Preparation of partially benzylated mono-, di-, and trisaccharides by selective cleavage of the β-fructofuranosidic linkage in fully benzylated sucrose and sucrose-related oligosaccharides under acidic conditions

Article abstract of DOI:10.1016/j.carres.2008.03.024

Several partially benzylated mono-, di-, and trisaccharides having an anomeric hydroxyl group were successfully prepared by selective cleavage of the β-fructofuranosidic linkage in fully benzylated sucrose and sucrose-related oligosaccharides derived from lactosucrose, raffinose, melezitose, stachyose, and nystose under acidic conditions using 1:10 75% aqueous sulfuric acid-dioxane at room temperature for 1 h.

Full text of DOI:10.1016/j.carres.2008.03.024

Available online at www.sciencedirect.com
Carbohydrate Research 343 (2008) 1366–1372
Note
Preparation of partially benzylated mono-, di-, and trisaccharides
by selective cleavage of the b-fructofuranosidic linkage in fully
benzylated sucrose and sucrose-related oligosaccharides under
acidic conditions
Takashi Yamanoi,a,* Noriko Misawa,a,b Sho Matsudaa and Mikio Watanabeb
aThe Noguchi Institute, 1-8-1 Kaga, Itabashi-ku, Tokyo 173-0003, Japan
bDepartment of Chemistry, School of Science, Tokai University, Kitakaname 1117, Hiratsuka, Kanagawa 259-1292, Japan
Received 21 August 2007; received in revised form 14 March 2008; accepted 17 March 2008
Available online 25 March 2008
Abstract—Several partially benzylated mono-, di-, and trisaccharides having an anomeric hydroxyl group were successfully
prepared by selective cleavage of the b-fructofuranosidic linkage in fully benzylated sucrose and sucrose-related oligosaccharides
derived from lactosucrose, raffinose, melezitose, stachyose, and nystose under acidic conditions using 1:10 75% aqueous sulfuric
acid–dioxane at room temperature for 1 h.
Ó 2008 Elsevier Ltd. All rights reserved.
Keywords: Partially benzylated sugars; Acidic hydrolysis; b-Fructofuranosidic linkage; Sucrose-related oligosaccharides; Benzylated oligosaccharides
Partially benzylated sugars are significant reagents
in synthetic carbohydrate chemistry. In particular, par-
tially benzylated sugar derivatives having a free ano-
meric hydroxyl group are often used as glycosyl
donors in glycosidation studies.1 Partially benzylated
sugar derivatives can be produced by cleaving the glyco-
sidic bonds of fully benzylated oligosaccharides.
Our recent study showed that fully benzylated cyclo-
maltohexaose was hydrothermolyzed into 2,3,6-tri-O-
benzyl-D-glucopyranose and partially benzylated
maltooligosaccharides.2
Ness et al. reported that acidic hydrolysis of fully
benzylated sucrose 13 using 2 M sulfuric acid–acetic acid
at 65 °C for 6 h gave 2,3,4,6-tetra-O-benzyl-D-gluco-
pyranose (2) and 1,3,4,6-tetra-O-benzyl-D-fructo-
furanose (3) in 76% and 17% yields, respectively.4
Their study indicated that the b-fructofuranosidic link-
age in fully benzylated sucrose could be easily cleaved
under acidic conditions, though more appropriate
hydrolysis conditions were necessary for increasing the
yield of 3.
Our attention focused on sucrose-related oligosaccha-
rides, such as commercially available lactosucrose, raffi-
nose, melezitose, stachyose, and nystose, which are
otherwise effective for the development of bifidobacte-
ria.5 As they have the b-fructofuranosidic linkage and
consist of sucrose and one or two more sugar moieties
(glucose, galactose, or fructose), we expected that the
selective cleavage of the b-fructofuranosidic linkages in
the fully benzylated derivatives of these sucrose-related
oligosaccharides (4–8) under acidic conditions could
produce the partially benzylated disaccharides
Galb1?4Glu 9, Gala1?6Glu 10, Glua1?3Fru 11,
and trisaccharide Gala1?6Gala1?6Glu 12 in addition
to the partially benzylated monosaccharides 2, 3, and
3,4,6-tri-O-benzyl-D-fructofuranose (13) (see Scheme
1). They are all synthetically useful sugar derivatives
having a free anomeric hydroxyl group. For example,
some of them are appropriate reagents for preparing
glycosphingolipids and their analogs.6
*
Corresponding author. Tel./fax: +81
tyama@noguchi.or.jp
3
5944 3213; e-mail:
0008-6215/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2008.03.024

T. Yamanoi et al. / Carbohydrate Research 343 (2008) 1366–1372
1367
OR
RO
OR
OR
O
OR
RO
RO
O
OBn
O
1'
O 1'
RO
RO
RO
BnO
OH
BnO
1
O
BnO
OH
BnO
O
O
RO
O
1
RO
BnO
BnO
BnO
O
RO
RO
O
RO
RO
O
O
RO
OBn
OH
O
OH
1
RO
O
1
BnO
RO
1
BnO
RO
RO
RO
RO
2
3
13
OR
O
1'
OR
RO
O
1''
RO
RO
Lactosucrose: R= H
Sucrose: R= H
OR
OBn
4: R= Bn
1''
1: R= Bn
RO
BnO
BnO
Raffinose: R= H
O
1'
OBn
O
5: R= Bn
OBn
BnO
BnO
1'
O
O
O
BnO
BnO
1
BnO
BnO
OR
O
BnO
1
Hydrolysis
OH
OR
BnO
RO
RO
9
O
BnO
10
OH
RO
RO
O
1
OR
O
1''
RO
O
RO
RO
RO
RO
O
O
1
RO
RO
OBn
O
RO
BnO
OH
O
RO
O
O
O
BnO
BnO
O
1'
O
1'
RO
RO
RO
1''
O
RO
OBn
1 OBn
O
O
BnO
BnO
BnO
OR
1' OR
O
RO
OBn
OBn
RO
1'
O
RO
1''
OR
OR
O
1
O
RO
RO
O
1''
O
1'
RO
RO
RO
BnO
O
BnO
BnO
11
O
O
RO
O
RO
RO
Melezitose: R= H
O
OR
BnO
OR
1
1'''
1'''
RO
BnO
RO
6: R= Bn
BnO
OH
Stachyose: R= H
Nistose: R= H
12
7: R= Bn
8: R= Bn
Scheme 1.
