Highly β-Selective Glycosylation Reactions for the Synthesis of ω-Functionalized Alkyl β-Maltoside as a Co-crystallizing Detergent

Article abstract of DOI:10.1134/S1070428020100231

Abstract: Methods have been reported for the preparation of ω-functionalized alkyl maltoside and glycoside detergents via a simple and inexpensive synthetic route. The key step was stannic chloride-mediated glycosylation of long-chain alcohols or thiols with maltose octaacetate at 0 or –10°C, respectively, within a very short time (isolated yield 17–44%), which provided more than 98% β-selectivity.

Full text of DOI:10.1134/S1070428020100231

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2020, Vol. 56, No. 10, pp. 1806–1814. © Pleiades Publishing, Ltd., 2020.
Highly β-Selective Glycosylation Reactions
for the Synthesis of ω-Functionalized Alkyl β-Maltoside
as a Co-crystallizing Detergent
M. A. Hossaina,b,*, S. M. A. Hakim Siddikib,c, M. Eliasa, M. M. Rahmana, and M. A. R. Jamilc
a Department of Chemistry, Jagannath University, Dhaka, 1100 Bangladesh
b Graduate School of Material Science, University of Hyogo, Hyogo, 678-1297 Japan
c Institute of Catalysis, Hokkaido University, Sapporo, 001-0021 Japan
*e-mail: awlad1975@yahoo.com
Received May 29, 2020; revised June 11, 2020; accepted June 29, 2020
Abstract—Methods have been reported for the preparation of ω-functionalized alkyl maltoside and glycoside
detergents via a simple and inexpensive synthetic route. The key step was stannic chloride-mediated
glycosylation of long-chain alcohols or thiols with maltose octaacetate at 0 or –10°C, respectively, within a very
short time (isolated yield 17–44%), which provided more than 98% β-selectivity.
Keywords: maltoside detergent, glycosylation, maltose octaacetate, β-selectivity, ω-functionalized glycoside
DOI: 10.1134/S1070428020100231
INTRODUCTION
with 25% yield via glycosylation using acetobromo-
maltose as intermediate and silver carbonate as catalyst
[6]. Matsumoto and co-workers [7] synthesized decyl
β-lactoside detergent with 78% yield through solvolysis
of decyl β-lactose heptaacetate which was prepared by
reaction with maltose octaacetate using boron tri-
fluoride as Lewis acid with 25% yield. Hoheisel and
Frauenrath [8] reported glycosylation of propargyl al-
cohol with pentaacetyl-β-D-glucose in 79% yield using
boron trifluoride–ethyl ether complex at room tempera-
ture. An enzyme-based method for the synthesis of
alkyl glycosides using C1–C12 unbranched primary
alcohols was described in [9]; however, it required
a long reaction time. The synthesis of C7–C16-alkyl
maltosides in the presence of tin(IV) chloride as
a Lewis acid catalyst is also time dependent, and
prolonged reaction time favored the formation of
α-anomeric glycoside [10].
Alkyl glycoside detergents are necessary for the
crystallization of membrane proteins. The history of
X-ray crystallography of cytochrome c oxidase clearly
indicates that selectivity and purity of detergent are the
most significant factors to achieve high structural
resolution. Decyl maltoside detergent forms crystals
with high resolution as revealed by X-ray crystal-
lography [1–4]. High anomeric selectivity of the
glycosylation reaction is very crucial for the synthesis
of detergents.
Several β-selective glycosylation reactions have
already been reported. Banoub and Bundle prepared
a glycoside with high β-selectivity (61–68%) by reac-
tion of maltose octaacetate with ethyl 9-hydroxy-
nonanoate using stannic chloride at –10°C and at long
reaction time [5]. Ferguson-Miller and co-workers [4]
synthesized a glycoside of n-octanol by reaction with
glucose pentaacetate through aceto-bromoglucose
intermediate by using silver carbonate and iodine at
room temperature. After preparation of octyl β-D-glu-
cose peracetate, they synthesized octyl β-D-glucoside
(detergent) with 60% isolated yield via solvolysis.
However, the β/α-anomer ratio was not clearly men-
tioned in that report. The same research team also
reported the synthesis of lauryl β-D-maltoside detergent
There are several types of detergents that have
already been synthesized and used for crystallization of
membrane proteins. Generally, the nature of the lipo-
philic chain of detergents plays an important role in the
quality of protein crystals. However, detergents func-
tionalized at the ω-position of the lipophilic chain, as
well as those derived from long-chain thiols have not
been synthesized as yet. Therefore, we focused on the
synthesis of new ω-functionalized detergents to im-
1806

HIGHLY β-SELECTIVE GLYCOSYLATION REACTIONS
1807
Scheme 1.
AcO
AcO
SnCl4 (2 equiv)
CH2Cl2 (1.0 mL/mmol)
0°C, 80 min
O
O
AcO
AcO
AcO
AcO
AcO
AcO
+
RXH
AcO
AcO
O
O
O
O
AcO
AcO
OAc
X
R
OAc
OAc
Maltose octaacetate
3 equiv
Alkyl β-maltose peracetate (β:α > 98:2)
HO
O
Et3N/H2O/MeOH (1:1:2)
50°C, 18 h
HO
HO
HO
HO
O
HO
O
X
R
OH
1–13
Alkyl β-maltoside (β:α > 98:2)
1–10, 12, X = O; 11, 13, X = S; 1, R = CH2=CH(CH2)8; 2, R = Cl(CH2)9; 3, R = MeO(CH2)8; 4, R = Me(CH2)8; 5, R = CH2=CH(CH2)9;
6, Me(CH2)10; 7, R = Me(CH2)13; 8, R = Me2CH(CH2)7; 9, R = Me2CH(CH2)8; 10, R = 8-cyclopropyloctyl; 11, R = Me(CH2)11;
12, 13, R = Me(CH2)6.
prove the quality of crystals that could be obtained
with their use.
ω-Functionalized alcohols and thiols with different
lipophilic chain lengths were involved in the glyco-
sylation reaction. In case of thiols, the reaction
occurred in a relatively short time due to high nucleo-
philicty of sulfur atom. The isolated yield varied from
17 to 44% (Table 1). In some cases, the isolated yield
was relatively poor since it referred to the pure product
after column chromatography, and isolation of the
product by column chromatography was difficult due
to overlapping with impurities. The overall β-selec-
Herein, we present the synthesis of ω-functionalized
detergents from maltose octaacetate via glycosylation
reaction using tin(IV) chloride as Lewis acid at 0°C
with over 98% β-selectivity (68–88% yield). Stannic
chloride is less expensive and easy to handle. We also
prepared glucopyranoside detergent from pentaacetyl-
β-D-glucose and achieved 78–80% yield using boron
trifluoride–diethyl ether complex at room temperature
with over 99% β-selectivity. To the best of our knowl-
edge, this is the highest β-selectivity of maltoside
detergent preparation through glycosylation reaction.
1
tivity was over 98% according to the H NMR data. It
was assumed that there was no effect of ω-functional
groups on the selectivity.
After glycosylation, the corresponding alkyl β-malt-
osides were prepared by solvolysis (deacetylation).
