Simple preparations of alkyl and cycloalkyl α-glycosides of maltose, cellobiose, and lactose

Article abstract of DOI:10.1016/j.carres.2004.07.016

Alkyl, cycloalkyl, allyl, 4-pentenyl, and benzyl α-glycosides of maltose, cellobiose, and lactose were prepared via direct reaction of the free bioses with a binary AcBr-AcOH system, followed by glycosidation with alcohol using FeCl₃ in MeNO₂ or CH₂Cl₂, Zemple?n deacetylation, and the chromatographic resolution of the mixture. The respective β-biosides were obtained via the glycosidation in MeCN. Alkyl, cycloalkyl, allyl, 4-pentenyl, and benzyl α-glycosides of maltose, cellobiose, and lactose were prepared (17-77% yield; α/β = 70/30-96/4) via a direct reaction of the free disaccharides with a binary AcBr-AcOH mixture, followed by glycosidation with alcohol using FeCl₃ in MeNO₂ or CH₂Cl₂, Zemple?n deacetylation, and resolution of the anomeric mixture of glycosides by chromatography. Using MeCN as solvent for the glycosidation step, the corresponding β-biosides were also prepared (16-61% yield; α/β = 25/75-5/95).

Full text of DOI:10.1016/j.carres.2004.07.016

Carbohydrate
RESEARCH
Carbohydrate Research 339 (2004) 2415–2424
Note
Simple preparations of alkyl and cycloalkyl a-glycosides
of maltose, cellobiose, and lactose
Shinkiti Koto,* Motoko Hirooka, Takako Tashiro, Motokazu Sakashita,
Masaharu Hatachi, Takayuki Kono, Miho Shimizu, Nahoko Yoshida, Sayaka Kurasawa,
Natsuko Sakuma, Sunao Sawazaki, Akihiro Takeuchi, Naomi Shoya and Emi Nakamura
School of Pharmaceutical Sciences, Kitasato University, Shirokane, Minato-ku, Tokyo 108-8641, Japan
Received 5 May 2004; accepted 10 July 2004
This paper is dedicated to Dr. Yukio Ito
Abstract—Alkyl, cycloalkyl, allyl, 4-pentenyl, and benzyl a-glycosides of maltose, cellobiose, and lactose were prepared (17–77%
yield; a/b = 70/30–96/4) via a direct reaction of the free disaccharides with a binary AcBr–AcOH mixture, followed by glycosidation
´
with alcohol using FeCl3 in MeNO2 or CH2Cl2, Zemplen deacetylation, and resolution of the anomeric mixture of glycosides by
chromatography. Using MeCN as solvent for the glycosidation step, the corresponding b-biosides were also prepared (16–61% yield;
a/b = 25/75–5/95).
ꢀ 2004 Elsevier Ltd. All rights reserved.
Keywords: a-Glycosidation; Iron(III) chloride; Glycosyl bromide; Disaccharide
Methyl, allyl, 4-pentenyl, and benzyl glycosides of
such disaccharides as maltose (1), cellobiose (2), and
lactose (3), are of diverse use as starting materials for
various syntheses. Longer-chain alkyl biosides are
widely used as nonionic surfactants1 and are known to
form liquid crystalline phases.2 They are used as sugar
acceptors for enzymatic glycosylation3 and as the
lipophile-carrying head-moiety of artificial bioactive
sugar clusters.4 Several biosides are probe-guests
combining to receptor proteins5 and artificial recep-
tors.6,7 Some long-chain alkyl maltosides enhance the
nasal insulin absorption8 and the bioavailability of
calcitonin.9
We present here convenient preparations of alkyl,
cycloalkyl, allyl, 4-pentenyl, and benzyl a-glycosides of
the common disaccharides, 1, 2, and 3, directly from
the respective free bioses, as shown in Figure 1. The pro-
cedure consists of (i) direct reaction of the bioses with a
binary AcBr–AcOH system for 0.5h, (ii) condensation
of the alcohol with the crude biosyl bromides in the
presence of FeCl3 (1–2mol amount to the starting
bioses) in MeNO2 or CH2Cl2 for 1h, (iii) deacetylation
with methanolic NaOMe, and (iv) chromatographic res-
olution of the anomeric mixture of glycosides formed.
When MeCN was used as the solvent in the glycosida-
tion step for 1h, as shown in Figure 2, the corresponding
b-biosides were obtained.
The Fischer method has been used to prepare alkyl
a-glycosides directly from glycoses, but its application
to a disaccharide (biose) such as 1 is difficult,10 because
of concurrent alcoholysis of the interglycosidic link-
age.11–13 For example,13 the reaction of 1 with MeOH
containing HCl (1%) at 20–25ꢁC for 4days affords the
corresponding disaccharide glycosides (biosides) in ꢀ35%
yield (a/b = ꢀ50/50). The direct glycosidation of 3 with
neat 4-penten-1-ol by refluxing at 110ꢁC for 9h w ith
10-camphorsulfonic acid14 w as reported to give an ano-
meric mixture of the corresponding biosides, but their
yields were not given. At present, alkyl a-biosides are
best prepared indirectly; thus, the in situ anomerizing
*
Corresponding author. E-mail: kotos@pharm.kitasato-u.ac.jp
0008-6215/$ - see front matter ꢀ 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2004.07.016

2416
S. Koto et al. / Carbohydrate Research 339 (2004) 2415–2424
OH
OH
O
O
HO
HO
HO
HO
OH
OH
a,b,c
OH
OH
O
O
O
O
HO
HO
OH
OH
OH
OR
OR
1
4A~4L
OH
OH
OH
OH
O
OH
O
O
HO
HO
HO
HO
HO
d,b,c
a,b,c
O
HO
O
O
OH
OH
OH
OH
2
5A~5L
OR
HO
OH
OH
HO
OH
O
OH
O
OH
O
O
HO
HO
O
HO
O
HO
OH
OH
OH
OH
6A~6L
3
Me
A
H
B
C
D
E
I
J
Ph
Me
K
L
F
Me
G
Me
Figure 1. Preparation of a-biosides: (a) AcBr/AcOH, room temperature (rt, ca. 25ꢁC), 0.5h; (b) ROH+FeCl3/MeNO2 or CH2Cl2, rt, 1h; (c) NaOMe/
MeOH, rt, overnight; (d) AcBr/AcOH, 60ꢁC, 0.5h.
glycosylation starting from the respective biose
octaacetates is the most useful for obtaining alkyl
in the system, took over 5h at room temperature. In
this study, we found that this went to completion within
0.5h at 60ꢁC. It was also found that reactions of 1 and 3
finished within 0.5h at room temperature (ꢀ25ꢁC). This
binary AcBr–AcOH system is more efficient than the ter-
nary Ac2O–HBr–AcOH system for the direct acetobro-
mination of free bioses; the latter takes more than 2h
for completion.31,32
As the condensation reagent for the subsequent gly-
cosidation using biosyl bromides, we used FeCl3, since
it was used as an a-glycosidation reagent for the conden-
sation between biose octaacetates and alcohols in CHCl3
at the reflux temperature,33 but not for the Koenigs–
Knorr reaction using the glycosyl bromides, which are
expected to be more reactive than the glycosyl acetates.
