solid;
1H NMR (600 MHz, CD3OD): d 4.37 (m, 2H), 4.18 (dd,
J¼8.5, 8.5 Hz, 1H), 4.13 (m, 1H), 4.02 (dd, J¼5.0,
11.3 Hz, 1H), 3.84–3.80 (m, 2H), 3.71–3.62 (m, 4H), 3.52
(m, 1H), 1.46 (s, 3H, H-10); 13C NMR (150 MHz,
CD3OD): d 177.1, 102.9, 83.0, 76.3, 75.4, 75.3, 73.4, 73.2,
71.3, 71.1, 62.7, 61.5, 21.6.
4.3.24. 1-Deoxy-a-D-manno-hept-2-ulosyl-(2/4)-D-man-
nono-1,5-lactone (20cc). Colorless amorphous solid; [a]D25
+76.8 (c 0.48, CH3OH); 1H NMR (600 MHz, CD3OD):
d 4.47 (d, J¼3.0 Hz, 1H, H-2), 4.34 (ddd, J¼5.2, 5.5,
3.3 Hz, 1H, H-5), 4.12 (dd, J¼2.2, 5.2 Hz, 1H, H-4), 4.01
(ddd, J¼3.0, 2.2 Hz, 1H, H-3), 3.78 (dd, J¼3.3, 12.4 Hz,
1H, H-6), 3.74 (dd, J¼2.2, 11.8 Hz, 1H, H-70), 3.73–3.69
(m, 2H, H-40, H-6), 3.59 (dd, J¼6.1, 11.8 Hz, 1H, H-70),
3.54 (d, J¼3.3 Hz, 1H, H-30), 3.48 (dd, J¼9.6, 9.9 Hz, 1H,
H-50), 3.39 (ddd, J¼2.2, 6.1, 9.9 Hz, 1H, H-60), 1.45 (s,
3H, H-10); 13C NMR (150 MHz, CD3OD): d 174.4, 104.4,
83.7, 76.2, 75.1, 74.8, 72.5, 70.5, 69.5, 67.9, 63.4, 63.0, 21.7.
4.3.25. 1-Deoxy-a-D-galacto-hept-2-ulosyl-(2/6)-D-gal-
actono-1,5-lactone (21bb). Colorless amorphous solid; H
1
NMR (600 MHz, CD3OD): d 4.26 (d, J¼8.8 Hz, 1H, H-2),
4.17 (dd, J¼8.3, 8.8 Hz, 1H, H-3), 4.08 (dd, J¼3.3,
8.3 Hz, 1H, H-4), 3.80–3.78 (m, 2H, H-5, H-50), 3.70 (dd,
J¼3.3, 9.9 Hz, 1H, H-40), 3.68 (m, 1H, H-60), 3.61 (dd,
J¼6.9, 11.3 Hz, 1H), 3.58 (dd, J¼5.5, 11.3 Hz, 1H), 3.55
(dd, J¼5.8, 9.6 Hz, 1H), 3.51 (dd, J¼6.3, 9.6 Hz, 1H),
3.47 (dd, J¼9.9 Hz, 1H, H-30), 1.34 (s, 3H, H-10).
13. (a) RajanBabu, T. V.; Reddy, G. S. J. Org. Chem. 1986, 51,
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14. For synthetic procedures of compounds 7–10, see Supplemen-
tary data.
15. CCDC 610513 contains the supplementary crystallographic
data for compound 14cc. These data can be obtained free of
charge from The Cambridge Crystallographic Data Center
via www.ccdc.cam.ac.uk/data_request/cif.
16. Tvaroska, I.; Travel, F. R. Carbon–proton coupling constants in
the conformational analysis of sugar molecules. In Advances in
Carbohydrate Chemistry and Biochemistry; Horton, D., Ed.;
Academic: San Diego, CA, 1995; Vol. 51, pp 15–61.
17. Bieg, T.; Szeja, W. Synthesis 1985, 76–77.
Acknowledgements
We are grateful to Ms. J. Shimode and Ms. A. Tonoki for per-
forming the spectroscopic measurements. This work was
partially supported by a Grant-in-Aid for Scientific Research
from the Ministry of Education, Science, Sports, and Culture
of Japan.
Supplementary data
18. Liu, H.-J.; Yip, J. Tetrahedron Lett. 1997, 38, 2253–2256.
19. Schuda, P. F.; Cichowicz, M. B.; Heimann, M. R. Tetrahedron
Lett. 1983, 24, 3829–3830.
Supplementary data associated with this article can be found
in the online version, at doi:10.1016/j.tet.2006.07.032.
20. Binkley, R. W.; Hehmann, D. G. J. Org. Chem. 1990, 55,
378–380.
References and notes
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786; (b) Angibeaud, P.; Defaye, J.; Gadelle, A.; Utille, J.-P.
Synthesis 1985, 1123–1125.
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23. In some cases, decomposition of debenzylated disaccharides
15, 16, 20, and 21 was observed during work-up. Filtration
through a celite pad caused decomposition, and therefore filter
paper was used for separation of the catalyst.
24. For the peak assignments in 1H and 13C NMR spectra for com-
pounds 11–14, see Supplementary data.
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