The solvolysis smoothly proceeded without loss of α/β
ratio. The isolated yields were 68–88% (Scheme 1).
The products were isolated by column chromatography
on Dowex (OH) using methanol as eluent. The α/β
ratio and chemical purity were determined, respec-
RESULTS AND DISCUSSION
The glycosylation of 9-chlorononan-1-ol with
maltose octaacetate was carried out at room tempera-
ture, but the fraction of the α-anomer was very high
(β/α ratio 65/35; isolated yield 39%). We then per-
formed this glycosylation at 0°C for about 1 h and
achieved high β-selectivity (β/α >98%; isolated yield
18%). Prolongation of the reaction time in combination
with higher temperature increased the fraction of
α-glycosides due to β/α anomerization according to the
mechanism described in [5, 11]. The other glycosyla-
tion reactions were performed under the optimized
conditions (Scheme 1) using a very small amount of
solvent (CH2Cl2) over a very short time maintaining
the temperature at 0°C; the β-selectivity was higher
than that reported in [12].
1
tively, by H NMR and HPLC (GL Sciences ODS-3
column, 4.6×250 mm, refractive index detector, eluent
30% H2O in MeOH, flow rate 1.0 mL/min). The
specific rotations were also in good agreement with
β-selectivity [13, 14].
We also synthesized glucopyranoside detergents
(Scheme 2). The glycosylation step was performed
using tin(IV) chloride as catalyst. However, in the case
of boron trifluoride–diethyl ether complex, the amount
of impurities was lower, isolation of the products was
relatively easier, and the β-selectivity was over 99%
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 10 2020

HOSSAIN et al.
1808
Scheme 2.
BF3·Et2O (1.2 equiv)
CH2Cl2 (10 mL/mmol)
0°C to r.t., 24 min
AcO
AcO
O
O
+
Me(CH2)6YH
2 equiv
OAc
Y
Me
AcO
AcO
AcO
AcO
( )6
OAc
AcO
HO
Et3N/H2O/MeOH (1:1:2)
50°C, 14 h
O
Y
Me
HO
HO
( )6
OH
(1H NMR). The isolated yields were 27 (X = O) and
34% (X = S). Both isolation and analysis methods were
the same as in the preparation of maltoside detergents.
Thus, both maltoside and glucopyranoside detergents
may be perfect detergents to enhance the quality of
protein crystals.
bond (orbital structure), and C11 derivative 10 with
a terminal cyclopropyl group is more polar than un-
branched C11 derivative 6. Higher polarity of the lipo-
philic chain of the glycoside detergent may favor
crystallization of membrane proteins. Hence, maltoside
detergent 3 with an ω-methoxy-substituted group could
be efficient in co-crystallization system [15].
Table 1 also contains the HPLC retention times of
detergents 1–13, which were used to estimate their
polarity. The polarity increases as the retention time
decreases. The polarity depends on the length of lipo-
philic chain and ω-functional group. Very high polarity
was observed for C8-detergent 3 with a methoxy group,
and detergent 11 with a long lipophilic chain (C12) and
a sulfur atom was characterized by very low polarity.
Compound 1 with a terminal C=C bond in the C10
chain is more polar than its saturated analog since C=C
double bond is more polar than the single carbon–
carbon bond. Cyclopropyl group behaves like a double
EXPERIMENTAL
Commercial tin(IV) chloride and Dowex (OH form)
resin were used without any further treatment. Maltose
octaacetate was prepared as described in [13, 16, 17];
dec-9-en-1-ol, nonan-1-ol, undec-10-en-1-ol, undecan-
1-ol, tetradecan-1-ol, dodecane-1-thiol, heptan-1-ol,
and heptane-1-thiol were commercial products; 8-me-
thoxyoctan-1-ol, 9-chlorononan-1-ol, 8-methylnonan-
1-ol, 8-cyclopropyloctan-1-ol, and 9-methyldecan-1-ol
were prepared according to reported procedures.
Table 1. Yields of alkyl hepta-O-acetyl-β-maltosides and HPLC retention times of the corresponding alkyl β-maltosides
Number of carbon Yield of alkyl hepta-O-
Retention
Alcohol
Dec-9-en-1-ol
Alkyl β-maltoside
atoms
acetyl-β-maltoside,a %
time,b min
10
9
30
18
28
27
19
37
44
32
17
28
17c
22
38c
1
2
11.08
8.69
9-Chlorononan-1-ol
8-Metoxyoctan-1-ol
Nonan-1-ol
8
3
4.11
9
4
11.09
18.28
31.17
Undec-10-en-1-ol
Undecan-1-ol
11
11
14
10
11
11
12
7
5
6
Tetradecan-1-ol
7
8-Methylnonan-1-ol
9-Methyldecan-1-ol
8-Cyclopropyloctan-1-ol
Dodecane-1-thiol
Heptan-1-ol
8
15.42
29.11
9
10
11
12
13
19.88
64.19
5.90/6.22
6.96/7.46
Heptane-1-thiol
7
a
b
c
Isolated yield.
HPLC; RI detector, ODS-3 column (GL Sciences), 30% H2O in MeOH, flow rate 1.0 mL/min.
Temperature –10°C, reaction time 55 min.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 10 2020

HIGHLY β-SELECTIVE GLYCOSYLATION REACTIONS
1809
1
1
The H NMR spectra were recorded on a a JEOL
tin(IV) chloride. Yield 1.06 g (18%). H NMR spec-
trum (CDCl3), δ, ppm: 1.14–1.18 m (8H), 1.30 m (2H),
1.44 m (2H), 1.65 m (2H), 1.90 s (6H), 1.91 s (3H),
1.92 s (3H), 1.93 s (3H), 1.99 s (3H), 2.04 s (3H),
3.37 q (1H, J = 15.9 Hz), 3.42 t (1H, J = 6.6 Hz),
3.58 d (1H, J = 9.6 Hz), 3.74 q (1H, J = 15.9 Hz),
3.87 d (1H, J = 10.2 Hz), 3.90 t (1H, J = 9.2 Hz),
3.94 d (1H, J = 12.0 Hz), 4.14 d.t (2H), 4.37 d.d (1H,
J = 1.18, 12.6 Hz), 4.42 d (1H, J = 7.8 Hz), 4.71 t (1H,
J = 8.4 Hz), 4.75 d.d (1H, J = 4.2, 10.2 Hz), 4.95 t (1H,
J = 12.6 Hz), 5.15 t (1H, J = 9.6 Hz), 5.26 t (1H, J =
10.2 Hz), 5.31 d (1H, J = 3.6 Hz).
ECA-600 spectrometer operating at 600.17 MHz; the
chemical shifts were measured relative to the residual
proton signal of the solvent, and the coupling constants
were measured with an accuracy of ±0.1 Hz. The
optical rotations were measured with a Perkin Elmer
243B polarimeter. The high resolution mass spectra
were run on Jeol JMS-AX505HF (electron impact) and
Jeol JMS-T100LC (electronspray ionization) instru-
ments. HPLC analyses were carried out using a Hitachi
L-6200 intelligent pump, Shimadzu SPD-10A RI
detector, and GL Sciences ODS-3 column.