Table 1. Benzylation of sucrose, and sucrose-related oligosaccharides
This paper describes the effective preparation of the
partially benzylated mono-, di-, and trisaccharide
derivatives 2, 3, 9–13 by selective cleavage of the b-fruc-
tofuranosidic linkage in the fully benzylated sucrose-
related oligosaccharides 4–8 under acidic conditions.
Preparation of fully benzylated sucrose and sucrose-
related oligosaccharides: As the benzylation of sucrose
using benzyl bromide, silver oxide, and barium oxide
in dimethylformamide gave 1 in only 29% yield,3a we
introduced benzyl groups into sucrose, lactosucrose, raf-
finose, melezitose, stachyose, and nystose by a different
benzylation method using benzyl bromide and sodium
hydride in DMF.3b The benzylation method could suc-
cessfully produce 1, and 4–8 in yields of 79%, 67%,
78%, 89%, 53%, and 84%, respectively. The purity and
the hydration of these commercial sucrose-related oligo-
saccharides likely influence the benzylation yields. The
results are summarized in Table 1.
Entrya
Starting material
Product
Yield (%)
1b
2c
3c
4c
5g
6g
Sucrose
1
4
5
6
7
8
79
67
78
89
53
84
Lactosucrosed
Raffinosee
Melezitosef
Stachyoseh
Nystose
a Reaction was done using NaH and benzyl bromide in DMF
overnight.
b NaH (32 equiv), benzyl bromide (9.2 equiv).
c NaH (44 equiv), benzyl bromide (15 equiv).
d The purity was ca. 90%.
e 5 Hydrate was used.
f 1 Hydrate was used.
g NaH (56 equiv), benzyl bromide (28 equiv).
h 4 Hydrate was used.
using 1:1 3 M HCl–THF at reflux for 1 day scarcely pro-
moted the hydrolysis of 1. In contrast, conditions$ using
1:10 75% aqueous sulfuric acid–1,4-dioxane at room
temperature for 1 h smoothly hydrolyzed 1 to 2 and 3
in yields of 94% and 85%, respectively. The method
was applicable to the hydrolysis of 1 on a multigram
scale (see Section 1).
Hydrolysis of fully benzylated sucrose and sucrose-
related oligosaccharides: First, we investigated the acidic
conditions for hydrolyzing 1 into 2 and 3. Conditionsà
It was reported that 2 M H2SO4–AcOH at 90 °C for 24 h hydrolyzed
methyl 2,3,4,6-tetra-O-benzyl-a-D-glucopyranoside into 2 in 30%
yield.7
à It was reported that 3 M HCl–THF under reflux for 48 h could
hydrolyze benzyl 2-acetamido-2-deoxy-3,4,6-tri-O-benzyl-2-deoxy-b-
D-glucopyranoside into 2-amino-2-deoxy-3,4,6-tri-O-benzyl-2-deoxy-
D-glucopyranose.8
$ It was reported that 1:10 75% aq H2SO4–1,4-dioxane at 100 °C for 3 h
could hydrolyze fully benzylated cyclomaltoheptaose into 2,3,6-tri-O-
benzyl-D-glucopyranose in 43% yield.9

1368
T. Yamanoi et al. / Carbohydrate Research 343 (2008) 1366–1372
Table 2. Preparation of mono-, di-, and trisaccharide units 2, 3, 9–13
by the acidic hydrolysis of 1, 4–8
Chemicals Industries, Ltd. MelezitoseꢀH2O, stach-
yoseꢀ4H2O, and nystoseꢀ3H2O were purchased from
Tokyo Chemical Industry Co., Ltd. The 1H and 13C
NMR spectra were recorded on an ECA-600 spectro-
meter (JEOL) in CDCl3 using TMS as the internal
standard. Optical rotations were recorded on a JASCO
DIP-360 digital polarimeter. HRMS was obtained on
a Mariner spectrometer (PerSeptive Biosystems Inc.).
Preparative TLC was performed on E. Merck Silica
Gel 60GF254. Column chromatography was conducted
using Silica Gel 60 N (40–50 lm, Kanto Chemical Co.,
Inc.).
Entrya Fully benzylated Partially benzylated product (yield/%)
sucrose-related
oligosaccharide
Di- or trisaccharide Monosaccharide
unit
unit
1
2
3
4
5
6
1
4
5
6
7
8
—
9 (85)
10 (92)
11 (77)
12 (92)
—
2 (94) 3 (85)
3 (91)
3 (90)
2 (94)
3 (86)
2 (78) 3 (88)
13 (54)
a Reaction conditions: 75% aq H2SO4–1,4-dioxane (v/v = 1/10); room
temperature; 1 h.
1.2. Benzylation of sucrose and sucrose-related
oligosaccharides
Next, the hydrolysis of 4–7 under the same acidic con-
ditions was examined in order to observe whether only
the b-fructofuranosidic linkage in 4–7 is selectively
cleaved, while the other aldopyranosidic linkages remain
uncleaved under the reaction conditions. Treatment of 4
by 1:10 75% aqueous H2SO4–1,4-dioxane at room tem-
perature for 1 h similarly produced the partially benz-
ylated mono- and disaccharides 3 and 9 in 91% and
85% yields. Similar reaction conditions promoted the
acidic hydrolysis of 5 to 3 and 10 in 90% and 92% yields.
The acidic hydrolysis of 6 similarly produced 2 and 11 in
94% and 77% yields. The reaction using 7 afforded 3 and
12 in 86% and 92% yields, respectively. This means that
hydrolysis under these conditions selectively cleaved the
b-fructofuranosidic linkages without cleaving the other
aldopyranosidic linkages of 4–7.
The same treatment of 8 produced 2, 3, and 13 in 78%,
88%, and 54% yields, respectively. We found that all the
three b-fructofuranosidic linkages in 8 were smoothly
cleaved under these conditions. These results are shown
in Table 2.
In summary, we were able to prepare the partially
benzylated mono-, di-, and trisaccharides 2, 3, 9–13
having a free anomeric hydroxyl group by selective
cleavage of the b-fructofuranosidic linkage in the fully
benzylated sucrose-related oligosaccharides 4–8 under
acidic conditions using 1:10 75% aqueous H2SO4–di-
oxane at room temperature for 1 h. This method is
expected to be applicable to the hydrolysis of other
benzylated sucrose-related oligosaccharides containing
a b-fructofuranosidic linkage.
