Efficient assembly of oligomannosides using the hydrophobically assisted switching phase method

Article abstract of DOI:10.1039/c5ob00730e

The hydrophobically assisted switching phase (HASP) method was applied in the assembly of oligomannosides. A new mannosyl donor with high reactivity was selected after a series of optimization studies, which was suitable for the synthesis of oligomannosides via the HASP method. The practicability of the HASP method towards the synthesis of branched oligosaccharides was explored and two branched penta-mannosides were assembled efficiently.

Full text of DOI:10.1039/c5ob00730e

Organic &
Biomolecular Chemistry
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Efficient assembly of oligomannosides using the
hydrophobically assisted switching phase method†
Cite this: Org. Biomol. Chem., 2015,
13, 6711
Shuai Meng, Tian Tian, Dong Han, Lin-Na Wang, Shao-Geng Tang, Xiang-Bao Meng
and Zhong-Jun Li*
The hydrophobically assisted switching phase (HASP) method was applied in the assembly of oligo-
mannosides. A new mannosyl donor with high reactivity was selected after a series of optimization
studies, which was suitable for the synthesis of oligomannosides via the HASP method. The practicability
of the HASP method towards the synthesis of branched oligosaccharides was explored and two branched
penta-mannosides were assembled efficiently.
Received 13th April 2015,
Accepted 28th April 2015
DOI: 10.1039/c5ob00730e
www.rsc.org/obc
philic protecting groups to protect glycosyl donors; thus, the
donors and glycosylation products could be isolated and puri-
Introduction
Oligosaccharides are known to play important roles in numer- fied by reverse-phase silica gel.40 A novel hydrophobically
ous biological processes such as cell–cell interactions, target assisted switching phase (HASP) strategy for oligosaccharide
recognition, inflammation, and viral infection.1–5 They are also preparation, first reported by Rademann et al. in 2005, shows
important tools in glycobiology research and can be used as great success in the synthesis of a pentarhamnoside, which
therapeutic agents in clinics.6–8 The chemical synthesis of also used a reverse-phase absorbent for purification.41 This
natural oligosaccharides and their analogues is important for strategy was also used to synthesize a glycolipid library.42 In
their study in biology and medical science. However, the com- the HASP strategy, a hydrophobic alkyl linker is attached to the
plexity of a carbohydrate structure makes it extremely difficult oligosaccharide for adsorption onto a C18 silica gel. The glyco-
and time-consuming to obtain a reasonable amount of oligo- sylation of a donor and hydrophobic alkyl linker tagged accep-
saccharides.9,10 Therefore, the establishment of a methodology tor is carried out in the solution phase, and subsequently the
for the rapid assembly of oligosaccharides draws great atten- reaction mixture is adsorbed onto C18 silica. As a result, the
tion. Wong and co-workers successfully developed a chemo- less hydrophobic materials are removed by washing with a
selective one-pot strategy for solution phase oligosaccharides hydrophilic solvent (MeOH/H2O) and clean products were
synthesis, which enables the sequential addition of building eluted with a hydrophobic solvent (CH2Cl2). Nishizawa and co-
blocks with decreasing reactivity and simplifies the purifi- workers synthesized segments of Clostridium botulinum C2
cation steps.11,12 Solid-phase synthesis provides a simpler puri- toxin ligand and demonstrated the usefulness of the HASP pro-
fication process.13–15 Furthermore, it enables easy access to a cedure for the construction of oligosaccharides in a convergent
large number of well-defined oligosaccharides without synthetic strategy.43 Chiba et al. presented the CBT (cyclo-
complex separation procedures and offers the opportunity alkane-based thermomorphic) system,
a convenient and
towards the automated synthesis of oligosaccharides.16,17 In practical method for oligosaccharide synthesis with liquid–
spite of its success, the heterogeneous reaction conditions liquid extraction (LLE) in 2008, which used a similar synthetic
makes solid-phase synthesis restricted and reaction monitor- principle to that used in the HASP strategy.44
ing is inconvenient.