General procedure for the synthesis of alkyl
hepta-O-acetyl-β-maltosides. Tin(IV) chloride
(2.0 equiv) was added very slowly to a solution of
maltose octaacetate (1.0 mmol) in anhydrous methy-
lene chloride (1.0 mL) at 0°C under a nitrogen atmo-
sphere. After 15 min, the corresponding alcohol or thiol
(3.0 equiv) was added slowly at 0°C (at –10°C in the
case of thiol), and the mixture was stirred 0°C (or
–10°C) for 80 min. The progress of the reaction was
monitored by TLC on silica gel plates using ethyl
acetate–hexane (1:1) as eluent. The mixture was diluted
with cold (0°C) ethyl acetate, quenched with water, and
extracted with ethyl acetate (3×50 mL). The combined
extracts were washed with brine, dried over Na2SO4
and concentrated under reduced pressure, and the
residue was purified by column chromatography on
Dowex (OH form) using ethyl acetate–hexane (15:100,
20:100, and 25:100) as eluent. The products were
isolated as colorless viscous oils.
8-Methoxyoctyl hepta-O-acetyl-β-maltoside was
synthesized from maltose octaacetate (1.0 g,
1.47 mmol) and 8-methoxyoctan-1-ol (707 mg,
4.41 mmol) using 0.34 mL (766 mg, 2.94 mmol) of
1
tin(IV) chloride. Yield 316 mg (28%). H NMR spec-
trum (CDCl3), δ, ppm: 1.10–1.15 m (8H), 1.33 m (2H),
1.42 m (2H), 1.85 s (3H), 1.86 s (3H), 1.87 s (3H),
1.88 s (3H), 1.90 s (3H), 1.96 s (3H), 2.00 s (3H),
3.18 s (3H), 3.22 t (2H, J = 6.9 Hz), 3.33 q (1H, J =
16.5 Hz), 3.70 q.d (1H, J = 9.0 Hz), 3.84 d (1H, J =
10.8 Hz), 3.87 t (1H, J = 9.3 Hz), 3.91 d (1H, J =
12.0 Hz), 4.12 m (2H), 4.33 d.d (1H, J = 1.8, 11.4 Hz),
4.39 d (1H, J = 7.8 Hz), 4.67 t (1H, J = 7.8 Hz),
4.72 d.d (1H, J = 4.2, 10.8 Hz), 4.91 t (1H, J = 9.6 Hz),
5.12 t (1H, J = 9.6 Hz), 5.22 t (1H, J = 10.8 Hz), 5.28 d
(1H, J = 3.6 Hz).
Nonyl hepta-O-acetyl-β-maltoside was synthe-
sized from maltose octaacetate (1.0 g, 1.47 mmol) and
nonan-1-ol (0.77 mL, 636 mg, 4.41 mmol) using
0.34 mL (766 mg, 2.94 mmol) of tin(IV) chloride.
Dec-9-en-1-yl hepta-O-acetyl-β-maltoside was
synthesized from maltose octaacetate (1.0 g,
1.47 mmol) and dec-9-en-1-ol (0.8 mL, 689 mg,
4.41 mmol) using 0.34 mL (766 mg, 2.94 mmol) of
1
Yield 300 mg (27%). H NMR spectrum (CDCl3), δ,
ppm: 0.84 t (3H, J = 6.3 Hz), 1.18–1.33 m (10H), 1.44–
1.58 m (4H), 1.97 s (6H), 1.98 s (3H), 1.99 s (3H),
2.01 s (3H), 2.07 s (3H), 2.11 s (3H), 3.43 q (1H, J =
15.3 Hz), 3.64 q.d (1H, J = 9.6), 3.81 q (1H, J =
15.3 Hz), 3.92 d (1H, J = 9.6 Hz), 3.97 t (1H, J =
9.6 Hz), 4.01 d (1H, J = 12.6 Hz), 4.21d.t (2H, J = 3.6,
11.4 Hz), 4.43 d (1H, J = 11.4 Hz), 4.48 d (1H,
J = 7.8 Hz), 4.78 t (1H, J = 7.8 Hz), 4.82 d.d (1H,
J = 4.2, 10.5 Hz), 5.02 t (1H, J = 9.6 Hz), 5.22 t (1H,
J = 9.6 Hz), 5.33 t (1H, J = 10.5 Hz), 5.38 d (1H,
J = 3.6 Hz).
1
tin(IV) chloride. Yield 336 mg (30%). H NMR spec-
trum (CDCl3), δ, ppm: 1.12–1.24 m (8H), 1.32–1.39 m
(4H), 1.52 m (2H), 1.97 s (6H), 1.98 s (3H), 1.99 s
(3H), 2.02 s (3H), 2.07 s (3H), 2.11 s (3H), 3.43 q (1H,
J = 8.3 Hz), 3.64 m (1H), 3.81 m (1H), 3.93 d (1H,
J = 9.6 Hz), 3.97 t (1H, J = 9.6 Hz), 4.01 d (1H, J =
12.0 Hz), 4.21 d.t (2H, J = 4.5, 12.0 Hz), 4.44 d.d (1H,
J = 2.4, 12.0 Hz), 4.78 t (1H, J = 8.4 Hz), 4.83 d.d (1H,
J = 4.2, 10.2 Hz), 4.90 d (1H, J = 9.6 Hz), 4.96 d (1H,
J = 16.8 Hz), 5.02 t (1H, J = 9.6 Hz), 5.22 t (1H, J =
9.0 Hz), 5.33 t (1H, J = 10.2 Hz), 5.39 d (1H, J =
3.6 Hz), 5.77 m (1H).
Undec-10-en-1-yl hepta-O-acetyl-β-maltoside
was synthesized from maltose octaacetate (1.0 g,
1.47 mmol) and undec-10-en-1-ol (0.88 mL,
4.41 mmol) using 0.34 mL (766 mg, 2.94 mmol) of
9-Chlorononyl hepta-O-acetyl-β-maltoside was
synthesized from maltose octaacetate (5.0 g,
7.37 mmol) and 9-chlorononan-1-ol (3.95 g,
22.11 mmol) using 1.73 mL (3.84 g, 14.74 mmol) of
1
tin(IV) chloride. Yield 215 mg (19%). H NMR spec-
trum (CDCl3), δ, ppm: 1.18–1.19 m (10H), 1.28–
1.32 m (4H), 1.48 m (2H), 1.93 s (6H), 1.94 s (3H),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 10 2020

HOSSAIN et al.