This reagent catalyzes the anomerization of methyl hep-
ta-O-acetyl-b-cellobioside,34 the a-glycosidation of fully
acetylated sugars,35 the Ferrier reaction,36 the Fischer
reaction,37 the formation of 1,6-anhydro sugars,38 and
the synthesis of b-glucosaminides.39 we thus considered
that FeCl3 would be a good substitute for the standard
a-biosides.15 However, the a-biosylation in the presence
15–19
of SnCl4 in CH2Cl2
takes more than 4h. Other
methods, starting from 1-thio sugar derivatives,20,21
1-O-(2,4,6-trimethylbenzoyl)sugars,22
1-OH sugar
derivatives,23 and b-glycosides,24 as well as enzymic
methods,25 require preparation of the particular
donors. In contrast, alkyl b-biosides are readily pre-
pared by the standard Koenigs–Knorr method.1 Such
b-biosides are also prepared by short reactions (2h)
using octaacetates and alcohol in the presence of
or BF3ÆEt2O19 in CH2Cl2.
15,17
SnCl4
Direct reaction of the free disaccharides, 1 and 3 with
AcBr26,27 is an old reaction, but is not frequently used,
probably because of the difficultly controllable violent
evolution of HBr.28 Some years ago, we reported that
direct preparation of the glycosyl bromides from free
disaccharides 1 and 3 could be carried out at room
temperature using a binary AcBr–AcOH mixture.29,30
However, this reaction with 2, which is sparingly soluble

S. Koto et al. / Carbohydrate Research 339 (2004) 2415–2424
2417
OH
OH
O
O
HO
HO
HO
HO
OH
OH
a,b,c
OH
OH
O
O
O
O
OR
OR
HO
HO
OH
OH
OH
1
7A~'7L
OH
OH
OH
OH
O
OH
O
O
HO
HO
HO
HO
HO
d,b,c
a,b,c
O
HO
O
O
OH
OH
OH
OH
2
8A~8L
HO
OH
OH
HO
OH
O
OH
O
OH
O
O
OR
HO
HO
O
HO
O
HO
OH
OH
OH
OH
9A~9L
3
Me
A
H
I
B
C
D
E
J
Ph
Me
K
L
F
Me
G
Me
Figure 2. Preparation of b-biosides: (a) AcBr/AcOH, room temperature (rt, ca. 25ꢁC), 0.5h; (b) ROH+FeCl3/MeCN, rt, 1h; (c) NaOMe/MeOH, rt,
overnight; (d) AcBr/AcOH, 60ꢁC, 0.5h.
reagents of the Koenigs–Knorr method. As shown in
Table 1, the reactive biosyl bromides were converted
within 1h at room temperature in MeNO2 or CH2Cl2
containing 1.0–1.5mol of FeCl3 relative to the starting
bioses. For lower alcohols, MeNO2 as solvent gave a-
biosides with acceptable yields and a-selectivity. For
higher ones, such as 1-hexadecanol and cyclopentade-
canol, CH2Cl2, in which they dissolve well, gave better
results. The condensation with allyl alcohol in MeNO2
containing only 1.0mol amount of FeCl3 to the starting
sugars proceeded smoothly to give 4B, 5B, and 6B in
ꢀ70% yield, whereas, in CH2Cl2 with a 1.5mol amount
of FeCl3, the yields were slightly low (<50%). Longer
reaction time (3h) in MeNO2 slightly diminished the
yield of biosides (ꢀ60%); but the selectivities were raised
(a/b = ꢀ95/5), whereas shorter ones (0.5h) in MeNO2
gave similar yields (65–70%) but with lower selectivities
(a/b = ꢀ80/20). The reactions with other metal salts
and 6D were low (ꢀ20%). When CH2Cl2 was used
as the solvent, yields were improved (>50%), but the
a-selectivities were low (a/b = ꢀ60/40). For the n-octyl
a-biosides, 4E, 5E, and 6E, the yields of the biosides
using PhCF3 as solvent were comparable to those
using MeNO2 but the selectivities were very low (a/b =
ꢀ50/50).
42
When the glycosidation was conducted in MeCN at
room temperature for 1h, as shown in Figure 2, the cor-
responding b-biosides were formed selectively (a/b = 25/
75–5/95), in spite of a depression of the yields (Table 1).
It seems that MeCN weakens the promoting effects of
FeCl3, both for condensation and anomerization. In
most cases, the amount of FeCl3 could be increased to
2.0mol to the starting bioses without significantly by
raising the content of the a anomers. However, espe-
cially in synthesis of the lactosides of cycloalkanols,
the anomeric ratios of the products were sensitive to
the reaction time; thus extension of the reaction time
to only 1.5h raised the content of the a anomers. The
b-biosides were thus obtained selectively in ꢀ40% yield
40
41
such as CoBr2 and ZnCl2 for 3h resulted similar
yields, but with lower selectivities (a/b = 60/40–40/60).
In the case of benzyl alcohol, the yields of 4D, 5D,

2418
S. Koto et al. / Carbohydrate Research 339 (2004) 2415–2424
Table 1. Results of preparations of disaccharides
Alcohol
FeCl3/mol amount
Solvent
Yield/% (a/b)
Maltosides
Cellobiosides
Lactosides
Methanol
Methanol
1.5
2.0
1.0
2.0
1.5
1.5
1.5
2.0
1.5
2.0
1.5
2.0
1.5
2.0
1.5
2.0
1.5
2.0
1.0
2.0
1.5
2.0
1.5
2.0
N
A
N
A
N
A
N
A
N
A
N
A
D
A
N
A
N
A
N
A
N
A
D
A
60 (95/5)
26 (11/89)
71 (87/13)
52 (14/86)
26 (70/30)
39 (13/87)
22 (86/14)
34 (9/91)
65 (93/7)
39 (9/91)
69 (91/9)
34 (18/82)
56 (95/5)
49 (5/95)
63 (87/13)a
20 (17/83)
69 (84/16)
25 (22/78)
21 (86/14)
16 (17/83)
50 (88/12)
26 (5/95)
74 (87/13)
32 (17/83)
56 (87/13)
33 (5/95)
77 (89/11)
61 (17/83)
28 (73/27)
43 (17/83)
17 (94/6)
58 (7/93)
65 (96/4)
30 (8/92)
57 (91/9)
40 (18/82)
62 (85/15)
21 (5/95)
71 (88/12)
32 (17/83)
66 (86/14)
30 (10/90)
22 (94/6)
19 (20/80)
56 (91/9)
26 (17/83)
65 (92/8)
24 (6/94)
52 (89/11)
27 (9/92)
Allylalcohol
Allylalcohol
65 (90/10)
58 (20/80)
30 (75/25)
45 (16/84)
19 (92/8)
4-Penten-l-ol
4-Penten-l-ol
Benzylalcohol
Benzylalcohol
1-Octanol
57 (7/93)
67 (92/8)
1-Octanol
34 (20/80)
60 (98/11)
31(19/81)
50 (95/5)
1-Dodecanol
1-Dodecanol
1-Hexadecanol
1-Hexadecanol
Cyclopentanol
Cyclopentanol
Cyclohexanol
Cyclohexanol
Cyclooctanol
Cyclooctanol
Cyclododecanol
Cyclododecanol
Cyclopentadecanol
Cyclopentadecanol
27 (20/80)
52 (87/13)
40 (23/77)b
73 (87/13)
34 (23/77)b
26 (86/14)
22 (25/75)
51 (95/5)
43 (22/78)b
55 (91/9)
25 (5/95)b
a FeCl3 (1.0mol amount) was used.