Although successful in the synthesis of linear oligosacchar-
Recently, several strategies have been reported, incorporat- ides up to penta-saccharides, its application in the synthesis of
ing the advantages of both solid-phase and liquid-phase syn- more complex oligosaccharides, especially branched ones, still
thesis such as the capture-release strategy, fluorous tag and remains unexplored. Its general applicability is still unclear.
ionic liquid approaches.18–39 In 2000, Vince Pozsgay used lipo- Therefore, the fast construction of larger and more complex
oligosaccharides using the HASP strategy became our research
interest. Oligomannosides are widely present in nature and
have great potential applications. Many novel receptors can
recognize oligomannosides such as DC-SIGN and mannose-
binding lectin. Therefore, we have focused on the efficient syn-
The State Key Laboratory of Natural and Biomimetic Drugs, School of
Pharmaceutical Sciences, Peking University, Beijing 100191, China.
E-mail: zjli@bjmu.edu.cn
†Electronic supplementary information (ESI) available: Selective 1H and 13C
thesis of oligomannosides using the HASP method. In the
NMR spectra. See DOI: 10.1039/c5ob00730e
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present study, we have prepared an efficient mannosyl donor 80 : 20. In order to obtain a more pure product, 90% MeOH
suitable for the HASP strategy and applied it in the synthesis has to be used as the washing solvent, which led to the loss of
of two linear oligomannosides. The synthesis of branched product 3-3a (Table 2). We propose that the presence of several
oligomannosides using the HASP strategy was also explored.
benzyl groups, which are highly hydrophobic, may reduce the
hydrophobicity difference between the target product and
other undesired compounds, decreasing the separation
efficiency of the HASP method. Although donor 2 had high
reactivity, we had to give it up as the separation efficiency was
too low.
Results and discussion
Optimization of the mannosyl donor
To apply the HASP strategy in oligomannoside synthesis, an
efficient glycosyl donor is necessary. During the HASP pro-
cedure, the linker is fixed so that the donor is the key factor
influencing the HASP separation efficiency. Considering the
separation principle of the HASP strategy,38 we believed that
the protecting groups used have great influence on the adsorp-
tion of the compounds onto C-18 silica and may affect the sep-
aration efficiency. Therefore, we first screened different donors
to investigate whether they were suitable for HASP separation.
At the same time, as a supporter-assisted synthesis strategy,
the HASP strategy requires the acceptor to be consumed com-
pletely. Thus, the donor should have high reactivity, which was
also investigated.
At the beginning, we synthesized compound 2 as the donor
and 1 as the acceptor. The separation procedure was carried
out as described by Rademann.41 Different glycosylation con-
ditions were tried and the results are shown in Table 1.
Because of its highest yield, we chose entry 3 glycosylation con-
ditions (3 equiv. of donor 2 and 0.5 equiv. of BF3·Et2O as pro-
moter) for use in the following experiments. After the removal
of the 2-O-Ac group, 3-1a was converted to a new acceptor 3-1b
Therefore, we designed and synthesized donor 4, with the
expectation that the 3,4-BDA protection group could facilitate
HASP separation although it would reduce the reactivity of the
donor. However, the reactivity was much lower than we
expected. In order to achieve the complete consumption of the
acceptor, a large excess of donor 4 and TMSOTf had to be
used, which led to the production of more undesired com-
pounds and more difficult separation.
To improve the reactivity, the 6-benzyl group of donor 4 was
replaced with a TBS protecting group. However, the TBS group
was not very stable in the presence of BF3·Et2O and TMSOTf.
TBDPS, the most stable silicon ether, was subsequently used
as the 6-O-protecting group. The results indicated that donor 8
had high reactivity and a lower amount of it could be used,
which would benefit HASP separation. Furthermore, donor 8
was orthogonally protected, which could enable the assembly
of various oligomannosides with different linkages. All the
glycosylation tests are shown in Table 3.