1810
1.96 s (3H), 1.97 s (3H), 2.03 s (3H), 2.07 s (3H),
3.39 q (1H, J = 15.6 Hz), 3.61 q.d (1H, J = 9.0 Hz),
3.77 q (1H, J = 15.6 Hz), 3.89 d (1H, J = 4.2 Hz),
3.94 t (1H, J = 9.3 Hz), 3.97 d (1H, J = 12.6 Hz),
4.18 d.t (2H, J = 3.6, 12.0 Hz), 4.40 d.d (1H, J = 1.8,
12.0 Hz), 4.45 d (1H, J = 8.4 Hz), 4.74 t (1H, J =
8.4 Hz), 4.79 d.d (1H, J = 4.2, 10.8 Hz), 4.85 d (1H,
J = 10.8 Hz), 4.92 d (1H, J = 17.4 Hz), 4.98 t (1H, J =
9.9 Hz), 5.18 t (1H, J = 9.9 Hz), 5.29 t (1H, J =
9.9 Hz), 5.35 d (1H, J = 3.6 Hz), 5.73 m (1H).
4.20 d.t (2H, J = 4.2, 11.4 Hz), 4.41 d (1H, J =
10.8 Hz), 4.46 d (1H, J = 8.4 Hz), 4.75 t (1H, J =
10.2 Hz), 4.80d.d (1H, J = 4.2, 10.2 Hz), 4.99 t (1H,
J = 9.6 Hz), 5.19 t (1H, J = 9.6 Hz), 5.30 t (1H, J =
10.2 Hz), 5.36 d (1H, J = 3.6 Hz).
9-Methyldecyl hepta-O-acetyl-β-maltoside was
synthesized from maltose octaacetate (543 mg,
0.8 mmol) and 9-methyldecan-1-ol (414 mg, 2.4 mmol)
using 0.19 mL (417 mg, 1.6 mmol) of tin(IV) chloride.
1
Yield 105 mg (17%). H NMR spectrum (CDCl3), δ,
Undecyl hepta-O-acetyl-β-maltoside was synthe-
sized from maltose octaacetate (1.0 g, 1.47 mmol) and
undecan-1-ol (0.92 mL, 4.41 mmol) using 0.34 mL
(766 mg, 2.94 mmol) of tin(IV) chloride. Yield 430 mg
ppm: 0.83 d (6H, J = 6.0 Hz), 1.12 m (2H), 1.19–
1.32 m (9H), 1.45–1.54 m (4H), 1.98 s (6H), 1.99 s
(3H), 2.00 s (3H), 2.02 s (3H), 2.08 s (3H), 2.12 s (3H),
3.40 q (1H, J = 16.2 Hz), 3.65 q (1H, J = 12.6 Hz),
3.82 q (1H, J = 16.2 Hz), 3.93 d (1H, J = 10.8 Hz),
3.98 t (1H, J = 9.0 Hz), 4.01 d (1H, J = 13.2 Hz),
4.22 d.t (2H, J = 4.2, 12.0 Hz), 4.44 d.d (1H, J = 2.4,
12.0 Hz), 4.49 d (1H, J = 7.8 Hz), 4.79 t (1H, J =
7.8 Hz), 4.83 d.d (1H, J = 3.6, 10.8 Hz), 5.03 t (1H, J =
9.6 Hz), 5.23 t (1H, J = 9.6 Hz), 5.34 t (1H, J =
10.2 Hz), 5.39 d (1H, J = 4.2 Hz).
1
(37%). H NMR (CDCl3), δ, ppm: 0.86 t (3H, J =
6.9 Hz), 1.22–1.25 m (12H), 1.54 s (6H), 1.98 s (6H),
1.99 s (3H), 2.00 s (3H), 2.02 s (3H), 2.08 s (3H),
2.12 s (3H), 3.44 q (1H, J = 15.9 Hz), 3.65 q.d (1H, J =
9.6), 3.82 q (1H, J = 15.9 Hz), 3.93 d (1H, J =
10.2 Hz), 3.98 t (1H, J = 9.3 Hz), 4.01 d (1H, J =
13.2 Hz), 4.22 d.t (2H, J = 3.6, 12.0 Hz), 4.45 d.d (1H,
J = 2.4, 12.0 Hz), 4.49 d (1H, J = 8.4 Hz), 4.79 t (1H,
J = 8.4 Hz), 4.84 d (1H, J = 10.2 Hz), 5.03 t (1H, J =
9.9 Hz), 5.23 t (1H, J = 9.9 Hz), 5.34 t (1H, J =
9.9 Hz), 5.40 d (1H, J = 3.6 Hz).
8-Cyclopropyloctyl hepta-O-acetyl-β-maltoside
was synthesized from maltose octaacetate (2.12 g,
3.13 mmol) and 8-cyclopropyloctan-1-ol (1.60 g,
9.40 mmol) using 0.73 mL (1.63 g, 6.26 mmol) of
Tetradecyl hepta-O-acetyl-β-maltoside was syn-
thesized from maltose octaacetate (1.0 g, 1.47 mmol)
and tetradecan-1-ol (946 mg, 4.41 mmol) using
0.34 mL (766 mg, 2.94 mmol) of tin(IV) chloride.
1
tin(IV) chloride. Yield 686 mg (28%). H NMR spec-
trum (CDCl3), δ, ppm: 0.06 q (2H, J = 9.6 Hz). 0.33 q
(2H, J = 12.6 Hz), 1.11–1.34 m (11H), 1.43 m (2H),
1.96 s (6H), 1.97 s (3H), 1.98 s (3H), 2.00 s (3H),
2.06 s (3H), 2.12 s (3H), 3.42 q (1H, J = 16.2 Hz),
3.63 q.d (1H, J = 9.6 Hz), 3.80 q (1H, J = 16.2 Hz),
3.93 d (1H, J = 10.2 Hz), 3.98 t (1H, J = 9.0 Hz),
4.01 d (1H, J = 12.6 Hz), 4.22 d.t (2H, J = 4.2,
12.0 Hz), 4.42 d.d (1H, J = 1.8, 12.0 Hz), 4.47 d (1H,
J = 8.4 Hz), 4.77 t (1H, J = 8.4 Hz), 4.81 d.d (1H,
J = 4.2, 10.2 Hz), 5.01 t (1H, J = 9.9 Hz), 5.21 t (1H,
J = 9.9 Hz), 5.32 t (1H, J = 9.9 Hz), 5.37 d (1H,
J = 4.2 Hz).