b FeCl3 (1.5mol amount) was used.
at best, except for the allyl b-biosides, 7B, 8B, and 9B,
(50–60% yield; a/b = ꢀ20/80).
pared are given in Tables 2 and 3 and their 13C NMR
data are in Tables 4 and 5.ꢀ
1.2. Synthesis of biosides
1. Experimental
A mixture of 1 or 3 (monohydrate, 1.0g, 2.8mmol),
AcBr (3.6mL, 44.4mmol), and AcOH (19mL) was
stirred at room temperature (ꢀ25ꢁC) for 0.5h to give
a homogeneous solution. The mixture was concentrated
below25torr at 30 ꢁC, co-evaporated three times with
dry PhMe (5mL), and evacuated below25torr at
50ꢁC for 15min to give a foam [HRMS (FAB) Found:
from 1, m/z 721.0964 and from 3, m/z 721.0990. Calcd
for C26H35BrNaO11 [M+Na]+: 721.0955]. To the crude
bromide, the solvent (10mL), alcohol (5.6mmol), and
FeCl3 were added with vigorous stirring at room tem-
perature for 1h. To the mixture, aq KBr (10%, 25mL)
and then PhMe (60mL) were added under stirring.
The organic phase was washed with aq KBr (10%,
25mL, twice), aq NaHCO3 (5%, 25mL), and H2O
(25mL, twice). The organic layer was evaporated to dry-
ness. The resultant mixture was dissolved in MeOH
(30mL) containing methanolic NaOMe (7%, 2mL)
and the solution stirred at room temperature overnight.
After the addition of AcOH (0.2mL), the mixture was
1.1. General methods
The solvent systems for column chromatography on
silica gel (Kanto Kagaku, No 37047; gradient elusion)
and thin-layer chromatography (TLC) (Merck, DC-
Plastikfolien Kieselgel 60 F 254, Art. 5735) were
CHCl3–MeOH (CM) and PhMe–butanone (TK), and
that for column chromatography on Dowex 1 · 2 w as
a pyridine–MeOH (PM) system.
Solvents were evaporated from solutions obtained at
35–45ꢁC under diminished pressure, unless otherwise
noted. The melting points were determined on a Yanaco
Micro Melting Point Apparatus (Yanagimoto).
Optical rotations were measured on a Jasco DIP-180
1
digital polarimeter at room temperature. The H and
13C NMR spectra were recorded with a Varian
XL-400 spectrometer, along with measurements of
H,H-COSY, C,H-COSY, and DEPT spectra. Spectral
assignments were made by auxiliary measurements of
HOHAHA, HMQC, HMBC, GHMQC, and differential
NOE spectra. HRMS were recorded with a Jeol
ꢀ Note added in proof: the supplementary NMR data are available at
http://kitasato-u.ac.jp/medicinal.
JMS-AX505HA spectrometer or
1
a
spectrometer. The H NMR data of the biosides pre-
Jeol JMS-700

S. Koto et al. / Carbohydrate Research 339 (2004) 2415–2424
2419
Table 2. 1H NMR data of selected a-biosides determined at 400MHz (M = CD3OD, W = D2O)
Compounds (Solv.) 4A (W) 4E (W) 4F (M) 4L (M) 5A (W) 5E (W) 5F (M) 5L (M) 6A (W) 6E (W) 6F (M) 6L (M)
H-1I
J1,2
4.78
4.0
4.86
4.0
4.77
4.0
4.89
4.0
4.78
4.0
4.85
4.0
4.77
4.0
4.89
4.0
4.77
4.0
4.86
3.5
4.78
4.0
4.88
4.0
H-2I
3.56
3.56
9.0
3.45
3.43
3.58
3.57
9.5
3.45
9.5
3.44
3.57
9.5
3.58
9.0
3.46
9.5
3.44
9.5
J2,3
10.0
10.0
10.0
10.0
10.0
H-3I
J3,4
3.89
9.0
3.92
9.0
3.88
9.0
3.86
9.5
3.76
9.0
3.80
8.5
3.76
9.0
3.75
9.0
3.75
3.82
9.0
3.77
8.5
3.75
10.0
3.61
10.0
10.0
3.55
10.0
H-4I
3.62
9.0
3.66
9.5
3.51
3.53
9.5
3.61
3.64
9.5
3.54
9.5
3.36
9.5
3.67
9.0
3.54
J4,5
10.0
10.0
10.0
H-5I
J5,6a
J5,6b
H-6aI
H-6bI
J6a,b
3.73
4.5
3.64
6.0
3.62
4.5
3.70
2.0
3.78
4.0
3.70
5.5
3.68
2.0
3.77
2.0
3.73
5.0
3.72
5.5
3.69
2.0
3.79
2.0
2.0
2.0
2.0
6.0
2.0
3.0
4.5
4.0
2.0
3.5
4.0
4.0
3.77
3.85
3.76
3.83
3.81
3.83
3.77
3.86
3.82
3.89
3.79
3.91
3.80
3.88
3.76
3.91
3.81
3.89
3.78
3.91
3.81
3.86
3.80
3.89
12.0
13.0
12.0
12.0
12.0
11.0
12.0
12.0
12.0
10.0
12.0
12.0
H-1II
J1,2
5.36
4.0
5.28
4.0
5.15
4.0
5.15
4.0
4.48
8.0
4.50
8.0
4.40
8.0
4.41
8.0
4.40
8.0
4.42
8.0
4.35
7.5
4.36
7.5
H-2II
3.53
3.56
9.5
3.45
3.45
9.5
3.29
3.32
9.0
3.24
8.5
3.24
9.0
3.50
3.55
3.55
9.5
3.55
9.5
J2,3
10.0
10.0
10.0
10.0
10.0
H-3II
J3,4
3.65
9.0
3.66
9.5
3.63
9.0
3.61
9.0
3.48
9.0
3.49
9.5
3.38
9.0
3.88
9.0
3.62
3.5
3.65
3.5
3.48
3.0
3.49
3.0
H-4II
3.38
9.5
3.41
9.5
3.27
3.26
9.5
3.39
9.0
3.38
9.0
3.32
3.33
9.5
3.88
1.0
3.90
1.0
3.82
1.0
3.82
1.0
J4,5
10.0
10.0
H-5II
J5,6a
J5,6b
H-6aII
H-6bII
J6a,b
3.68
5.5
3.66
5.0
3.69
6.0
3.67
5.5
3.46
6.0
3.46
5.5
3.35
5.0
3.37
5.5
3.66
4.0
3.70
3.5
3.59
4.5
3.59
4.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
7.0
8.0
7.5
6.0
3.73
3.82
3.76
3.79
3.68
3.83
3.65
3.84
3.70
3.90
3.70
3.89
3.67
3.88
3.67
3.88
3.70
3.77
3.72
3.78
3.70
3.79
3.70
3.79
12.0
12.0
11.5
12.0
11.5
11.0
11.5
11.5
13.0
12.0
11.5
12.0
Aglycon; 4A: 3.38 (s, Me); 4E: 0.85 (t, J = 6.5Hz, Me); 4F: 0.90 (t, J = 7.0Hz, Me); 5A: 3.40 (s, Me); 5E: 0.84 (t, J = 6.5Hz, Me); 5F: 0.90
(t, J = 7.0Hz, Me); 6A: 3.53 (s, Me); 6E: 0.85 (t, J = 6.0Hz, Me); 6F: 0.90 (t, J = 6.0Hz, Me).