Rapid assembly of linear oligomannosides with donor 8
for the next glycosylation step. Coupling of 3-1b with donor 2, Having found the highly reactive donor 8 and the optimized
followed by HASP separation, afforded 3-2a in 95% yield. Simi- glycosylation conditions, we attempted the synthesis of oligo-
larly, 3-2a was converted to acceptor 3-2b and when reacted mannosides with HASP separation. Linear oligomannosides
with donor 2, undesired compounds were observed in the were initially selected as our target because they are easier to
product eluted by CH2Cl2 after washing with MeOH : H2O = assemble. The glycosylation was conducted under the opti-
Table 1 Glycosylation test of 1 and 2
Entrya
Donor (equiv.)
Temp. (°C)
Catalyst (equiv.)
Yield of 3-1a
1
2
3
4
2 (3)
2 (3)
2 (3)
2 (2)
2 (3)
2 (3)
2 (3)
0
0
0
0
0
−20
−40
TMSOTf (0.05)
TMSOTf (0.5)
BF3·Et2O (0.5)
BF3·Et2O (0.5)
BF3·Et2O (0.2)
BF3·Et2O (0.5)
BF3·Et2O (0.5)
51
57
98
86
89
31
Trace
5
6b
7b
a All the reactions were complete in 20 minutes except entries 6 and 7. After the mixture was adsorbed onto C-18 silica, MeOH : H2O = 80 : 20 was
used as the hydrophilic solvent to wash the silica and CH2Cl2 was used as the hydrophobic solvent to elute the product. b The reactions were not
complete after 6 hours. The low yield was due to the low solubility of 1 at low temperatures.
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construction of a α(1 → 6) linkage. The deprotected products,
as new acceptors for next glycosylation step, were also purified
by HASP separation. For the α(1 → 2) linked oligomannoside,
we synthesized a hexamannoside in a total yield of 37%
(Table 4). When synthesizing pentamannoside 10-5a and hexa-
mannoside 10-6a, we found that the impurities were difficult
to remove using MeOH : H2O = 90 : 10. TBDPS is also a hydro-
phobic group, which may influence the HASP separation
efficiency. When the glycosyl chain was extended, the excess
donor and by-products were hard to be washed away. The
content of MeOH in water was increased to 95% to wash away
the impurities. The decreased separation efficiency of HASP
for the larger oligomannoside made it challenging to syn-
thesize heptamannoside using our HASP system.
Table 2 Assembly of α(1 → 2) oligomannosides using donor 2
na
Acceptor
MeOH : H2O
Product
Yield
0
1
2
1
3-1b
3-2b
80 : 20
80 : 20
90 : 10
3-1a
3-2a
3-3a
98%
95%
84%
a All the reactions were complete in 30 minutes.
Similar separation challenges were also observed in the syn-
thesis of α(1 → 6) linked oligomannoside. Pentamannoside
11-5a, synthesized from 11-4b, was obtained in 88% yield
mized conditions: 1.5 equiv. of donor 8 with 0.2 equiv. of using MeOH : H2O = 95 : 5 as the washing solvent and dichloro-
TMSOTf as catalyst in dry CH2Cl2 stirred at °C for methane as the releasing solvent (Table 5).
30 minutes. The reaction was monitored by TLC and when the
The two models showed that the HASP strategy has high
0
acceptor was consumed completely, the C-18 silica support separation efficiency in the synthesis of shorter oligomanno-
was added to the mixture and the CH2Cl2 was evaporated. sides; however, the efficiency decreased as the saccharide
After washing three times with 90% MeOH in water, the pure chain was extended. The protecting group is the main factor
glycosylation products were eluted with CH2Cl2. Subsequent influencing the HASP separation efficiency.
removal of the 2-O-Ac group with 0.05 MeONa in MeOH
Rapid assembly of branched oligomannosides with donor 8
yielded the new acceptor for the synthesis of α(1 → 2) linked
oligomannoside, and the removal of the 6-O-TBDPS group
After the synthesis of linear oligomannosides, we attempted to
with 2.0 equiv. of TBAF in THF yielded the acceptor for the
assemble branched oligomannosides. Removal of the 2-O-Ac
Table 3 Glycosylation test of 1 and 4, and 6 and 8
Entrya
Donor (equiv.)