1
Yield 547 mg (44%). H NMR spectrum (CDCl3), δ,
ppm: 0.71 t (3H, J = 6.6 Hz), 1.03–1.21 m (22H),
1.39 m (2H), 1.84 s (6H), 1.86 s (3H), 1.87 s (6H),
1.93 s (3H), 1.98 s (3H), 3.31 q (1H, J = 15.0 Hz),
3.53 q.d (1H, J = 9.0 Hz), 3.68 q (1H, J = 15.0 Hz),
3.82 d (1H, J = 12.6 Hz), 3.84 t (1H, J = 9.6 Hz),
3.88 d (1H, J = 12.6 Hz), 4.09 d.t (2H), 4.30 d (1H, J =
12.0 Hz), 4.37 d (1H, J = 7.8 Hz), 4.64 t (1H, J =
7.8 Hz), 4.69 d.d (1H, J = 4.2, 10.2 Hz), 4.89 t (1H,
J = 10.2 Hz), 5.09 t (1H, J = 9.0 Hz), 5.20 t (1H, J =
9.9 Hz), 5.26 d (1H, J = 3.6 Hz).
Dodecyl hepta-O-acetyl-1-thio-β-maltoside was
synthesized from maltose octaacetate (500 mg,
0.74 mmol) and dodecane-1-thiol (0.53 mL, 449 mg,
2.22 mmol) using 0.17 mL (385 mg, 1.48 mmol) of
8-Methylnonyl hepta-O-acetyl-β-maltoside was
synthesized from maltose octaacetate (875 mg,
1.29 mmol) and 8-methylnonan-1-ol (612 mg,
3.87 mmol) using 0.3 mL (672 mg, 2.58 mmol) of
1
tin(IV) chloride. Yield 103 mg (17%). H NMR spec-
1
trum (CDCl3), δ, ppm: 0.82 t (3H, J = 6.6 Hz), 1.19–
1.37 m (18H), 1.52 m (2H), 1.95 s (6H), 1.96 s (3H),
1.97 m (3H), 1.99 m (3H), 2.01 m (3H), 2.05 m (3H),
2.08 s (3H), 2.54 m (2H), 3.63 q (1H), 3.92 m (1H),
3.99 t (1H, J = 10.2 Hz), 4.20 d.t (2H), 4.35 t (1H, J =
10.2 Hz), 4.40 d.d (1H, J = 1.8, 11.0 Hz), 4.47 d (1H,
J = 9.6 Hz), 4.80 t (1H), 4.85 d.d (1H, J = 5.4, 9.6 Hz),
tin(IV) chloride. Yield 319 mg (32%). H NMR spec-
trum (CDCl3), δ, ppm: 0.79 d (6H, J = 6.6 Hz), 1.18–
1.21 m (11H), 1.40 m (2H), 1.94 s (6H), 1.95 s (3H),
1.96 s (3H), 1.98 s (6H), 2.04 s (3H), 2.08 s (3H),
3.41 q (1H, J = 15.0 Hz), 3.62 q.d (1H, J = 9.0 Hz),
3.79 q (1H, J = 15.0 Hz), 3.90 d (1H, J = 9.6 Hz),
3.94 t (1H, J = 9.6 Hz), 3.98 d (1H, J = 12.6 Hz),
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HIGHLY β-SELECTIVE GLYCOSYLATION REACTIONS
1811
5.01 m (1H), 5.23 t (1H, J = 9.6 Hz), 5.34 t (1H, J =
11.0 Hz), 5.47 d (1H, J = 5.4 Hz).
spectrum (DMSO-d6), δ, ppm: 1.21–1.36 m (12H),
2.00 q (2H, J = 13.8 Hz), 2.97m (1H), 3.05 m (1H),
3.20 m (2H), 3.28 t (2H, J = 9.9 Hz), 3.35–3.46 m
(4H), 3.54 m (1H), 3.59 m (1H), 3.67 m (1H), 3.74 m
(1H), 4.13 d (1H, J = 7.2 Hz), 4.46 t (1H, J = 5.7 Hz),
4.51 t (1H), 4.89–4.93 m (3H), 4.96–5.01 m (2H),
5.06 d (1H, J = 3.6 Hz), 5.45 s (1H), 5.48 s (1H),
5.78 m (1H). 13C NMR spectrum (DMSO-d6), δC, ppm:
25.48, 28.26, 28.47, 28.82, 28.85, 29.24, 33.15, 60.62,
60.77, 68.67, 69.90, 72.45, 72.98, 73.29, 73.42, 75.12,
76.44, 79.64, 100.77, 102.69, 114.63, 138.84. Mass
spectrum (ESI): m/z 503.2413 [M + Na]+. Calculated
for C22H40O11Na: 503.2468.
Heptyl hepta-O-acetyl-β-maltoside was synthe-
sized from maltose octaacetate (4.0 g, 5.89 mmol) and
heptan-1-ol (2.5 mL, 2.05 g, 17.68 mmol) using
1.38 mL (3.07 g, 11.79 mmol) of tin(IV) chloride.
1
Yield 959 mg (22%). H NMR spectrum (CDCl3), δ,
ppm: 0.80 t (3H, J = 7.2 Hz), 1.15–1.31 m (8H),
1.47 m (2H), 1.93 s (6H), 1.94 s (3H), 1.95 s (3H),
1.97 s (3H), 2.03 s (3H), 2.07 s (3H), 3.40 q (1H, J =
16.2 Hz), 3.61 q.d (1H, J = 13.2 Hz), 3.77 q (1H, J =
16.2 Hz), 3.89 d (1H, J = 10.8 Hz), 3.93 t (1H, J =
9.6 Hz), 3.97 d (1H, J = 10.8 Hz), 4.17 d.t (2H, J =
4.8, 10.8 Hz), 4.39 d.d (1H, J = 2.4, 12.0 Hz), 4.45 d
(1H, J = 8.4 Hz), 4.74 t (1H, J = 8.4 Hz), 4.78 d.d (1H,
J = 4.2, 10.2 Hz), 4.98 t (1H, J = 9.9 Hz), 5.18 t (1H,
J = 9.9 Hz), 5.29 t (1H, J = 9.9 Hz), 5.34 d (1H,
J = 3.6 Hz).
9-Chlorononyl β-maltoside (2) was synthesized by
reacting 9-chlorononyl hepta-O-acetyl-β-maltoside
(1.06 g, 1.33 mmol) with triethylamine (0.9 mL,
673 mg, 6.65 mmol) and distilled water (0.9 mL). Yield
531 mg (79%), white crystalline solid; [α]D20 = +19.71°
(c = 0.718, MeOH). IR spectrum, ν, cm–1: 3409, 2929,
2856, 2360, 2067, 1641, 1378, 1148, 1073, 1026.
1H NMR spectrum (DMSO-d6), δ, ppm: 1.22–1.32 m
(10H), 1.36 m (2H), 1.69 m (2H), 2.97 m (1H), 3.05 m
(1H), 3.20 m (2H), 3.35–3.46 m (6H), 3.54 m (1H),
3.58–3.62 m (3H), 3.67 m (1H), 3.75 m (1H), 4.13 d
(1H, J = 6.6 Hz), 4.45 t (1H, J = 6.6 Hz), 4.50 t (1H),
4.89 t (2H, J = 4.8 Hz), 4.99 d (1H, J = 3.0 Hz), 5.06 d
(1H, J = 4.8 Hz), 5.44 s (1H), 5.48 s (1H). 13C NMR
spectrum (D2O), δC, ppm: 26.35, 27.47, 29.45, 29.95,
30.00, 30.07, 33.22, 46.03, 61.22, 61.48, 69.91, 71.17,
72.52, 73.52, 73.69, 73.71, 75.37, 77.00, 78.19, 100.84,
103.15. Mass spectrum (ESI): m/z 525.2108 [M + Na]+.
Calculated for C21H39O11ClNa: 525.2079.