1.2.1. 1,3,4,6-Tetra-O-benzyl-b-D-fructofuranosyl 2,3,4,6-
tetra-O-benzyl-a-D-glucopyranoside (1). To a soln of
sucrose (2.2 g, 6.4 mmol) and benzyl bromide
(7.0 mL, 59 mmol) in DMF (80 mL) was added NaH
(4.9 g, 0.21 mol) at 0 °C. The reaction mixture was then
stirred overnight at room temperature. Methanol
(5 mL) was slowly dropped into the reaction mixture,
and then water (20 mL) was added. The mixture was
then extracted with CH2Cl2 and dried over anhyd
Na2SO4. Concentration led to a crude product which
was purified by silica gel chromatography (8:1?4:1,
hexane–EtOAc) to give 13 (5.4 g, 79%) as a colorless
27
20
oil; ½aꢁD +34.7 (c 1.2, CHCl3); lit.3a ½aꢁD +31.6; lit.3b
20
1
½aꢁD +38.4. H NMR (CDCl3, 600 MHz): d 3.37 (1H,
dd, J 2.06 Hz, J 11.00 Hz, Ha-6), 3.49 (1H, dd,
J 3.44 Hz, J 6.87 Hz, H-2), 3.50 (1H, dd, J 3.44 Hz,
J 11.00 Hz, Hb-6), 3.54 (1H, d, J 11.00 Hz, Ha-10),
3.64 (1H, t, J 9.62 Hz, H-4), 3.67 (1H, dd, J 3.44 Hz,
J 10.31 Hz, Ha-60), 3.72 (1H, dd, J 5.50 Hz,
J
10.31 Hz, Hb-60), 3.74 (1H, d, J 11.00 Hz, Hb-10), 3.93
(1H, t, J 9.62 Hz, H-3), 4.06 (1H, m, H-5), 4.11 (1H,
m, H-50), 4.18 (1H, t, J 7.56 Hz, H-40), 4.43 (1H, d, J
7.56 Hz, H-30), 5.72 (1H, d, J 3.44 Hz, H-1); 13C
NMR (CDCl3, 150 MHz): d 68.41 (C-6), 70.53 (C-5),
71.20 (C-10), 71.37 (C-60), 72.15 (CH2Ph), 72.49
(CH2Ph), 72.96 (CH2Ph), 73.19 (CH2Ph), 73.34
(CH2Ph), 73.38 (CH2Ph), 74.78 (CH2Ph), 75.48
(CH2Ph), 77.58 (C-4), 79.57 (C-50), 79.79 (C-2), 81.90
(C-3), 82.39 (C-40), 83.86 (C-30), 89.89 (C-1), 104.58
(C-20). HRESIMS: calcd for C68H70O11ꢀNa+:
1085.4810; found: m/z 1085.4843.
1.2.2. 1,3,4,6-Tetra-O-benzyl-b-D-fructofuranosyl 2,3,6-
tri-O-benzyl-4-O-(2,3,4,6-tetra-O-benzyl-b-D-galactopyr-
anosyl)-a-D-glucopyranoside (4). The same procedure
as for 1 but using lactosucrose (563 mg, 1.11 mmol),
benzyl bromide (2.0 mL, 17.2 mmol) in DMF (40 mL)
and NaH (1.18 g, 49.1 mmol) was applied resulting in
1. Experimental
1.1. General
Lactosucrose (purity ca. 90%) was a gift from Hayashi-
bara Biochemical Laboratories, Inc. Sucrose and raffi-
noseꢀ5H2O were purchased from Wako Pure
27
4 (1.12 g, 67%) as a colorless oil; ½aꢁD +16.7 (c 1.1,
CHCl3). 1H NMR (CDCl3, 600 MHz): d 3.32–3.40

T. Yamanoi et al. / Carbohydrate Research 343 (2008) 1366–1372
1369
(4H, m, H-30, H-50, Ha-60, Ha-6), 3.45 (1H, dd, J 3.44 Hz,
J 9.62 Hz, H-2), 3.51 (1H, d, J 11.00 Hz, Ha-100), 3.54
(1H, t, J 8.94 Hz, Hb-6), 3.63 (1H, dd, J 4.12 Hz, J
10.31 Hz, Ha-600), 3.69–3.75 (3H, m, Hb-100, Hb-600, H-
20), 3.79 (1H, dd, J 3.44 Hz, J 10.31 Hz, Hb-60), 3.84
(1H, t, J 8.94 Hz, H-3), 3.90–3.93 (2H, m, H-4, H-40),
4.08–4.10 (2H, m, H-5, H-400), 4.13 (1H, m, H-500), 4.34
(1H, d, J 7.56 Hz, H-10), 4.45 (1H, d, J 3.44 Hz, H-300),
5.66 (1H, d, J 3.44 Hz, H-1). 13C NMR (CDCl3,
150 MHz): d 68.17 (C-6, C-60), 70.66 (C-5), 71.17 (C-
100), 71.78 (C-600), 72.51 (CH2Ph), 72.56 (CH2Ph), 72.75
(CH2Ph), 72.79 (CH2Ph), 72.96 (C-50), 73.05 (CH2Ph),
73.20 (CH2Ph), 73.32 (CH2Ph), 73.37 (CH2Ph), 73.70
(C-40), 74.68 (CH2Ph), 75.01 (CH2Ph), 75.26 (CH2Ph),
77.35 (C-4), 79.05 (C-2), 79.76 (C-500), 79.87 (C-20),
80.10 (C-3), 82.52 (C-30), 83.09 (C-400), 83.79 (C-300),
90.09 (C-1), 103.02 (C-10), 104.51 (C-200). HRESIMS:
calcd for C95H98O16ꢀNa+: 1517.6747; found: m/z
1517.6702. Anal. Calcd for C95H98O16ꢀH2O: C, 75.37;
H, 6.66. Found: C, 75.37; H, 6.69.