evaporated to dryness and chromatographed with the
CM system (100:1 ! 1:10) to give first the b anomer
and then a anomer. Accompanying bioses as impurities,
if any, were separated by chromatography on a Dowex
1 · 2 (OH form, 100–200mesh) with the PM system
(10:1 ! 1:10).43 Further purification was by recrystalli-
zation from the specified solvents or by repeated chro-
matography. The a/b values in Tables 1–3 are based
on the weights of the isolated anomers and those of frac-
tions containing both anomers whose anomeric ratios
of 4A,10,11,13,20,21 7A,11–13 5A,12,21 8A,12 6A,21 9A,44
9B,45 7D,46 8D,47 9D,48 7E,49 8E,50,51 7F,49,52–54
8F,50,53 8G,50 4I,10 8I,55 all showed correct m/z value
by HRMS (FAB), agreement with the reported data
within experimental error.
1.2.1. Allyl a-D-glucopyranosyl-(1 ! 4)-a-D-glucopyrano-
25
side (4B). Glass; ½aŠ þ 158 (c 0.8, H2O); HRMS
D
(FAB) Calcd for C15H26NaO11 [M+Na]+: 405.1373.
Found: m/z 405.1381.
1
were determined from their H NMR spectra. The Rf
values of the b anomers of each anomeric pair of bio-
sides were greater than those of the corresponding a
anomers by TLC using the CM system.
1.2.2. Allyl a-D-glucopyranosyl-(1 ! 4)-b-D-glucopyrano-
(FAB) Calcd for C15H26NaO11 [M+Na]+: 405.1373.
Found: m/z 405.1384.
25
side (7B). Glass; ½aŠ þ 70 (c 0.8, H2O); HRMS
D
The acetobromination of 2 was performed under
more-vigorous conditions as follows: a mixture of 2
(1.0g, 2.9mmol), AcBr (19mL, 0.23mmol), and AcOH
(19mL) was stirred at 60ꢁC for 0.5h (compound 2 from
Sigma needed longer warming, for 1h) to afford a homo-
geneous solution, which was evaporated to dryness as
before to give a crystalline solid [HRMS (FAB) Found:
m/z 721.0963. Calcd for C26H35BrNaO11 [M+Na]+:
721.0955].
1.2.3. Allyl b-D-glucopyranosyl-(1 ! 4)-a-D-glucopyrano-
25
side (5B). Glass; ½aŠ þ 82 (c 0.7, H2O); HRMS
D
(FAB) Calcd for C15H26NaO11 [M+Na]+: 405.1373.
Found: m/z 405.1371.
1.2.4. Allyl b-D-glucopyranosyl-(1 ! 4)-b-D-glucopyrano-
25
side (8B). Glass; ½aŠ ꢁ 22 (c 0.8, H2O); HRMS
D
The physical constants (melting points and specific
rotations in the specified solvents in the literature for)
(FAB) Calcd for C15H26NaO11 [M+Na]+: 405.1373.
Found: m/z 405.1376.

2420
S. Koto et al. / Carbohydrate Research 339 (2004) 2415–2424
Table 3. 1H NMR data of selected b-biosides determined at 400MHz (M = CD3OD, P = C5H5N with CD3OD, W = D2O)
Compounds (Solv.) 7A (W) 7E (W) 7F (M) 7L (M) 8A (W) 8E (W) 8F (P) 8L (P) 9A (W) 9E (M) 9F (P) 9L (P)
H-1I
J1,2
4.35
8.0
4.37
8.0
4.28
8.0
4.33
7.5
4.36
8.0
4.37
8.0
4.80
8.0
4.90
8.0
4.37
8.0
4.28
8.0
4.78
8.0
4.88
8.0
H-2I
3.25
9.5
3.28
9.0
3.23
9.0
3.20
8.5
3.26
9.5
3.30
9.0
4.03
9.0
4.00
9.0
3.27
9.0
3.24
8.0
4.03
8.5
4.00
8.5
J2,3
H-3I
J3,4
3.73
9.0
3.72
9.0
3.62
9.0
3.62
9.0
3.60
9.5
3.59
9.0
4.27
9.0
4.29
9.0
3.60
3.52
9.0
4.27
9.0
4.28
9.0
10.0
3.61
10.0
H-4I
3.59
3.62
9.5
3.54
9.5
3.56
9.0
3.58
9.0
3.61
4.33
9.5
4.35
9.0
3.57
9.0
4.33
9.0
4.35
9.0
J4,5
10.0
10.0
H-5I
J5,6a
J5,6b
H-6aI
H-6bI
J6a,b
3.55
4.5
3.48
4.5
3.37
4.5
3.35
3.5
3.57
4.5
3.50
5.0
3.90
2.5
3.93
2.5
3.58
4.0
3.40
5.0
3.87
3.0
3.89
3.0
2.0
2.0
2.0
2.5
2.0
2.0
4.0
4.0
2.0
2.0
4.0
4.0
3.73
3.90
3.77
3.87
3.81
3.88
3.66
3.87
3.77
3.95
3.82
3.89
4.49
4.56
4.48
4.57
3.77
3.95
3.84
3.90
4.49
4.56
4.47
4.56
12.0
12.0
12.0
11.0
12.5
12.0
12.0
12.0
12.0
12.5
12.0
12.0
H-1II
J1,2
5.36
4.0
5.34
4.0
5.17
4.0
5.16
4.0
4.46
8.0
4.50
8.0
5.19
8.0
5.20
8.5
4.41
8.0
4.47
7.5
5.14
8.0
5.15
8.0
H-2II
3.54
3.55
9.5
3.45
9.5
3.45
9.5
3.27
9.5
3.30
9.0
4.09
8.5
4.08
8.5
3.50
3.56
4.54
9.0
4.52
J2,3
10.0
10.0
10.0
10.0
H-3II
J3,4
3.64
9.0
3.65
9.5
3.65
9.0
3.58
9.0
3.46
9.0
3.45
9.5
4.21
9.0
4.21
9.0
3.63
3.5
3.49
3.5
4.17
3.5
4.16
3.0
H-4II
3.37
3.39
9.5
3.27
9.5
3.26
9.0
3.37
9.0
3.39
4.17
9.0
4.16
9.0
3.88
1.0
3.82
1.0
4.49
1.0
4.49
1.0
J4,5
10.0
10.0
H-5II
J5,6a
J5,6b
H-6aII
H-6bII
J6a,b
3.67
5.0
3.67
5.0
3.69
6.5
3.69
4.0
3.44
5.5
3.47
5.5
4.01
6.0
4.00
6.0
3.68
4.0
3.59
4.0
4.15
5.0
4.13
4.5
2.0
2.0
2.0
2.5
2.0
2.0
2.5
2.5
7.5
7.0
7.0
6.0
3.73
3.82
3.74
3.81
3.75
3.89
3.80
3.87
3.69
3.88
3.71
3.89
4.29
4.53
4.27
4.52
3.70
3.75
3.70
3.78
4.37
4.46
4.36
4.44
12.0
12.5
11.0
12.0
12.5
12.5
12.0
11.5
12.0
11.0
11.0
11.0
Aglycon; 7A: 3.53 (s, Me); 7E: 0.84 (t, J = 7.0Hz, Me); 7F: 0.91 (t, J = 6.5Hz, Me); 8A: 3.53 (s, Me); 8E: 0.84 (t, J = 6.5Hz, Me); 8F: 0.89
(t, J = 7.0Hz, Me); 9A: 3.53 (s, Me); 9E: 0.89 (t, J = 6.5Hz, Me); 9F: 0.88 (t, J = 6.0Hz, Me).