Heptyl hepta-O-acetyl-1-thio-β-maltoside was
synthesized from maltose octaacetate (1.0 g,
1.47 mmol) and heptan-1-thiol (0.7 mL, 583 mg,
4.41 mmol) using 0.34 mL (766 mg, 2.94 mmol) of
1
tin(IV) chloride. Yield 423 mg (38%). H NMR spec-
trum (CDCl3), δ, ppm: 0.86 t (3H, J = 6.9 Hz), 1.24–
1.34 m (6H), 1.53–1.59 m (4H), 1.98 s (3H), 1.99 s
(3H), 2.00 s (3H), 2.01 s (3H), 2.03 s (3H), 2.08 s (3H),
2.12 s (3H), 2.63 m (2H), 3.67 d (1H, J = 9.6 Hz),
3.93 d (1H, J = 9.6 Hz), 3.97 t (1H, J = 9.6 Hz), 4.02 d
(1H, J = 11.4 Hz), 4.21 d.t (2H, J = 4.2, 12.6 Hz),
4.44 d.d (1H, J = 1.8, 12.6 Hz), 4.50 d (1H, J =
9.6 Hz), 4.83–4.85 m (2H), 5.03 t (1H, J = 9.9 Hz),
5.26 t (1H, J = 9.6 Hz), 5.34 t (1H, J = 9.9 Hz), 5.39 d
(1H, J = 4.2 Hz).
8-Methoxyoctyl β-maltoside (3) was synthesized
by reacting 8-methoxyoctyl hepta-O-acetyl-β-malto-
side (316 mg, 0.41 mmol) with triethylamine (0.3 mL,
205 mg, 2.03 mmol) and distilled water (0.3 mL). Yield
147 mg (75%), white crystalline solid; [α]D20 = +22.59°
(c = 0.509, MeOH). IR spectrum, ν, cm–1: 3419,
General procedure for the synthesis of alkyl
β-maltosides 1–13. Triethylamine (5.0 equiv) and
distilled water were added at room temperature under
a nitrogen atmosphere to a solution of alkyl hepta-O-
acetyl-β-maltoside in methanol. The mixture was
warmed to 50°C stirred for 18 h at that temperature
(TLC, CHCl3–MeOH, 1:2), and concentrated under
reduced pressure. The residue was purified by column
chromatography on Dowex (OH form) using methanol
as eluent.
1
2067, 1636, 1540, 1456, 1027. H NMR spectrum
(DMSO-d6), δ, ppm: 1.22–1.32 m (10H), 1.47 m (2H),
2.97 t (1H), 3.05 m (1H), 3.19 s (3H), 3.27 t (2H, J =
6.3 Hz), 3.35–3.45 m (8H), 3.55 m (1H), 3.59 m (1H),
3.68 m (1H), 3.74 m (1H), 4.13 d (1H, J = 7.2 Hz),
4.46 t (1H), 4.51 t (1H), 4.90 t (2H), 4.99 d (1H, J =
4.2 Hz), 5.06 d (1H, J = 4.2 Hz), 5.45 s (1H), 5.48 s
(1H). 13C NMR spectrum (DMSO-d6), δC, ppm: 25.45,
25.63, 28.83, 28.86, 29.01, 29.23, 57.78, 60.61, 60.79,
68.68, 69.91, 71.91, 72.45, 72.96, 73.30, 73.44, 75.12,
76.43, 79.65, 100.78, 102.69. Mass spectrum (ESI):
m/z 507.2486 [M + Na]+. Calculated for C21H40O12Na:
507.2417.
Dec-9-en-1-yl β-maltoside (1) was synthesized by
reacting dec-2-en-1-yl hepta-O-acetyl-β-maltoside
(335 mg, 0.43 mmol) with triethylamine (0.3 mL,
219 mg, 2.15 mmol) and distilled water (0.3 mL). Yield
185 mg (88%), white crystalline solid; [α]D20 = +29.36°
(c = 2.064, MeOH). IR spectrum, ν, cm–1: 3420, 2089,
1
1636, 1558, 1540, 1507, 1473, 1456, 1026. H NMR
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HOSSAIN et al.
1812
Nonyl β-maltoside (4) was synthesized by reacting
(1H, J = 6.6 Hz), 4.46 t (1H, J = 6.6 Hz), 4.51 t (1H),
4.89 t (2H, J = 4.8 Hz), 4.99 d (1H, J = 4.2 Hz), 5.06 d
(1H, J = 4.8 Hz), 5.45 s (1H), 5.48 s (1H). 13C NMR
spectrum (DMSO-d6), δC, ppm: 13.95, 22.08, 25.51,
28.70, 28.92, 29.01 (2C), 29.03, 29.26, 31.29, 60.62,
60.79, 68.68, 69.92, 72.40, 72.96, 73.30, 73.44, 75.13,
76.45, 79.65, 100.78, 102.70. Mass spectrum (ESI):
m/z 519.2735 [M + Na]+. Calculated for C23H44O11Na:
519.2781.
nonyl hepta-O-acetyl-β-maltoside (300 mg,
0.39 mmol) with triethylamine (0.27 mL, 2.0 mmol)
and distilled water (0.27 mL). Yield 125 mg (68%),
white crystalline solid; [α]D20 = +18.75° (c = 0.201,
MeOH). IR spectrum, ν, cm–1: 3420, 2067, 1636, 1541,
1
1507, 1456, 1028. H NMR spectrum (DMSO-d6), δ,
ppm: 0.85 t (3H, J = 6.6 Hz), 1.21–1.35 m (10H),
2.97 t (1H), 3.04 m (1H), 3.20 m (2H), 3.28 t (2H),
3.37–3.46 m (4H), 3.54 m (1H), 3.60 m (1H), 3.68 m
(1H), 3.74 m (1H), 4.13 d (1H, J = 7.2 Hz), 4.46 t (1H,
J = 7.2 Hz), 4.51 t (1H), 4.89 t (2H, J = 4.8 Hz), 4.99 d
(1H, J = 3.0 Hz), 5.06 d (1H), 5.45 s (1H), 5.48 s (1H).
13C NMR spectrum (DMSO-d6), δC, ppm: 13.95,
22.08, 25.51, 28.66, 28.92, 28.99, 29.26, 31.29, 60.57,
60.81, 68.68, 69.91, 72.45, 73.00, 73.30, 73.44, 75.12,
76.45, 79.64, 100.78, 102.69. Mass spectrum (ESI):
m/z 491.2485 [M + Na]+. Calculated for C21H40O11Na:
491.2468.
Tetradecyl β-maltoside (7) was synthesized by
reacting tetradecyl hepta-O-acetyl-β-maltoside
(547 mg, 0.66 mmol) with triethylamine (0.46 mL,
3.3 mmol) and distilled water (0.46 mL). Yield 283 mg
(80%), white crystalline solid; [α]D20 = +26.44° (c =
0.191, MeOH). IR spectrum, ν, cm–1: 3397, 2922,
2853, 2360, 1647, 1457, 1027, 794. 1H NMR spectrum
(DMSO-d6), δ, ppm: 0.84 t (3H, J = 6.6 Hz), 1.18–
1.35 m (24H), 2.98 m (1H), 3.05 m (1H), 3.20 m (2H),
3.28 t (2H), 3.35–3.46 m (4H), 3.55 m (1H), 3.60 m
(1H), 3.68 m (1H), 3.75 m (1H), 4.13 d (1H, J =
7.2 Hz), 4.46 t (1H, J = 7.2 Hz), 4.51 t (1H, J =
6.6 Hz), 4.89 t (2H, J = 6.6 Hz), 4.99 d (1H, J =
3.0 Hz), 5.06 d (1H, J = 5.4 Hz), 5.44 d (1H, J =
5.4 Hz), 5.47 d (1H). 13C NMR spectrum (DMSO-d6),
δC, ppm: 13.96, 22.09, 25.53, 28.70, 28.93, 29.01,
29.03, 29.05 (4C), 29.27, 31.29, 60.63, 60.80, 68.72,
69.90, 72.45, 73.01, 73.32, 73.45, 75.15, 76.51, 79.70,
100.80, 102.70. Mass spectrum (ESI): m/z 561.3225
[M + Na]+. Calculated for C26H50O11Na: 561.3251.