(545 mg, 1.1 mmol), benzyl bromide (2.0 mL, 17 mmol)
in DMF (40 mL) and NaH (1.14 g, 48 mmol) resulting
27
in 6 (1.38 g, 89%) as a colorless oil; ½aꢁD +47.8 (c 0.87,
1
CHCl3); H NMR (CDCl3, 600 MHz): d 3.32 (1H, d, J
9.62 Hz, Ha-6), 3.44 (2H, m, Ha-10, Ha-600), 3.50 (1H,
dd, J 3.44 Hz, J 9.62 Hz, H-2), 3.54 (1H, dd, J
3.44 Hz, J 10.31 Hz, H-200), 3.54–3.57 (2H, m, Ha-60,
Hb-6), 3.62 (1H, t, J 9.62 Hz, H-4), 3.64 (1H, dd, J
2.06 Hz, J 11.00 Hz, Hb-600), 3.74 (1H, t, J 9.62 Hz,
H-40), 3.76–3.82 (2H, m, Hb-10, Hb-60), 3.84 (1H, t, J
9.62 Hz, H-3), 3.99 (1H, m, H-5), 4.01 (1H, t, J
8.25 Hz, H-400), 4.05 (1H, t, J 9.62 Hz, H-300), 4.11 (1H,
m, H-500), 4.16 (1H, m, H-50), 4.54–4.58 (1H, m,
H-30), 5.12 (1H, d, J 3.44 Hz, H-100), 5.48 (1H, d, J
3.44 Hz, H-1); 13C NMR (CDCl3, 150 MHz):
d
68.10 (C-600), 68.56 (C-6), 70.33 (C-10), 70.54 (C-5),
70.93 (C-500), 71.72 (C-60), 72.29 (CH2Ph), 72.93
(CH2Ph), 73.07 (CH2Ph), 73.23 (CH2Ph), 73.28
(CH2Ph), 73.30 (CH2Ph), 73.36 (CH2Ph), 74.54
(CH2Ph), 74.88 (CH2Ph), 75.59 (CH2Ph), 75.79
(CH2Ph), 77.51 (C-4), 77.74 (C-40), 79.37 (C-50), 79.57
(C-2 or C-200), 79.61 (C-2 or C-200), 81.07 (C-400), 82.11
(C-300), 82.39 (C-3), 84.47 (C-30), 89.78 (C-1), 99.88 (C-
100), 103.81 (C-20). HRESIMS: calcd for C95H98O16ꢀNa+:
1517.6747; found: m/z 1517.6714. Anal. Calcd for
C95H98O16ꢀH2O: C, 75.37; H, 6.66. Found: C, 75.37;
H, 6.38.
1.2.3. 1,3,4,6-Tetra-O-benzyl-b-D-fructofuranosyl 2,3,4-
tri-O-benzyl-6-O-(2,3,4,6-tetra-O-benzyl-a-D-galactopyr-
anosyl)-a-D-glucopyranoside (5). The same procedure
as for 1 was followed starting from raffinoseꢀ5H2O
(780 mg, 1.55 mmol), benzyl bromide (3.3 mL, 28 mmol)
in DMF (60 mL) and NaH (1.18 g, 49 mmol). This led
27
to 5 (1.8 g, 78%) as a colorless oil; ½aꢁD +39.6 (c 1.2,
1.2.5. 1,3,4,6-Tetra-O-benzyl-b-D-fructofuranosyl 2,3,4-
tri-O-benzyl-6-O-[2,3,4-tri-O-benzyl-6-O-(2,3,4,6-tetra-O-
benzyl-a-D-galactopyranosyl)-a-D-galactopyranosyl]-a-D-
glucopyranoside (7). The same procedure as for 1 was
followed starting from stachyoseꢀ4H2O (262 mg,
0.39 mmol), benzyl bromide (1.3 mL, 11 mmol) in
DMF (10 mL) and NaH (0.54 g, 22 mmol) resulting in
1
CHCl3); H NMR (CDCl3, 600 MHz): d 3.30 (1H, dd,
J 3.44 Hz, J 9.62 Hz, H-2), 3.46 (1H, dd, J 5.50 Hz, J
8.94 Hz, Ha-60), 3.50–3.55 (4H, m, Ha-100, Ha-600, Hb-60,
Ha-6), 3.65–3.70 (2H, m, Hb-100, Hb-600), 3.72 (1H, dd,
J 2.75 Hz, J 12.37 Hz, Hb-6), 3.78 (1H, t, J 9.62 Hz,
H-4), 3.87–3.92 (4H, m, H-3, H-30, H-40, H-50), 4.01
(1H, dd, J 3.44 Hz, J 7.56 Hz, H-20), 4.02 (1H, m,
H-5), 4.09 (1H, m, H-500), 4.15 (1H, t, J 7.56 Hz,
H-400), 4.37 (1H, m, H-300), 5.10 (1H, d, J 3.44 Hz,
H-10), 5.63 (1H, d, J 3.44 Hz, H-1); 13C NMR (CDCl3,
150 MHz): d 65.73 (C-6), 68.79 (C-60), 69.20 (C-50),
71.21 (C-100 or C-600), 71.25 (C-100 or C-600), 71.32
(C-40), 71.94 (CH2Ph), 72.40 (CH2Ph), 72.55
(CH2Ph), 72.81 (CH2Ph), 72.85 (CH2Ph), 73.17
(CH2Ph), 73.35 (CH2Ph ꢂ 2), 74.76 (CH2Ph), 74.80
(CH2Ph), 75.07 (C-5), 75.30 (CH2Ph), 76.68 (C-20),
77.46 (C-4), 78.13 (C-30), 79.49 (C-500), 80.13 (C-2),
81.81 (C-3), 82.42 (C-400), 83.74 (C-300), 89.93 (C-1),
98.06 (C-10), 104.51 (C-200). HRESIMS: calcd for
C95H98O16ꢀNa+: 1517.6747; found: m/z 1517.6774.
Anal. Calcd for C95H98O16: C, 76.28; H, 6.60. Found:
C, 76.37; H, 6.73.