Catalyst (equiv.)
Yield
1
2
3
4
5
6
7
8
4 (3)
4 (5)
4 (3)
4 (3)
4 (5)
6 (3)
6 (3)
6 (3)
6 (3)
6 (3)
8 (2)
8 (1.5)
8 (1.5)
8 (1.5)
8 (1.5)
BF3·Et2O(0.5)
BF3·Et2O(0.5)
TMSOTf (0.2)
TMSOTf (0.5)
TMSOTf (0.5)
TMSOTf (0.05)
TMSOTf (0.2)
TMSOTf (0.5)
BF3·Et2O (0.5)
BF3·Et2O (0.05)
TMSOTf (0.5)
TMSOTf (0.5)
TMSOTf (0.2)
TMSOTf (0.05)
BF3·Et2O (0.2)
60%
71%
63%
88%
95%
<10%
<10%
<10%
Trace
Trace
98%
98%
98%
92%
93%
9
10
11
12
13
14
15
a All the reactions were complete in 30 minutes. After the mixture was adsorbed onto C-18 silica, MeOH : H2O = 90 : 10 was used to wash the silica
and CH2Cl2 was used to elute the product.
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Table 4 Rapid assembly of α(1 → 2) oligomannosides 10-na
Table 5 Rapid assembly of α(1 → 6) oligomannosides 11-na
na
Acceptor
MeOH : H2O
Product
Yield
na
Acceptor
MeOH : H2O
Product
Yield
0
1
2
3
4
1
90 : 10
90 : 10
90 : 10
90 : 10
95 : 5
9
98%
96%
93%
91%
88%
0
1
2
3
4
5
1
90 : 10
90 : 10
90 : 10
90 : 10
95 : 5
9
98%
93%
92%
88%
83%
74%
11-1b (96% from 9)
11-2b (96% from 11-2a)
11-3b (94% from 11-3a)
11-4b (95% from 11-4a)
11-2a
11-3a
11-4a
11-5a
10-1b (98% from 9)
10-2b (97% from 10-2a)
10-3b (97% from 10-3a)
10-4b (95% from 10-4a)
10-5b (95% from 10-5a)
10-2a
10-3a
10-4a
10-5a
10-6a
95 : 5
a All the reactions were complete in 30 minutes.
a All the reactions were complete in 30 minutes.
Scheme 1 Synthesis of branched oligomannosides.
and 6-O-TBDPS groups from 9 yielded a new acceptor 12, synthesis of α(1 → 2) linked branched pentamannoside 15 and
which was then glycosylated to produce a branched trimanno- the TBDPS group removed for the synthesis of α(1 → 6) linked
side 13. The acetyl groups were subsequently removed for the branched pentamannoside 17 (Scheme 1).
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Scheme 2 Deprotection procedure.
The branched pentamannoside 15 and 17 were prepared in mannosyl donor 8 was found suitable for HASP separation,
an overall yield of 35% and 64% from 12, respectively. which showed great efficiency in glycosylation and purifi-
However, we observed that the branched oligomannosides cation. During the HASP synthesis and separation, we found
were much more difficult to purify through HASP separation that the protecting groups have a great influence on both the
than linear ones. We propose that the bulky branched oligo- glycosylation step and purification efficiency. Once a suitable
mannosides interacted with the C-18 silica less strongly, donor with desired protecting group was found, the synthetic
leading to the loss of product during the washing step. Fur- and separation could be carried out smoothly. The HASP strat-
thermore, the lower yield of α(1 → 2) linked branched penta- egy could be used as a facile and economic way to assemble
mannoside 15 (42% from 14) was likely caused by the presence oligomannosides and other types of oligosaccharides for
of the bulkier TBDPS groups, when comparing with the higher biological studies.
yield of 17 (78% from 16).