Undec-10-en-1-yl β-maltoside (5) was synthesized
by reacting undec-10-en-1-yl hepta-O-acetyl-β-malto-
side (215 mg, 0.27 mmol) with triethylamine (0.20 mL,
138 mg, 1.37 mmol) and distilled water (0.20 mL).
Yield 103 mg (76%), white crystalline solid; [α]D20
=
+23.47° (c = 1.255, MeOH). IR spectrum, ν, cm–1:
3375, 3019, 2926, 2855, 2399, 1640, 1426, 1214, 1073,
1
1027, 756. H NMR spectrum (DMSO-d6), δ, ppm:
1.21–1.38 m (14H), 1.99 q (2H, J = 8.4 Hz), 2.98 m
(1H), 3.05 m (1H), 3.20 m (2H), 3.28 t (2H), 3.35–
3.40 m (3H), 3.45 t (2H), 3.55 m (1H), 3.59 m (1H),
3.67 m (1H), 3.73 m (1H), 4.13 d (1H, J = 7.2 Hz),
4.46 t (1H, J = 6.0 Hz), 4.50 t (1H, J = 6.0 Hz), 4.88–
4.93 m (3H), 4.97–4.99 m (2H), 5.06 d (1H, J =
4.8 Hz), 5.44 s (1H), 5.48 s (1H), 5.78 m (1H).
13C NMR spectrum (DMSO-d6), δC, ppm: 25.49, 28.26,
28.50, 28.82, 28.88, 28.98, 29.24, 33.16, 60.59, 60.79,
68.67, 69.86, 72.45, 72.98, 73.28, 73.44, 75.12, 76.44,
79.66, 100.79, 102.69, 114.63, 138.83. Mass spectrum
(ESI): m/z 517.2592 [M + Na]+. Calculated for
C23H42O11Na: 517.2625.
8-Methylnonyl β-maltoside (8) was synthesized by
reacting 8-methylnonyl hepta-O-acetyl-β-maltoside
(319 mg, 0.41 mmol) with triethylamine (0.3 mL,
207 mg, 2.1 mmol) and distilled water (0.3 mL). Yield
153 mg (77%), white crystalline solid; [α]D20 = +21.33°
(c = 0.6, MeOH). IR spectrum, ν, cm–1: 3375,
1
2924, 1653, 1541, 1458, 1031. H NMR spectrum
(DMSO-d6), δ, ppm: 0.84 d (6H, J = 7.2 Hz), 1.11–
1.32 m (11H), 1.48 m (2H), 2.98 m (1H), 3.05 m (1H),
3.20–3.28 m (4H), 3.34–3.45 m (4H), 3.55 m (1H),
3.60 m (1H), 3.68 m (1H), 3.73 q (1H, J = 6.6 Hz),
4.13 d (1H, J = 8.4 Hz), 4.45 t (1H, J = 5.4 Hz), 4.49 t
(1H), 4.87m (2H), 4.99 d (1H, J = 3.0 Hz), 5.04 d
(1H), 5.43 s (1H), 5.47 s (1H). 13C NMR spectrum
(DMSO-d6), δC, ppm: 22.54 (2C), 25.53, 26.78, 27.41,
28.97, 29.27, 29.31, 38.50, 60.62, 60.79, 68.70, 69.92,
72.47, 73.02, 73.32, 73.46, 75.14, 76.47, 79.66, 100.80,
102.71. Mass spectrum (ESI): m/z 505.2595 [M + Na]+.
Calculated for C22H42O11Na: 505.2625.
Undecyl β-maltoside (6) was synthesized by react-
ing undecyl hepta-O-acetyl-β-maltoside (430 mg,
0.54 mmol) with triethylamine (0.37 mL, 273 mg,
2.7 mmol) and distilled water (0.37 mL). Yield 227 mg
(84%), white crystalline solid; [α]D20 = +20.13° (c =
0.755, MeOH). IR spectrum, ν, cm–1: 3375, 2923,
2853, 2360, 1641, 1548, 1411, 1213, 1026, 748.
1H NMR spectrum (DMSO-d6), δ, ppm: 0.84 t (3H, J =
6.6 Hz), 1.18–1.36 m (18H), 2.97 m (1H), 3.05 m (1H),
3.20 m (2H), 3.28 t (2H), 3.35–3.46 m (4H), 3.54 m
(1H), 3.59 m (1H), 3.68 m (1H), 3.74 m (1H), 4.13 d
9-Methyldecyl β-maltoside (9) was synthesized by
reacting 9-methyldecyl hepta-O-acetyl-β-maltoside
(105 mg, 0.21 mmol) with triethylamine (0.15 mL,
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HIGHLY β-SELECTIVE GLYCOSYLATION REACTIONS
1813
107 mg, 1.06 mmol) and distilled water (0.15 mL).
4.2 Hz), 5.43 s (1H), 5.47 s (1H). 13C NMR spectrum
(DMSO-d6), δC, ppm: 13.96, 22.09, 28.37, 28.45,
28.63, 28.65, 28.70, 28.97, 29.02, 29.04, 29.30, 31.29,
60.78, 69.90, 71.05, 72.44, 72.64, 73.32, 73.76, 77.90,
79.53, 79.76, 85.01, 100.82. Mass spectrum (ESI):
m/z 549.2698 [M + Na]+. Calculated for C24H46O10NaS:
549.2709.
Yield 55 mg (83%), white crystalline solid; [α]D20
=
+17.47° (c = 0.518, MeOH). IR spectrum, ν, cm–1:
1
3397, 2923, 1652, 1540, 1456, 1030. H NMR spec-
trum (DMSO-d6), δ, ppm: 0.84 d (6H, J = 7.2 Hz),
1.13–1.36 m (13H), 1.47 m (2H), 2.97 m (1H), 3.04 m
(1H), 3.20 m (2H), 3.28 t (2H), 3.36–3.44 m (4H),
3.55 m (1H), 3.59 m (1H), 3.68 m (1H), 3.74 m (1H),
4.13 d (1H, J = 7.8 Hz), 4.46 t (1H, J = 6.0 Hz), 4.49 t
(1H), 4.88 m (2H), 4.99 d (1H, J = 3.6 Hz), 5.03 d
(1H), 5.44 s (1H), 5.48 s (1H). 13C NMR spectrum
(DMSO-d6), δC, ppm: 22.53 (2C), 25.52, 26.79, 27.39,
28.92, 29.06, 29.26, 29.28, 38.49, 60.61, 60.81, 68.69,
69.93, 72.46, 73.01, 73.31, 73.45, 75.16, 76.47, 79.66,
100.78, 102.70. Mass spectrum (ESI): m/z 519.2735
[M + Na]+. Calculated for C23H44O11Na: 519.2781.