26
7 (363 mg, 53%) as a colorless oil; ½aꢁD +69.8 (c 1.0,
1
CHCl3). H NMR (CDCl3, 600 MHz): d 3.26 (1H, dd,
J 3.44 Hz, J 9.62 Hz, H-2), 3.47–3.58 (4H, m, Ha-1000,
Ha-6, H-600), 3.66–3.71 (5H, m, Hb-1000, H-6000, H-60),
3.74 (1H, d, J 12.37 Hz, Hb-6), 3.80 (1H, t, J 10.31 Hz,
H-4), 3.88–3.92 (5H, m, H-3, H-30, H-50, H-300, H-500),
3.97–4.04 (5H, m, H-5, H-20, H-40, H-200, H-400), 4.10–
4.15 (2H, m, H-4000, H-5000), 4.43 (1H, m, H-3000), 4.83
(1H, d, J 3.44 Hz, H-100), 5.10 (1H, d, J 3.44 Hz, H-10),
5.62 (1H, d, J 3.44 Hz, H-1); 13C NMR (CDCl3,
150 MHz): d 65.95 (C-6), 66.69 (C-60), 68.85 (C-600),
68.99 (C-50), 69.65 (C-500), 71.31 (C-1000), 71.56 (C-6000),
71.72 (C-5), 72.12 (CH2Ph), 72.60 (CH2Ph), 72.68
(CH2Ph), 72.73 (CH2Ph), 72.82 (CH2Ph), 73.05
(CH2Ph), 73.37 (CH2Ph), 73.55 (CH2Ph), 73.69
(CH2Ph), 73.78 (CH2Ph), 74.86 (CH2Ph), 74.97
(CH2Ph ꢂ 2), 75.01 (C-40, C-400), 75.48 (CH2Ph), 76.37
(C-200), 76.81 (C-20), 77.48 (C-4), 78.34 (C-30 or C-300),
79.41 (C-30 or C-030000), 79.78 (C-5000), 80.31 (C-2), 81.97
(C-3), 82.76 (C-4 ), 83.97 (C-3000), 90.24 (C-1), 98.47
(C-10), 98.92 (C-100), 104.75 (C-2000); HRESIMS: calcd
1.2.4. 1,4,6-Tri-O-benzyl-3-O-(2,3,4,6-tetra-O-benzyl-a-
D-glucopyranosyl)-b-D-fructofuranosyl 2,3,4,6-tetra-O-
benzyl-a-D-glucopyranoside (6). The same procedure
as for 1 was followed starting from melezitoseꢀH2O

1370
T. Yamanoi et al. / Carbohydrate Research 343 (2008) 1366–1372
for C122H126O21ꢀNa+: 1949.8684; found: m/z 1949.8634.
Anal. Calcd for C122H126O21: C, 75.99; H, 6.59. Found:
C, 75.94; H, 6.46.
organic layer dried over anhyd Na2SO4. After concen-
tration, the crude products were purified by silica gel
chromatography (4:1?1:1 hexane–EtOAc) to give 27
(127 mg, 94%) as white crystals and 34 (115 mg, 85%)
as a colorless syrup. A reaction on a multigram scale
was also performed as follows: To a soln of 1 (2.12 g,
2.0 mmol) in dioxane (10 ml) was added 75% aq
H2SO4 (1 mL), and the reaction mixture was stirred
for 1 h at room temperature. Aq NaHCO3 (20 mL)
was then added and the mixture was extracted with
EtOAc. The organic solvent was dried over anhyd
Na2SO4. Concentration led to the crude products which
were separated by silica gel chromatography (4:1?1:1
hexane–EtOAc) to give 34 (947.4 mg, 94%). 27
(807 mg, 75%) was obtained as white crystals from
1.2.6.
3,4,6-Tri-O-benzyl-1-O-[3,4,6-tri-O-benzyl-1-O-
(1,3,4,6-tetra-O-benzyl-b-D-fructofuranosyl)-b-D-fructo-
furanosyl]-b-D-fructofuranosyl 2,3,4,6-tetra-O-benzyl-a-
D-glucopyranoside (8). The same procedure as for 1
was followed starting from nystoseꢀ3H2O (219 mg,
0.3 mmol), benzyl bromide (1 mL, 8.5 mmol) in DMF
(10 mL) and NaH (0.41 g, 17 mmol) resulting in 8
23
(490 mg, 84%) as a colorless oil; ½aꢁ365 ꢃ11.4 (c 1.6,
1
CHCl3); H NMR (CDCl3, 600 MHz): d 3.24 (1H, d, J
11.00 Hz, Ha-6), 3.39 (1H, d, J 10.31 Hz, Hb-6), 3.44
(1H, dd, J 3.44 Hz, J 9.62 Hz, H-2), 3.49 (1H, d, J
10.31 Hz, Ha-100 or Ha-1000), 3.54 (1H, d, J 10.31 Hz,
Hb-100 or Hb-1000), 3.59–3.70 (7H, m, H-4, H-60, H-600,
H-6000), 3.84 (1H, d, J 10.31 Hz, Ha-100 or Ha-1000), 3.91–
3.94 (2H, m, Hb-100 or Hb-1000, H-3), 4.00–4.09 (7H, m,
H-10, H-40 or H-400 or H-4000, H-50, H-500, H-5000, H-5),