Deprotection of α(1 → 6) linked branched pentamannoside 17
Experimental section
General experimental methods
Since we had synthesized our four target oligomannosides and
the HASP strategy showed great advantages in the rapid assem-
bly of oligosaccharides, we needed to establish a deprotection
without further purification, unless otherwise noted. Dichloro-
procedure. The linker was easily removed by hydrogenation
under 4 atm of hydrogen. The 2-O-Ac and 6-O-TBDPS groups
were removed in a 90% yield over two steps. Finally, the 3,4-
BDA group was hydrolyzed using 90% TFA in water to afford
pentamannose 21 in 66% overall yield from protected 17
All chemicals were purchased as reagent grade and used
methane was distilled over calcium hydride. Analytical TLC
was performed on silica gel60 F254 pre-coated on glass plates,
with visualization by fluorescence and/or staining with 5%
concentrated sulfuric acid in EtOH. Column chromatography
was performed employing silica gel (230–400 mesh). HASP sep-
aration was conducted with bulk reversed phase Grom-Sil
(Scheme 2).
ODS-4 HE Silica Gel (50 μ, 120 Å). Optical rotations were
recorded using an Optical Activity AA-10R type polarimeter. 1H
Conclusions
NMR and 13C NMR spectra were recorded on Advance spectro-
In conclusion, four oligomannosides associated with gp120 meters. Chemical shifts (in ppm) were referenced with tetra-
were synthesized successfully using the HASP strategy. A new methylsilane (δ = 0 ppm) for 1H NMR and CDCl3 (δ =
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77.00 ppm) for 13C NMR in deuterated chloroform. Mass α-D-mannopyranoside (3-2a). 1H NMR (300 MHz, CDCl3) δ:
spectra were measured using an autoflex MALDI-TOF with 7.35–7.13 (m, 34H), 5.54 (s, 1H), 5.07 (s, 1H), 4.97 (s, 1H),
α-cyano-4-hydroxycinnamic acid (CHCA) as the matrix. High- 4.85–3.67 (m, 27H), 3.54–3.40 (m, 9H), 2.11 (s, 3H), 1.56 (m,
resolution mass spectrometry was performed on an FT-ICR 4H), 1.25 (s, 60H), 0.88 (t, 6H); 13C NMR (75 MHz, CDCl3) δ:
mass spectrometer.
170.1, 138.6, 138.4, 138.3, 138.1, 137.9, 136.4, 128.3, 128.1,
128.0, 127.8, 127.5, 99.6, 98.1, 79.7, 78.1, 75.2, 75.0, 74.9, 74.5,
74.2, 73.3, 72.0, 72.0, 71.9, 71.8, 71.6, 70.9, 69.1, 68.8, 68.6,
General procedure of HASP separation
Reversed-phase silica gel (1 g of C-18 silica gel per 0.057 mmol 31.9, 29.7, 29.5, 29.3, 26.1, 22.7, 21.1, 14.1. MALDI-TOF-MS:
of donor) was added to the glycosylation solution and then the m/z calcd 1623.07 M+, found 1646.2 [M + Na]+, 1662.2 [M + K]+.
solvents were removed by evaporation. The adsorbed dry
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-[2-O-
reversed-phase silica gel was transferred to a peptide synthesis (2-O-acetyl-3,4,6-tri-O-benzyl-α-D-mannopyranosyl)-3,4,5-tri-O-
vessel solid phase inner joint. The C-18 silica gel was washed benzyl-α-D-mannopyranosyl]-3,4,6-tri-O-benzyl-α-D-mannopyra-
three times with methanol/water (80 : 20–95 : 5, 20 mL) by vig- noside (3-3a). 1H NMR (300 MHz, CDCl3) δ: 7.36–7.13 (m,
orous shaking for 10 min. Then, anhydrous MgSO4 (equal 49H), 5.54 (s, 1H), 5.19 (s, 1H), 5.05 (s, 1H), 5.03 (s, 1H),
weight of RP-silica) and distilled CH2Cl2 (20 mL) were added 4.84–3.36 (m, 48H), 2.12 (s, 3H), 1.54 (m, 4H), 1.25 (s, 60H),
for washing three times. The filtrate of CH2Cl2 containing the 0.88 (t, 6H); 13C NMR (75 MHz, CDCl3) δ: 170.1, 138.5, 138.3,
desorbed compounds was collected and concentrated to give 138.0, 137.9, 136.5, 128.3, 128.1, 127.9, 127.8, 127.7, 127.5,
the final product.