Table 4. 13C NMR data of selected a-biosides determined at 100MHz (M = CD3OD, W = D2O)
Compounds (Solv.) 4A (W) 4E (W) 4F (M) 4L (M) 5A (W) 5E (W) 5F (M) 5L (M) 6A (W) 6E (W) 6F (M) 6L (M)
C-lI
101.7
73.7
76.2
79.5
72.7
63.20
101.1
73.8
76.2
80.7
73.1
63.0
100.0
73.2
74.9
81.8
72.3
62.1
98.4
73.0
74.7
81.6
72.3
61.8
101.7
73.7
74.7
81.3
72.9
62.6
100.9
73.8
74.5
81.2
73.1
62.6
99.9
73.3
73.5
81.0
72.1
61.8
98.9
73.9
73.7
81.5
72.7
62.2
101.7
73.58
74.4
81.1
72.9
62.6
101.0
73.8
74.5
80.8
73.2
62.6
98.7
72.1
72.3
79.8
70.9
60.7
198.4
73.4
73.2
80.9
72.2
61.8
C-2I
C-3I
C-4I
C-5I
C-6I
C-1II
C-2II
C-3II
C-4II
C-5II
C-6II
102.3
74.4
75.5
72.0
75.3
63.15
103.2
74.6
75.8
71.7
75.5
63.1
102.9
74.3
75.1
71.5
74.7
62.7
102.8
74.1
74.9
71.4
74.6
62.6
105.2
75.8
78.2
72.1
78.8
63.3
105.2
75.8
78.4
72.2
78.7
63.4
104.6
74.9
77.9
71.4
78.1
62.4
105.0
75.4
78.3
71.8
78.6
62.9
105.6
73.63
75.2
71.2
78.0
63.7
105.6
73.6
75.4
71.3
78.0
63.8
103.9
71.4
73.6
69.1
76.0
61.3
105.1
72.6
74.8
70.3
77.0
62.5
Aglycon; 4A: 57.7 (Me); 4E: 16.5, 25.2, 28.5, 31.8 (2C), 31.9, 34.4, 71.1 (n-octyl); 4F: 14.4, 23.7, 27.3, 30.5, 30.6 (2C), 30.7 (2C), 30.8 (2C), 33.1, 69.3
(n-dodecyl); 4L: 24.0, 24.4, 27.5 (3C), 27.67, 27.74 (3C), 27.9, 28.2, 28.3, 32.5, 34.1, 78.1 (cyclopentadecyl); 5A: 57.8 (Me); 5E: 16.4, 25.1, 28.5, 31.8
(2C), 31.9, 34.4, 71.2 (n-octyl); 5F: 14.4, 23.7, 27.3, 30.5, 30.6 (2C), 30.7 (2C), 30.75, 30.77, 33.1, 69.3 (n-dodecyl); 5L: 24.7, 25.1, 28.2 (3C), 28.3, 28.4
(3C), 28.6, 28.9, 29.0, 33.2, 34.7, 78.8 (cyclopentadecyl); 6A: 57.8 (Me); 6E: 16.4, 25.2, 28.5, 31.8, 31.88, 31.93, 34.4, 71.2 (n-octyl); 6F: 13.3, 22.5, 26.2,
29.3, 29.4(2C), 29.5, 29.56, 29.59(2C), 31.9, 68.2 (n-dodecyl); 6L: 24.2, 24.6, 27.7 (3C), 27.8, 27.9 (3C), 28.1, 28.4, 28.5, 32.7, 34.2, 78.3
(cyclopentadecyl).
1.2.5. Allyl b-D-galactopyranosyl-(1 ! 4)-a-D-glucopyr-
(FAB) Calcd for C15H26NaO11 [M+Na]+: 405.1373.
Found: m/z 405.1366.
1.2.6. 4-Pentenyl a-D-glucopyranosyl-(1 ! 4)-a-D-gluco-
HRMS (FAB) Calcd for C17H30NaO11 [M+Na]+:
433.1686. Found: m/z 433.1681.
25
anoside (6B). Glass; ½aŠ þ 106 (c 1.1, H2O); HRMS
25
pyranoside (4C). Glass; ½aŠ þ 146 (c 0.8, H2O);
D
D

S. Koto et al. / Carbohydrate Research 339 (2004) 2415–2424
2421
Table 5. 13C NMR data of selected b-biosides determined at 100MHz (M = CD3OD, P = C5H5N with CD3OD, W = D2O)
Compounds (Solv.) 7A (W) 7B (W) 7C (M) 7D (M) 8E (W) 8F (W) 8G (P) 8H (P) 8I (W) 8J (M) 8K (P) 8L (P)
C-lI
105.8
75.7
78.9
79.4
77.2
63.4
105.0
75.6
79.0
79.9
77.3
63.4
104.2
74.6
77.8
81.2
76.5
62.7
103.0
74.7
77.8
81.2
76.4
62.7
105.7
75.5
77.0
81.3
77.4
62.7
105.1
75.5
77.2
81.5
77.4
62.9
104.5
74.86
76.9
81.4
76.7
62.2
103.3
75.01
76.9
81.6
76.6
62.4
105.8
75.5
77.1
81.1
77.4
62.7
104.2
74.7
76.4
80.7
76.4
61.9
104.5
74.9
76.7
81.9
76.6
62.2
103.2
75.0
76.7
82.0
76.5
62.3
C-2I
C-3I
C-4I
C-5I
C-6I
C-lII
102.2
74.3
75.5
72.0
75.4
63.2
102.6
74.4
75.4
71.9
75.6
63.2
102.8
74.1
75.0
71.4
74.7
62.1
102.7
74.1
75.0
71.5
74.7
62.1
105.2
75.8
78.2
72.1
78.6
63.2
105.3
75.9
78.3
72.1
78.7
63.3
105.1
74.91
78.3
71.6
78.6
62.5
105.1
74.96
78.3
71.6
78.6
62.5
105.6
73.6
75.2
71.2
78.0
63.7
105.1
72.5
74.8
70.3
77.0
62.5
105.8
72.6
75.2
70.2
77.3
62.2
105.8
72.6
75.2
70.3
77.3
62.2
C-2II
C-3II
C-4II
C-5II
C-6II
Aglycon; 7A: 59.8 (Me); 7E: 16.4, 25.1, 28.2, 31.7, 31.81, 31.84, 34.3, 73.1 (n-octyl); 7F: 14.5, 23.8, 27.1, 30.5, 30.6, 30.76 (3C), 30.80 (2C), 33.1, 70.9
(n-dodecyl); 7L: 24.0, 24.3, 27.7 (2C), 27.76, 27.82, 27.9 (2C), 27.97, 28.03, 28.48, 28.52, 32.9, 34.3, 79.8 (cyclopentadecyl); 8A: 59.9 (Me); 8E: 16.4,
25.2, 28.3, 31.9 (3C), 34.4, 73.2 (n-octyl); 8F: 14.5, 23.1, 26.6, 29.8, 30.0, 30.10 (3C), 30.14, 30.5 32.3, 70.2 (n-dodecyl); 8L: 23.3, 23.6, 27.0 (3C), 27.27
(4C), 27.33, 27.85, 27.92, 32.4, 34.0, 78.8 (cyclopentadecyl); 9A: 59.9 (Me); 9E: 14.4, 23.7, 27.1, 30.4, 30.5, 30.8, 33.0, 71.0 (n-octyl); 9F: 14.4, 23.1,
26.6, 29.8, 30.0, 30.07 (3C), 30.10, 30.4, 32.3, 70.1; 9L: 23.3, 23.6, 27.0 (3C), 27.2 (4C), 27.3, 27.8, 27.9, 32.4, 33.9, 78.8 (cyclopentadecyl).
1.2.7. 4-Pentenyl a-D-glucopyranosyl-(1 ! 4)-b-D-gluco-
HRMS (FAB) Calcd for C17H30NaO11 [M+Na]+:
433.1686. Found: m/z 433.1691.
HRMS (FAB) Calcd for C19H28NaO11 [M+Na]+:
455.1529. Found: m/z 455.1552.
25
pyranoside (7C). Glass; ½aŠ þ 59 (c 1.5, H2O);
D
1.2.15. n-Octyl a-D-glucopyranosyl-(1 ! 4)-a-D-gluco-
23
pyranoside (4E). Glass; ½aŠ þ 138 (c 1.1, MeOH);
D
1.2.8. 4-Pentenyl b-D-glucopyranosyl-(1 ! 4)-a-D-gluco-
HRMS (FAB) Calcd for C20H38NaO11 [M+Na]+:
477.2312. Found: m/z 477.2324.
25
pyranoside (5C). Glass; ½aŠ þ 72 (c 1.0, H2O);
D
HRMS (FAB) Calcd for C17H30NaO11 [M+Na]+:
433.1686. Found: m/z 433.1675.
1.2.16. n-Octyl b-D-glucopyranosyl-(1 ! 4)-a-D-gluco-
26
pyranoside (5E). Glass; ½aŠ þ 61 (c 0.6, MeOH);
D
1.2.9. 4-Pentenyl b-D-glucopyranosyl-(1 ! 4)-b-D-gluco-
HRMS (FAB) Calcd for C20H38NaO11 [M+Na]+:
477.2312. Found: m/z 477.2352.
25
pyranoside (8C). Glass; ½aŠ ꢁ 16 (c 1.0, H2O);
D
HRMS (FAB) Calcd for C17H30NaO11 [M+Na]+:
433.1686. Found: m/z 433.1697.
1.2.17. n-Octyl b-D-galactopyranosyl-(1 ! 4)-a-D-gluco-
27
pyranoside (6E). Glass; ½aŠ þ 87 (c 0.9, MeOH);
D
1.2.10. 4-Pentenyl b-D-galactopyranosyl-(1 ! 4)-a-D-
HRMS (FAB) Calcd for C20H38NaO11 [M+Na]+:
477.2312. Found: m/z 477.2310.
25
glucopyranoside (6C). Glass; ½aŠ þ 89 (c 1.1, H2O);
D
HRMS (FAB) Calcd for C17H30NaO11 [M+Na]+:
433.1686. Found: m/z 433.1664.
1.2.18. n-Octyl b-D-galactopyranosyl-(1 ! 4)-b-D-gluco-
25
pyranoside (9E). Glass; ½aŠ þ 3 (c 0.8, MeOH);
D
1.2.11. 4-Pentenyl b-D-galactopyranosyl-(1 ! 4)-b-D-
HRMS (FAB) Calcd for C20H38NaO11 [M+Na]+:
477.2312. Found: m/z 477.2340.
26
glucopyranoside (9C). Glass; ½aŠ þ 2 (c 0.5, H2O);
D
HRMS (FAB) Calcd for C17H30NaO11 [M+Na]+:
433.1686. Found: m/z 433.1703.
1.2.19. n-Dodecyl a-D-glucopyranosyl-(1 ! 4)-a-D-gluco-
25
pyranoside (4F). Glass; ½aŠ þ 122 (c 0.9, C5H5N);
D
1.2.12. Benzyl a-D-glucopyranosyl-(1 ! 4)-a-D-glucopyr-
HRMS (FAB) Calcd for C24H46NaO11 [M+Na]+:
533.2938. Found: m/z 533.2909.
25
anoside (4D). Glass; ½aŠ þ 162 (c 0.4, H2O); HRMS
D
(FAB) Calcd for C19H28NaO11 [M+Na]+: 455.1529.
Found: m/z 455.1537.
1.2.20. n-Dodecyl b-D-glucopyranosyl-(1 ! 4)-a-D-gluco-
24
pyranoside (5F). Crystals (from MeOH); mp 150–
1.2.13. Benzyl b-D-glucopyranosyl-(1 ! 4)-a-D-glucopyr-
153ꢁC; ½aŠ þ 46 (c 0.5, C5H5N); HRMS (FAB) Calcd
D
25
anoside (5D). Glass; ½aŠ þ 85 (c 0.5, H2O); HRMS
for C24H46NaO11 [M+Na]+: 533.2938. Found: m/z
533.2939. Anal. Calcd for C24H46O11ÆH20: C, 54.53, H,
9.15. Found: C, 54.83, H, 8.86.
D
(FAB) Calcd for C19H28NaO11 [M+Na]+: 455.1529.
Found: m/z 455.1553.