4.12 (1H, t, J 5.50 Hz, H-40 or H-400 or H-4000), 4.20
(1H, t, J 8.25 Hz, H-40 or H-400 or H-4000), 4.31 (1H,
dd, J 2.06 Hz, J 6.87 Hz, H-30 or H-300 or H-3000),
4.44 (1H, m, H-30 or H-300 or H-3000), 4.56 (1H, m, H-30
or H-300 or H-3000), 5.74 (1H, d, J 4.12 Hz, H-1). 13C
1
EtOH. Compound 2 (71:29 a/b mixture); a Form: H
NMR (CDCl3, 600 MHz): d 3.50 (1H, dd, J 3.44 Hz, J
8.94 Hz, H-2), 3.54–3.57 (2H, m, H-4, Ha-6), 3.62 (1H,
m, Hb-6), 3.90 (1H, t, J 8.94 Hz, H-3), 3.96 (1H, m,
H-5), 5.15 (1H, d, J 3.44 Hz. H-1); 13C NMR (CDCl3,
150 MHz): d 68.56 (C-6), 70.27 (C-5), 73.23 (CH2Ph),
73.46 (CH2Ph), 74.98 (CH2Ph), 75.68 (CH2Ph), 77.66
(C-4), 79.97 (C-2), 81.71 (C-3), 91.28 (C-1); b Form:
1H NMR (CDCl3, 600 MHz): d 3.32 (1H, t, J 8.25 Hz,
H-2), 3.44 (1H, m, H-5), 3.47 (1H, m, H-4), 3.54–3.59
(2H, m, H-3, Ha-6), 3.62 (1H, m, Hb-6), 4.63 (1H, d, J
8.25 Hz, H-1); 13C NMR (CDCl3, 150 MHz): d 68.87
(C-6), 73.50 (CH2Ph), 74.70 (C-5, CH2Ph), 74.96
(CH2Ph), 75.64 (CH2Ph), 77.78 (C-4), 83.09 (C-2),
NMR (CDCl3, 150 MHz):
d
63.59 (C-10), 64.49
(C-100 or C-1000), 70.45 (C-6), 70.65 (C-5), 70.94 (C-60 or
C-600 or C-6000), 71.32 (C-60 or C-600 or C-6000), 71.33
(C-60 or C-600 or C-6000), 71.59 (CH2Ph), 71.72 (C-100 or
C-1000), 72.17 (CH2Ph), 72.36 (CH2Ph), 72.40 (CH2Ph),
72.45 (CH2Ph ꢂ 2), 73.04 (CH2Ph), 73.07 (CH2Ph),
73.15 (CH2Ph ꢂ 2), 73.27 (CH2Ph), 73.49 (CH2Ph),
74.68 (CH2Ph), 75.43 (CH2Ph), 77.52 (C-4), 78.47
(C-50 or C-500 or C-5000), 78.93 (C-50 or C-500 or C-5000),
79.00 (C-50 or C-500 or C-5000), 79.29 (C-2), 81.50 (0C0 -40
or C-400 or C-4000), 82.10 (C-3), 83.62 (C-30 or C-3 or
C-3000 or C-40 or C-400 or C-4000), 83.66 (C-30 or C-300 or
C-3000 or C-40 or C-400 or C-4000), 83.69 (C-30 or C-300 or
C-3000 or C-40 or C-400 or C-4000), 84.80 (C-30 or C-300 or
C-3000), 84.99 (C-30 or C-300 or C-3000), 89.42 (C-1),
104.18 (C-200 or C-2000), 104.20 (C-200 or C-2000), 104.40
(C-20). HRESIMS: calcd for C122H126O21ꢀNa+:
1949.8684; found: m/z 1949.8695. Anal. Calcd for
1
84.55 (C-3), 97.45 (C-1). H NMR data were in accor-
dance with the lit. data.7 Compound 3 (23:77 a/b mix-
22
20
D
ture): ½aꢁD +6.6?+9.2 (25 h, c 1.4, CHCl3); lit.4 ½aꢁ
+6.5?+8.7 (25 h, c 1.4, CHCl3); a Form: 1H NMR
(CDCl3, 600 MHz): d 3.43 (1H, m, Ha-6), 3.52 (1H, m,
Hb-6), 3.58 (1H, d, J 10.31 Hz, Ha-1), 3.65 (1H, d, J
10.31 Hz, Hb-1), 3.85 (1H, dd, J 2.06 Hz, J 3.44 Hz,
H-4), 3.95 (1H, d, J 1.38 Hz, H-3), 4.32 (1H, m, H-5);
13C NMR (CDCl3, 150 MHz): d 70.06 (C-6), 70.93 (C-
1), 71.84 (CH2Ph), 71.89 (CH2Ph), 73.26 (CH2Ph),
73.79 (CH2Ph), 81.78 (C-5), 82.72 (C-4), 86.32 (C-3),
1
105.34 (C-2); b Form: H NMR (CDCl3, 600 MHz): d
3.43 (1H, dd, J 4.12 Hz, J 10.31 Hz, Ha-6), 3.49 (2H,
d, J 2.75 Hz, H-1), 3.52 (1H, dd, J 4.81 Hz, J
10.31 Hz, Hb-6), 4.02 (1H, m, H-5), 4.10 (1H, t, J
4.81 Hz, H-4), 4.15 (1H, d, J 4.81 Hz, H-3); 13C NMR
(CDCl3, 150 MHz): d 70.59 (C-6), 71.89 (C-1), 72.09
(CH2Ph), 72.68 (CH2Ph), 73.51 (CH2Ph), 73.59
(CH2Ph), 79.95 (C-5), 83.41 (C-4), 83.65 (C-3), 102.43
(C-2). HRESIMS (a/b mixture): calcd for C34H36O6ꢀK+:
579.2143; found: m/z 579.2184.
C
122H126O21: C, 75.99; H, 6.59. Found: C, 76.12; H,
6.68.