127.4, 100.6, 99.3, 98.3, 79.4, 78.1, 75.1, 74.9, 74.7, 74.6, 74.1,
73.2, 72.1, 71.9, 71.8, 71.6, 70.8, 68.9, 68.6, 31.9, 29.7, 29.6,
29.5, 29.3, 26.1, 22.6, 21.1, 14.1. MALDI-TOF-MS: m/z calcd
General procedure of glycosylation
The acceptor and donor were dissolved in dry DCM (1.0 mL 2056.76 M+, found 2079.72 [M + Na]+, 2096.65 [M + K]+.
per 30 mg of donor) under an N2 atmosphere at 0 °C. A cata-
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-acetyl-
lytic amount of TMSOTf was then added slowly to the solution. 3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-
The reaction was stirred for 30 min until TLC showed that the benzyl-α-D-mannopyranoside (5). 1H NMR (300 MHz, CDCl3)
entire acceptor was converted to product. After the glycosyla- δ: 7.35–7.26 (m, 9H), 5.10 (s, 1H), 4.91 (s, 1H), 4.71–4.47 (m,
tion was complete, the solution was neutralized with triethyl- 6H), 4.18 (dd, 1H), 4.09 (t, 1H), 3.97 (m, 1H), 3.75 (m, 2H), 3.70
amine and the HASP separation was conducted.
(m, 1H), 3.54 (m, 4H), 3.44 (t, 4H), 3.24 (s, 3H), 3.18 (s, 3H),
2.13 (s, 3H), 1.55 (m, 4H), 1.27 (s, 66H), 0.88 (t, 6H); 13C NMR
(75 MHz, CDCl3) δ: 170.6, 138.6, 138.3, 136.0, 128.2, 128.1,
General procedure for 6-O-TBDPS deprotection
The substrate was dissolved in THF (10 mL per 0.15 mmol) 127.7, 127.4, 100.1, 99.7, 97.4, 77.1, 73.4, 71.9, 71.7, 71.0, 70.5,
and TBAF (2.0 equiv. per TBDPS group) was added. The reac- 69.2, 68.4, 66.2, 63.5, 48.0, 47.9, 31.9, 29.7, 29.5, 29.3, 26.1,
tion was stirred at 40 °C until TLC showed that the reaction 22.7, 21.2, 17.8, 17.6, 14.1. MALDI-TOF-MS: m/z calcd 1124.85
was complete, after which the HASP separation was carried M+, found 1147.85 [M + Na]+, 1163.83 [M + K]+.
out.
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-acetyl-
3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-
O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranoside (9). 1H NMR
General procedure of 2-O-Ac deprotection
The substrate was dissolved in dry DCM (5 mL per 0.15 mmol) (400 MHz, CDCl3) δ: 7.77–7.26 (m, 14H), 5.11 (s, 1H), 4.88 (s,
and a 0.1 M solution of MeONa in MeOH (5 mL per 1H), 4.70 (s, 2H), 4.65 (d, 1H), 4.48 (d, 1H), 4.22 (m, 2H), 3.98
0.15 mmol) was added. The reaction was stirred at r.t. until (dd, 1H), 3.88–3.83 (m, 2H), 3.72 (t, 1H), 3.55 (m, 4H), 3.45 (t,
TLC showed that the reaction was complete, after which the 4H), 3.26 (s, 3H), 3.26 (s, 3H), 2.13 (s, 3H), 1.58 (m, 4H), 1.28
HASP separation was carried out.