1.2.14. Benzyl b-D-galactopyranosyl-(1 ! 4)-a-D-gluco-
1.2.21. n-Dodecyl b-D-galactopyranosyl-(1 ! 4)-a-D-
glucopyranoside (6F). Crystals (from MeOH); mp
24
pyranoside (6D). Glass; ½aŠ þ 118 (c 0.7, H2O);
D

2422
S. Koto et al. / Carbohydrate Research 339 (2004) 2415–2424
24
D
160–162ꢁC; ½aŠ þ 64 (c 0.7, C5H5N); HRMS (FAB)
1.2.29. Cyclopentyl a-D-glucopyranosyl-(1 ! 4)-b-D-
HRMS (FAB) Calcd for C17H30NaO11 [M+Na]+:
433.1686. Found: m/z 433.1686.
25
glucopyranoside (7H). Glass; ½aŠ þ 67 (c 1.5, H2O);
Calcd for C24H46NaO11 [M+Na]+: 533.2938. Found:
m/z 533.2924. Anal. Calcd for C24H46O11Æ0.5H20: C,
55.48, H, 9.12. Found: C, 55.21, H, 8.98.
D
1.2.22. n-Dodecyl b-D-galactopyranosyl-(1 ! 4)-b-D-
25
1.2.30. Cyclopentyl b-D-glucopyranosyl-(1 ! 4)-a-D-
HRMS (FAB) Calcd for C17H30NaO11 [M+Na]+:
433.1686. Found: m/z 433.1680.
25
glucopyranoside (5H). Glass; ½aŠ þ 75 (c 1.0, H2O);
glucopyranoside (9F). Crystals (from MeOH); mp
106–111ꢁC; ½aŠ þ 8 (c 0.6, C5H5N); HRMS (FAB)
D
D
Calcd for C24H46NaO11 [M+Na]+: 533.2938. Found:
m/z 533.2937. Anal. Calcd for C24H46O11Æ0.5H20: C,
55.48, H, 9.12. Found: C, 55.20, H, 8.84.
1.2.31. Cyclopentyl b-D-glucopyranosyl-(1 ! 4)-b-D-
25
glucopyranoside (8H). Glass; ½aŠ ꢁ 22 (c 1.0, H2O);
D
1.2.23. n-Hexadecyl a-D-glucopyranosyl-(1 ! 4)-a-D-
25
HRMS (FAB) Calcd for C17H30NaO11 [M+Na]+:
433.1686. Found: m/z 433.1688.
glucopyranoside (4G). Crystallized spontaneouslyꢁ;
mp 195–202ꢁC; ½aŠ þ 98 (c 0.5, C5H5N); HRMS
D
(FAB) Calcd for C28H54NaO11 [M+Na]+: 589.3564.
Found: m/z 589.3574.
1.2.32. Cyclopentyl b-D-galactopyranosyl-(1 ! 4)-a-D-
25
glucopyranoside (6H). Glass; ½aŠ þ 106 (c 1.1, H2O);
D
HRMS (FAB) Calcd for C17H30NaO11 [M+Na]+:
433.1686. Found: m/z 433.1689.
1.2.24. n-Hexadecyl a-D-glucopyranosyl-(1 ! 4)-b-D-
24
glucopyranoside (7G). Crystals (from MeOH); mp
111–116ꢁC; ½aŠ þ 45 (c 0.5, C5H5N); HRMS (FAB)
D
Calcd for C28H54NaO11 [M+Na]+: 589.3564. Found:
m/z 589.3533. Anal. Calcd for C28H54O11: C, 59.34, H,
9.60. Found: C, 59.12, H, 9.58.
1.2.33. Cyclopentyl b-D-galactopyranosyl-(1 ! 4)-b-D-
26
glucopyranoside (9H). Glass; ½aŠ þ 1 (c 0.5, H2O);
D
HRMS (FAB) Calcd for C17H30NaO11 [M+Na]+:
433.1686. Found: m/z 433.1672.
1.2.25. n-Hexadecyl b-D-glucopyranosyl-(1 ! 4)-a-D-
25
1.2.34. Cyclohexyl a-D-glucopyranosyl-(1 ! 4)-b-D-
HRMS (FAB) Calcd or C18H32NaO11 [M+Na]+:
447.1842. Found: m/z 447.1853.
glucopyranoside (5G). Crystals (from MeOH); mp
119–126ꢁC; ½aŠ þ 43 (c 0.5, C5H5N); HRMS (FAB)
25
glucopyranoside (7I). Glass; ½aŠ þ 74 (c 0.9, H2O);
D
D
Calcd for C28H54NaO11 [M+Na]+: 589.3564. Found:
m/z 589.3586. Anal. Calcd for C28H54O11Æ0.5H20: C,
58.41, H, 9.63. Found: C, 58.53, H, 9.57.
1.2.35. Cyclohexyl b-D-glucopyranosyl-(1 ! 4)-a-D-
HRMS (FAB) Calcd for C18H32NaO11 [M+Na]+:
447.1842. Found: m/z 447.1824.
26
glucopyranoside (5I). Glass; ½aŠ þ 69 (c 0.9, H2O);
1.2.26. n-Hexadecyl b-D-galactopyranosyl-(1 ! 4)-a-D-
23
D
glucopyranoside (6G). Crystals (from MeOH), mp
172–176ꢁC; ½aŠ þ 58 (c 0.9, pyridine); HRMS (FAB)
D
Calcd for C28H54NaO11 [M+Na]+: 589.3564. Found:
m/z 589.3527. Anal. Calcd for C28H54O11ÆH2O: C,
57.51, H, 9.65. Found: C, 57.77, H, 9.36.
1.2.36. Cyclohexyl b-D-galactopyranosyl-(1 ! 4)-a-D-
26
glucopyranoside (6I). Glass; ½aŠ þ 102 (c 1.3, H2O);
D
HRMS (FAB) Calcd for C18H32NaO11 [M+Na]+:
447.1842. Found: m/z 447.1846.
1.2.27. n-Hexadecyl b-D-galactopyranosyl-(1 ! 4)-b-D-
25
glucopyranoside (9G). Crystals (from MeOH), mp
175–178ꢁC; ½aŠ þ 9 (c 0.3, pyridine+Me2SO (1:1));
D
1.2.37. Cyclohexyl b-D-galactopyranosyl-(1 ! 4)-b-D-
HRMS (FAB) Calcd for C28H54NaO11 [M+Na]+:
589.3564. Found: m/z 589.3565. Anal. Calcd for
C28H54O11ÆH20: C, 57.51, H, 9.65. Found: C, 57.57, H,
9.47.
25
glucopyranoside (9I). Glass; ½aŠ þ 5 (c 1.0, H2O);
D
HRMS (FAB) Calcd for C18H32NaO11 [M+Na]+:
447.1842.
1.2.38. Cyclooctyl
a-D-glucopyranosyl-(1 ! 4)-a-D-
1.2.28. Cyclopentyl a-D-glucopyranosyl-(1 ! 4)-a-D-
HRMS (FAB) Calcd for C17H30NaO11 [M+Na]+:
433.1686. Found: m/z 433.1680.
24
D
25
glucopyranoside (4H). Glass; ½aŠ þ 156 (c 0.8, H2O);
glucopyranoside (4J). Glass; ½aŠ þ 124 (c 0.6,
D
MeOH); HRMS (FAB) Calcd for C20H36NaO11
[M+Na]+: 475.2155. Found: m/z 475.2179.