1.3. Hydrolysis of fully benzylated sucrose and sucrose-
related oligosaccharides
1.3.1. Preparation of 2,3,4,6-tetra-O-benzyl-D-gluco-
pyranose (2) and 1,3,4,6-tetra-O-benzyl-D-fructofuranose
(3) from 1. To a soln of 1 (265 mg, 0.25 mmol) in di-
oxane (6 mL) was added 75% aq H2SO4 (0.5 mL). The
reaction mixture was stirred for 1 h at room tempera-
ture. A saturated aq NaHCO3 soln (10 mL) was then
added, the reaction was extracted with EtOAc, and the
1.3.2. Preparation of 2,3,6-tri-O-benzyl-4-O-(2,3,4,6-
tetra-O-benzyl-b-D-galactopyranosyl)-D-glucopyranose (9)
and 3 from 4. The same procedure as for 1 was used
starting from 4 (61.5 mg, 0.041 mmol) in dioxane
(3 mL) and using 75% aq H2SO4 (0.3 mL) and then

T. Yamanoi et al. / Carbohydrate Research 343 (2008) 1366–1372
1371
stirring for 1 h at room temperature which resulted in
1.3.4. Preparation of 1,4,6-tri-O-benzyl-3-O-(2,3,4,6-
tetra-O-benzyl-a-D-glucopyranosyl)-D-fructofuranose (11)
from 6. The procedure used for 1 was applied to 6
(133 mg, 0.089 mmol) in dioxane (3 mL) to which was
added 75% aq H2SO4 (0.3 mL) resulting in 11 (66 mg,
77%) as a colorless syrup and 2 (45 mg, 94%) as white
910 (34 mg, 85%) and 3 (20 mg, 91%) both as colorless
1
syrups. Compound 9 (63:37 a/b mixture); a Form: H
NMR (CDCl3, 600 MHz): d 3.32–3.35 (2H, m, H-30,
H-50), 3.37 (1H, dd, J 5.50 Hz, J 8.94 Hz, Ha-60), 3.51
(1H, dd, J 3.44 Hz, J 9.62 Hz, H-2), 3.52–3.56 (2H, m,
Ha-6, Hb-60), 3.74 (H, dd, J 7.56 Hz, J 9.62 Hz, H-20),
3.82–3.86 (2H, m, H-3, Hb-6), 3.89–3.96 (3H, m, H-4,
H-5, H-40), 4.35 (1H, d, J 7.56 Hz, H-10), 5.16 (1H, d,
J 3.44 Hz, H-1); 13C NMR (CDCl3 150 MHz): d 68.01
(C-6), 68.16 (C-60), 70.37 (C-5), 72.55 (CH2Ph), 73.05
(C-50), 73.09 (CH2Ph), 73.37 (CH2Ph), 73.56 (CH2Ph),
73.69 (C-40), 74.66 (CH2Ph), 75.17 (CH2Ph), 75.36
(CH2Ph), 76.44 (C-4), 79.05 (C-2), 79.89 (C-20, C-3),
82.39 (C-30), 91.34 (C-1), 102.83 (C-10); b Form: 1H
NMR (CDCl3, 600 MHz): d 4.37 (1H, d, J 7.56 Hz, H-
10), 4.65 (1H, m, H-1); 13C NMR (CDCl3 150 MHz): d
68.03, 68.21, 72.61, 73.08, 73.09, 73.15, 73.42, 73.65,
73.75, 74.70, 75.23, 75.28, 75.41, 76.40, 79.11, 79.95,
82.45, 97.50 (C-1), 103.45 (C-10); HRESIMS (a/b
mixture): calcd for C61H64O11ꢀNa+: 995.4341; found:
m/z 995.4378. The 1H and 13C NMR data were in
accordance with the lit. data.10
1
crystals. Compound 11 (2:3 a/b mixture); a Form: H
NMR (CDCl3, 600 MHz): d 4.81 (1H, d, J 3.44 Hz, H-
10); 13C NMR (CDCl3 150 MHz): d 67.85, 70.45,
70.49, 70.88 (C-50), 71.48, 72.97, 73.07, 73.10, 74.70,
74.92, 75.54, 77.38, 79.17, 81.07, 81.94, 82.30, 82.57,
1
95.04 (C-10), 105.69 (C-2); b Form: H NMR (CDCl3,
600 MHz): 3.44 (1H, dd, J 3.44 Hz, J 10.31 Hz, Ha-6),
3.49 (1H, m, Ha-60), 3.54 (1H, d, J 10.31 Hz, Ha-1),
3.55–3.58 (2H, m, H-20, Hb-6), 3.61–3.69 (2H, m, H-40,
Hb-60), 3.74 (1H, d, J 10.31 Hz, Hb-1), 4.00 (1H, t, J
9.62 Hz, H-30), 4.04 (1H, m, H-50), 4.11 (1H, m, H-5),
4.24 (1H, t, J 6.19 Hz, H-4), 4.42 (1H, d, J 6.19 Hz,
H-3), 5.03 (1H, d, J 3.44 Hz, H-10); 13C NMR (CDCl3
150 MHz): d 68.28 (C-60), 70.31 (C-6), 70.85 (C-50),
71.24 (C-1), 71.26 (CH2Ph), 73.07 (CH2Ph), 73.41
(CH2Ph), 73.46 (CH2Ph), 73.50 (CH2Ph), 75.02
(CH2Ph), 75.63 (CH2Ph), 77.61 (C-40), 79.58 (C-5),
79.80 (C-20), 81.85 (C-30, C-4), 84.41 (C-3), 97.99 (C-
10), 102.54 (C-2). HRESIMS (a/b mixture): calcd for
C61H64O11ꢀNa+: 995.4341; found: m/z 995.4376. Anal.
Calcd for C61H64O11ꢀ0.5H2O: C, 74.60; H, 6.67. Found:
C, 74.68; H, 6.64.
1.3.3. Preparation of 2,3,4-tri-O-benzyl-6-O-(2,3,4,
6-tetra-O-benzyl-a-D-galactopyranosyl)-D-glucopyranose
(10) and 3 by the hydrolysis of 5. The procedure used
for 1 was applied starting from 5 (110 mg, 0.074 mmol)
in dioxane (3 mL) to which was added 75% aq H2SO4
(0.3 mL). resulting in 10 (66 mg, 92%) and 3 (36 mg,
90%), both as colorless syrups. Compound 10 (61:39
a/b mixture); a Form: 1H NMR (CDCl3, 600 MHz):
d 3.39 (1H, dd, J 3.44 Hz, J 8.94 Hz, H-2), 3.46–3.55
(4H, m, H-4, H-6, H-50), 3.73 (1H, dd, J 5.50 Hz, J
12.37 Hz, Ha-60), 3.85 (1H, dd, J 5.50 Hz, J 11.00 Hz,
Hb-60), 3.91 (1H, dd, J 2.75 Hz, J 10.31 Hz, H-40),
3.94 (1H, t, J 10.31 Hz, H-30), 3.95 (1H, t, J 9.62 Hz,