(s, 6H) 1.27 (s, 60H), 1.09 (s, 9H), 0.89 (t, 6H); 13C NMR
(100 MHz, CDCl3) δ: 170.5, 138.6, 136.1, 136.0, 135.5, 134.2,
133.2, 132.1, 129.7, 129.6, 129.5, 128.1, 127.7, 127.5, 127.4,
Compounds data
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-acetyl- 100.1, 99.7, 96.8, 77.2, 71.9, 71.7, 71.6, 71.0, 70.7, 68.7, 66.3,
3,4,6-tri-O-benzyl-α-D-mannopyranoside NMR 62.9, 61.9, 48.0, 47.9, 31.9, 29.7, 29.6, 29.5, 29.3, 26.8, 26.1,
(3-1a). 1H
(300 MHz, CDCl3) δ: 7.30–7.06 (m, 19H), 5.34 (m, 1H), 4.85 (d, 25.8, 22.7, 21.1, 19.4, 17.8, 17.6, 14.1. MALDI-TOF-MS: m/z
1H), 4.80–4.38 (m, 10H), 3.96–3.63 (m, 5H), 3.76 (t, 1H), 3.47 calcd 1295.91 [M + Na]+, found 1295.85 [M + Na]+.
(m, 4H), 3.34 (t, 4H), 2.06 (s,3H), 1.48 (m, 4H), 1.18 (s, 60H),
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl
3,4-O-
0.81 (t, 6H); 13C NMR (75 MHz, CDCl3) δ: 170.3, 138.6, 138.2, [(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-
138.1, 137.8, 135.8, 128.3, 128.2, 128.0, 127.8, 127.7, 127.6, (tert-butyl-dibenzyl)-silyl-α-D-mannopyranoside (10-1b). 1H NMR
127.5, 96.9, 78.3, 75.1, 74.2, 73.3, 71.8, 71.6, 71.5, 70.9, 68.9, (400 MHz, CDCl3) δ: 7.75–7.26 (m, 14H), 4.89 (s, 1H), 4.69 (s,
68.6, 31.8, 29.6, 29.3, 26.1, 22.6, 21.0, 14.1, 14.0. 2H), 4.68 (d, 1H), 4.48 (d, 1H), 4.05 (m, 2H), 3.92 (m, 4H), 3.71
MALDI-TOF-MS: m/z calcd 1190.87 M+, found 1213.8 (m, 1H), 3.53 (m, 4H), 3.43 (t, 4H), 3.26 (s, 3H), 3.14, 1.56 (m,
[M + Na]+, 1229.8 [M + K]+.
4H), 1.31 (s, 6H) 1.25 (s, 60H), 1.06 (s, 9H), 0.87 (t, 6H); 13C
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-(2-O- NMR (100 MHz, CDCl3) δ: 138.6, 136.2, 135.9, 135.6, 133.9,
acetyl-3,4,6-tri-O-benzyl-α-D-mannopyranosyl) 3,4,6-tri-O-benzyl- 133.4, 129.5, 129.5, 128.4, 127.7, 127.6, 127.5, 100.2, 99.8, 98.5,
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77.1, 71.8, 71.7, 71.0, 69.8, 68.5, 68.4, 63.1, 62.4, 48.1, 47.9, 133.2, 129.4, 129.3, 128.0, 127.6, 127.5, 127.49, 127.46, 127.40,
31.9, 29.7, 29.6, 29.5, 29.4, 26.8, 26.1, 22.7, 19.3, 17.8, 17.7, 127.3, 100.0, 99.8, 99.7, 99.5, 99.4, 99.3, 99.2, 98.8, 98.3, 77.2,
14.1. MALDI-TOF-MS: m/z calcd 1253.9 [M + Na]+, found 76.9, 74.4, 73.4, 72.3, 72.1, 71.7, 71.6, 70.8, 70.7, 69.1, 68.5,
1253.9 [M + Na]+.