Heptyl β-maltoside (12) was synthesized by
reacting heptyl hepta-O-acetyl-β-maltoside (959 mg,
1.3 mmol) with triethylamine (0.9 mL, 6.5 mmol) and
distilled water (0.9 mL). Yield 461 mg (80%), white
crystalline solid; [α]D20 = +28.05° (c = 0.164, MeOH).
IR spectrum, ν, cm–1: 3375, 2925, 2360, 1725, 1709,
1
1658, 1629, 1548, 1529, 1410, 1028. H NMR spec-
trum (DMSO-d6), δ, ppm: 0.85 t (3H, J = 7.2 Hz),
1.18–1.35 m (10H), 2.98 m (1H), 3.05 m (1H), 3.18–
3.29 m (4H), 3.38–3.45 m (4H), 3.55 m (1H), 3.59 m
(1H), 3.67 m (1H), 3.74 q (1H, J = 6.0 Hz), 4.13 d (1H,
J = 8.4 Hz), 4.46 t (1H, J = 5.4 Hz), 4.51 t (1H), 4.89 t
(2H, J = 5.4 Hz), 4.99 d (1H, J = 3.0 Hz), 5.07 d (1H,
J = 4.8 Hz), 5.45 s (1H), 5.48 d (1H). 13C NMR spec-
trum (DMSO-d6), δC, ppm: 13.95, 22.05, 25.46, 28.56,
29.25, 31.25, 60.59, 60.84, 68.67, 69.90, 72.41, 72.98,
73.28, 73.42, 75.17, 76.43, 79.67, 100.76, 102.69.
Mass spectrum (ESI): m/z 463.2129 [M + Na]+. Calcu-
lated for C19H36O11Na: 463.2155.
8-Cyclopropyloctyl maltoside (10) was synthe-
sized by reacting 8-cyclopropyloctyl hepta-O-acetyl-β-
maltoside (686 mg, 0.87 mmol) with triethylamine
(0.6 mL, 440 mg, 4.35 mmol) and distilled water
(0.6 mL). Yield 346 mg (81%), white crystalline solid;
[α]D20 = +23.71° (c = 0.464, MeOH). IR spectrum, ν,
cm–1: 3374, 2923, 2853, 1640, 1379, 1148, 1073, 1028.
1H NMR spectrum (DMSO-d6), δ, ppm: –0.038 q (2H),
0.35 q (2H), 1.24–1.35 m (12H), 1.61 m (2H), 1.94 m
(1H), 2.97 m (1H), 3.05 m (1H), 3.20 m (2H), 3.28 t
(2H, J = 9.3 Hz), 3.36–3.41 m (3H), 3.45 m (2H),
3.54 m (1H), 3.60 m (1H), 3.68 m (1H), 3.74 m (1H),
4.13 d (1H, J = 7.2 Hz), 4.46 t (1H, J = 5.4 Hz), 4.50 t
(1H, J = 6.0 Hz), 4.89 t (2H, J = 6.0 Hz), 4.99 d (1H,
J = 3.0 Hz), 5.05 d (1H, J = 5.4 Hz), 5.44 d (1H, J =
5.4 Hz), 5.47 d (1H, J = 3.0 Hz). 13C NMR spectrum
(DMSO-d6), δC, ppm: 4.28 (2C), 10.65, 25.46, 28.83,
28.88, 29.03, 29.13, 29.19, 34.01, 60.64, 60.77, 68.62,
69.86, 72.38, 72.96, 73.24, 73.40, 75.09, 76.40, 79.62,
100.75, 102.67. Mass spectrum (ESI): m/z 517.2590
[M + Na]+. Calculated for C23H42O11Na: 517.2625.
Heptyl 1-thio-β-maltoside (13) was synthesized
by reacting heptyl hepta-O-acetyl-1-thio-β-maltoside
(423 mg, 0.563 mmol) with triethylamine (0.4 mL,
2.82 mmol) and distilled water (0.4 mL). Yield 216 mg
(84%), white crystalline solid; [α]D20 = +28.5° (c = 0.6,
MeOH). IR spectrum, ν, cm–1: 3366, 2924, 2360, 1725,
1
1658, 1457, 1027. H NMR spectrum (DMSO-d6), δ,
ppm: 0.85 t (3H, J = 7.2 Hz), 1.18–1.35 m (10H),
2.60 m (2H), 3.01–3.07 m (2H), 3.24 m (2H), 3.37–
3.44 m (4H), 3.54 m (1H), 3.59 m (1H), 3.68 m (1H),
3.72 m (1H), 4.27 d (1H, J = 11.2 Hz), 4.46 t (1H, J =
5.4 Hz), 4.52 t (1H), 4.90 t (2H, J = 4.8 Hz), 5.00 d
(1H, J = 4.8 Hz), 5.20 d (1H), 5.44 s (1H), 5.57 s (1H).
13C NMR spectrum (DMSO-d6), δC, ppm: 13.96, 22.06,
28.29, 28.33, 28.88, 29.32, 31.20, 60.73, 60.85, 69.94,
72.50, 72.67, 73.33, 73.46, 77.88, 79.22, 79.51, 85.01,
100.76. Mass spectrum (ESI): m/z 479. [M + Na]+.
Calculated for C19H36O10NaS: 479.1927.
Dodecyl 1-thio-β-maltoside (11) was synthesized
by reacting dodecyl hepta-O-acetyl-1-thio-β-maltoside
(102 mg, 0.125 mmol) with triethylamine (0.1 mL,
63 mg, 0.625 mmol) and distilled water (0.1 mL). Yield
49 mg (74%), white crystalline solid; [α]D20 = +60.39°
(c = 0.255, MeOH). IR spectrum, ν, cm–1: 3581, 2922,
1725, 1658, 1548, 1529, 1481, 1466, 1410, 1057.
1H NMR spectrum (DMSO-d6), δ, ppm: 0.84 t (3H, J =
7.2 Hz), 1.18–1.32 m (18H), 1.48 m (2H), 2.60 m (2H),
3.02–3.07 m (2H), 3.22–3.29 m (4H), 3.49 m (2H),
3.53 m (1H), 3.60 m (1H), 3.66 m (1H), 3.76 m (1H),
4.26 d (1H, J = 9.6 Hz), 4.47 m (1H), 4.52 m (1H),
4.90 m (2H), 4.97 d (1H, J = 4.2 Hz), 5.00 d (1H, J =
ACKNOWLEDGMENTS
The authors are grateful to the Ministry of Education,
Culture, Sports, Science, and Technology (MEXT) &
University of Hyogo (Japan), Institute of Catalysis,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 10 2020

HOSSAIN et al.
1814
Hokkaido University (Japan), and Department of Chemistry,
Jagannath University (Bangladesh) for their invaluable con-
tributions to make this research successful.
8. Hoheisel, T.N. and Frauenrath, H., Org. Lett., 2008,
vol. 10, p. 4525.
https://doi.org/10.1021/ol801807a
9. Rather, M.Y. and Mishra, S., Sustainable Chem.
Processes, 2013, vol. 1, p. 1.
CONFLICT OF INTEREST
The authors declare no conflict of interest.
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