1.2.39. Cyclooctyl a-D-glucopyranosyl-(1 ! 4)-b-D-gluco-
HRMS (FAB) Calcd for C20H36NaO11 [M+Na]+:
475.2155. Found: m/z 475.2163.
26
pyranoside (7J). Glass; ½aŠ þ 51 (c 1.1, MeOH);
ꢁ Glasses obtained crystallized spontaneously but, on the addition of a
small amount of MeOH or EtOH, began to liquefy. The addition of
EtOAc, Me2CO, or Et2O to them did not afford crystals.
D

S. Koto et al. / Carbohydrate Research 339 (2004) 2415–2424
2423
1.2.40. Cyclooctyl b-D-glucopyranosyl-(1 ! 4)-a-D-gluco-
HRMS (FAB) Calcd for C20H36NaO11 [M+Na]+:
475.2155. Found: m/z 475.2176.
1.2.49. Cyclododecyl b-D-galactopyranosyl-(1 ! 4)-b-D-
25
26
pyranoside (5J). Glass; ½aŠ þ 55 (c 0.7, MeOH);
glucopyranoside (9K). Prisms (from MeOH), mp 212–
213ꢁC; ½aŠ þ 5 (c 0.6, pyridine); HRMS (FAB) Calcd
D
D
for C24H44NaO11 [M+Na]+: 531.2781. Found: m/z
531.2788. Anal. Calcd for C24H44O11: C, 56.68, H,
8.72. Found: C, 56.28, H, 8.78.
1.2.41. Cyclooctyl b-D-glucopyranosyl-(1 ! 4)-b-D-gluco-
25
pyranoside (8J). Glass; ½aŠ ꢁ 5 (c 1.1, MeOH);
D
HRMS (FAB) Calcd for C20H36NaO11 [M+Na]+:
475.2155. Found: m/z 475.2155.
1.2.50. Cyclopentadecyl a-D-glucopyranosyl-(1 ! 4)-a-D-
26
glucopyranoside (4L). Glass; ½aŠ þ 91 (c 0.8, pyr-
D
idine); HRMS (FAB) Calcd for C27H50NaO11
[M+Na]+: 573.3251. Found: m/z 573.3272.
1.2.42. Cyclooctyl b-D-galactopyranosyl-(1 ! 4)-a-D-
28
glucopyranoside (6J). Crystallized spontaneously1; mp
1.2.51. Cyclopentadecyl a-D-glucopyranosyl-(1 ! 4)-b-D-
120–125ꢁC; ½aŠ þ 72 (c 0.5, MeOH); HRMS (FAB)
23
glucopyranoside (7L). Glass; ½aŠ þ 41 (c 1.1, pyri-
D
Calcd for C20H36NaO11 [M+Na]+: 475.2155. Found:
m/z 475.2148.
D
dine); HRMS (FAB) Calcd for C27H50NaO11
[M+Na]+: 573.3251. Found: m/z 573.3268.
1.2.43. Cyclooctyl b-D-galactopyranosyl-(1 ! 4)-b-D-
HRMS (FAB) Calcd for C20H36NaO11 [M+Na]+:
475.2155. Found: m/z 475.2141.
1.2.52. Cyclopentadecyl b-D-glucopyranosyl-(1 ! 4)-a-D-
25
glucopyranoside (9J). Glass; ½aŠ þ 7 (c 0.9, MeOH);
27
glucopyranoside (5L). Glass; ½aŠ þ 44 (c 0.9, pyr-
D
D
idine); HRMS (FAB) Calcd for C27H50NaO11
[M+Na]+: 573.3251. Found: m/z 573.3224.
1.2.53. Cyclopentadecyl-b-D-glucopyranosyl-(1 ! 4)-b-D-
24
1.2.44. Cyclododecyl a-D-glucopyranosyl-(1 ! 4)-a-D-
24
glucopyranoside (8L). Crystals (from MeOH), mp 198–
206ꢁC; ½aŠ ꢁ 12 (c 0.8, pyridine); HRMS (FAB) Calcd
glucopyranoside (4K). Glass; ½aŠ þ 115 (c 0.5, pyr-
D
idine); Rf = 0.46 (CHCl3–MeOH = 2:1); HRMS (FAB)
Calcd for C24H44NaO11 [M+Na]+: 531.2781. Found:
m/z 531.2771.
D
for C27H50NaO11 [M+Na]+: 573.3251. Found: m/z
573.3258. Anal. Calcd for C27H50O11Æ0.5H2O: C,
57.02, H, 9.22. Found: C, 56.97, H, 9.06.
1.2.45. Cyclododecyl a-D-glucopyranosyl-(1 ! 4)-b-D-
25
1.2.54. Cyclopentadecyl-b-D-galactopyranosyl-(1 ! 4)-a-
25
glucopyranoside (7K). Crystals (from MeOH); mp
195–197ꢁC; ½aŠ þ 48 (c 0.9, pyridine); HRMS (FAB)
D-glucopyranoside (6L). Crystallized spontaneouslyꢁ;
mp 121–123ꢁC; ½aŠ þ 53 (c 0.8, pyridine); HRMS
D
Calcd for C24H44NaO11 [M+Na]+: 531.2781. Found:
m/z 531.2784. Anal. Calcd for C24H44O11Æ0.5H20: C,
55.69, H, 8.76. Found: C, 55.97, H, 8.53.
D
(FAB) Calcd for C27H50NaO11 [M+Na]+: 573.3251.
Found: m/z 573.3250.
1.2.55. Cyclopentadecyl-b-D-galactopyranosyl-(1 ! 4)-b-
25
1.2.46. Cyclododecyl b-D-glucopyranosyl-(1 ! 4)-a-D-
23
D-glucopyranoside (9L). Crystals (from MeOH); mp
154–158ꢁC; ½aŠ þ 5 (c 0.7, pyridine); HRMS (FAB)
glucopyranoside (5K). Crystals (from MeOH), mp
206–207ꢁC; ½aŠ þ 38 (c 1.2, pyridine); HRMS (FAB)
D
Calcd for C27H50NaO11 [M+Na]+: 573.3251. Found:
m/z 573.3245. Anal. Calcd for C27H50O11Æ0.5H20: C,
57.94, H, 9.18. Found: C, 58.00, H, 9.08.
D
Calcd for C24H44NaO11 [M+Na]+: 531.2781. Found:
m/z 531.2801. Anal. Calcd for C24H44O11Æ0.5H20: C,
55.69, H, 8.76. Found: C, 55.70, H, 8.64.
1.2.47. Cyclododecyl b-D-glucopyranosyl-(1 ! 4)-b-D-
23
References
glucopyranoside (8K). Crystals (from MeOH), mp
231–238ꢁC; ½aŠ ꢁ 12 (c 1.0, pyridine); HRMS (FAB)
D
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