H-3), 4.02 (1H, dd, J 3.44 Hz, J 10.31 Hz, H-20), 4.05
(1H, m, H-5), 4.99 (1H, d, J 3.44 Hz, H-10), 5.09
1.3.5. Preparation of 2,3,4-tri-O-benzyl-6-O-[2,3,4-tri-
O-benzyl-6-O-(2,3,4,6-tetra-O-benzyl-a-D-galactopyran-
osyl)-a-D-galactopyranosyl]-D-glucopyranose (12) and 3
from 7. The procedure used for 1 was applied starting
from 7 (278 mg, 0.14 mmol) in dioxane (8 mL) to
which was added 75% aqueous H2SO4 (0.8 mL), result-
ing in 12 (187 mg, 92%) and 3 (67 mg, 86%) both as
colorless syrups. Compound 12 (19:31 a/b mixture); a
1
Form: H NMR (CDCl3, 600 MHz): d 3.34–3.37 (1H,
m, H-2), 3.48–3.83 (9H, m, H-6, H-50, H-60, H-200,
H-500, H-600), 3.90–4.04 (4H, m, H-3, H-4, H-5, H-20),
4.77–4.82 (1H, m, H-100), 5.00 (1H, d, J 3.44 Hz,
H-10), 5.05 (1H, d, J 2.75 Hz, H-1); 13C NMR (CDCl3
150 MHz): d 66.77 (C-6), 67.22 (C-60), 68.70 (C-600a or
C-600b), 68.90 (C-600a or C-600b), 69.17 (C-50), 69.40
(C-500), 70.69 (C-5), 75.36 (C-4), 78.21 (C-20a or
C-400b), 78.23 (C-20a or C-400b), 78.73 (C-200), 80.26
(C-2), 90.95 (C-1), 97.85 (C-10), 98.23 (C-100); b Form:
1H NMR (CDCl3, 600 MHz): d 3.17 (1H, dd, J
7.56 Hz, J 8.97 Hz, H-2), 3.34–3.37 (1H, m,0 H-300),
3.48–3.83 (11H, m, H-3, H-4, H-6, H-50, H-6 , H-400,
H-500, H-600), 3.90–4.04 (3H, m, H-5, H-20, H-200), 4.54
(1H, d, J 7.56 Hz, H-1), 4.77–4.82 (1H, m, H-100),
4.90–4.93 (1H, m, H-10); 13C NMR (CDCl3,
150 MHz): d 67.33 (C-6), 67.50 (C-60), 68.70 (C-600a
(1H, d,
J
2.75 Hz, H-1); 13C NMR (CDCl3
150 MHz): d 67.59 (C-60), 69.21 (C-6), 69.50 (C-50),
70.69 (C-5), 72.53 (CH2Ph), 72.95 (CH2Ph), 73.13
(CH2Ph), 73.36 (CH2Ph), 74.68 (CH2Ph), 74.97 (C-40,
CH2Ph), 75.59 (CH2Ph), 76.67 (C-20), 77.99 (C-4),
78.43 (C-30), 80.30 (C-2), 81.75 (C-3), 90.97 (C-1),
98.36 (C-10); b Form: 1H NMR (CDCl3, 600 MHz):
4.67 (1H, d, J 7.56 Hz, H-1), 5.00 (1H, d, J 3.44 Hz,
H-10); 13C NMR (CDCl3 150 MHz): d 67.78, 69.24,
72.92, 73.09, 73.48, 74.34, 74.65, 74.79, 74.86, 74.97,
75.10, 75.35, 76.63, 77.84, 78.67, 83.47, 84.47, 97.16
(C-1), 98.26 (C-10); HRESIMS (a/b mixture): calcd
for C61H64O11ꢀK+: 1011.4080; found: m/z 1011.4113;
Anal. Calcd for C61H64O11ꢀ0.5H2O: C, 74.60; H, 6.67.
Found: C, 74.52; H, 6.48.

1372
T. Yamanoi et al. / Carbohydrate Research 343 (2008) 1366–1372
or C-600b), 68.90 (C-600a or C-600b), 69.02 (C-500), 69.37
(C-50), 75.18 (C-4), 78.21 (C-20a or C-400b), 78.23
(C-20a or C-400b), 78.24 (C-300), 78.39 (C-3), 81.63
(C-20), 83.88 (C-2), 84.53 (C-200), 97.20 (C-1), 97.49
(C-10), 98.44 (C-100); HRESIMS (a/b mixture): calcd
for C88H92O16ꢀNa+: 1427.6278; found: m/z 1427.6254.
Anal. Calcd for C88H92O16: C, 75.19; H, 6.60. Found:
C, 75.51; H, 6.76.
Acknowledgment
We thank Hayashibara Biochemical Laboratories, Inc.,
for the gift of lactosucrose.
References
1. Toshima, K.; Tatsuta, K. Chem. Rev. 1993, 93, 1503–
1531.
1.3.6. Preparation of 3,4,6-tri-O-benzyl-D-fructofuranose
(13), 2 and 3 from 8. The procedure used for 1 was
applied starting from 8 (97 mg, 0.05 mmol) in dioxane
(3 mL) to which was added 75% aq H2SO4 (0.3 mL)
resulting in 2 (21 mg, 78%) as white crystals, 3 (24 mg,
88%) and 13 (24 mg, 54%) both as colorless syrups. Com-
pound 13 (8:17 a/b mixture); a Form: 1H NMR (CDCl3,
600 MHz): d 3.51–3.56 (2H, m, H-1), 3.69 (1H, dd, J
7.56 Hz, J 11.69 Hz, Ha-6), 3.78 (1H, dd, J 4.12 Hz, J
11.69 Hz, Hb-6), 4.02–4.04 (2H, m, H-3, H-4), 4.36
(1H, m, H-5); 13C NMR (CDCl3 150 MHz): d 64.25
(C-1), 69.63 (C-6), 72.05 (CH2Ph), 72.20 (CH2Ph),
73.30 (CH2Ph), 81.02 (C-5), 82.08 (C-4), 86.36 (C-3),
2. Yamanoi, T.; Inoue, N.; Fujimoto, M.; Sasaura, H.;
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1
105.36 (C-2); b Form: H NMR (CDCl3, 600 MHz): d
3.50 (1H, dd, J 4.12 Hz, J 10.31 Hz, Ha-6), 3.57 (1H,
dd, J 4.81 Hz, J 10.31 Hz, Hb-6), 3.59–3.62 (2H, m,
H-1), 4.11 (1H, m, H-5), 4.16–4.17 (2H, m, H-3, H-4);
13C NMR (CDCl3 150 MHz): d 65.15 (C-1), 70.67
(C-6), 72.02 (CH2Ph), 72.85 (CH2Ph), 73.52 (CH2Ph),
80.55 (C-5), 83.29 (C-3), 83.49 (C-4), 103.08 (C-2); HRE-
SIMS (a/b mixture): calcd for C27H30O6ꢀNa+: 473.1935;
found: m/z 473.1940. Anal. Calcd for C27H30O6: C,
71.98; H, 6.71. Found: C, 72.14; H, 6.88.
10. Ishii, K.; Kubo, H.; Yamasaki, R. Carbohydr. Res. 2002,
337, 11–20.