68.4, 66.0, 63.5, 63.4, 62.8, 62.5, 62.1, 61.7, 53.3, 48.1, 47.9,
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-[2-O- 47.8, 47.7, 47.5, 29.6, 29.5, 29.4, 29.3, 26.7, 26.72, 26.69, 26.0,
acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]- 22.6, 21.1, 20.9, 19.4, 19.1, 17.7, 17.67, 17.6, 17.54, 17.53,
6-O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl]-3,4-O-[(1′S,2′S)- 17.48, 14.3, 14.0. MALDI-TOF-MS: m/z calcd 2324.4 [M + Na]+,
1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-dibenzyl)- found 2324.1 [M + Na]+.
silyl-α-D-mannopyranoside (10-2a). 1H NMR (400 MHz, CDCl3)
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-{2-O-
δ: 7.76–7.18 (m, 24H), 5.25 (s, 1H), 5.23 (s, 1H), 4.82 (s, 1H), [3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-
4.62 (m, 2H), 4.67 (d, 1H), 4.35 (d, 1H), 4.26–3.80 (m, 12H), O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl]-3,4-O-[(1′S,2′S)-
3.67 (m, 1H), 3.53 (m, 4H), 3.44 (t, 4H), 3.27 (s, 3H), 3.24 (s, 1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-
3H), 3.22 (s, 3H), 3.20 (s, 3H), 1.55 (m, 4H), 1.31 (s, 3H), 1.28 dibenzyl)-silyl-α-D-mannopyranosyl}-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-
(s, 3H), 1.27 (s, 3H), 1.23 (s, 3H), 1.25 (s, 60H), 1.05 (s, 9H), 1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-
1.04 (s, 9H), 0.88 (t, 6H); 13C NMR (100 MHz, CDCl3) δ: 171.1, α-D-mannopyranoside (10-3b). 1H NMR (400 MHz, CDCl3) δ:
170.0, 163.3, 138.2, 136.4, 136.0, 135.7, 135.6, 135.5, 134.2, 7.78–7.15 (m,34H), 5.28 (s, 1H), 5.26 (s, 1H), 5.24 (s, 1H), 4.87
133.8, 133.4, 133.3, 129.6, 129.5, 129.4, 128.1, 127.7, 127.6, (s, 1H), 4.64 (m, 2H), 4.61 (s, 2H), 4.41–3.66 (m, 17H), 3.66 (m,
127.5, 127.4, 100.0, 99.8, 99.36, 99.4, 98.8, 98.7, 77.2, 74.5, 1H), 3.51 (m, 4H), 3.42 (t, 4H), 3.24 (s, 3H), 3.16 (s, 3H), 3.13
72.3, 71.9, 71.8, 71.6, 70.8, 70.4, 68.9, 68.6, 66.2, 63.5, 62.9, (s, 3H), 3.10 (s, 3H), 2.80 (s, 3H), 1.56 (m, 4H), 1.32 (s, 3H),
62.6, 62.0, 60.4, 48.0, 47.9, 47.8, 31.9, 29.7, 29.6, 29.5, 29.3, 1.28 (s, 3H), 1.10 (s, 3H), 1.00 (s, 3H), 1.25 (s, 60H), 1.05 (s,
26.8, 26.1, 22.7, 21.1, 21.0, 19.4, 19.2, 17.8, 17.7, 17.6, 14.2, 9H), 1.03 (s, 18H), 0.88 (t, 6H); 13C NMR (100 MHz, CDCl3) δ:
14.1. MALDI-TOF-MS: m/z calcd 1810.1 [M + Na]+, found 138.2, 136.5, 136.0, 135.8, 135.7, 135.5, 135.5, 134.2, 133.9,
1810.1 [M + Na]+.
133.8, 133.5, 133.4, 129.5, 129.4, 129.3, 128.0, 127.6, 127.5,
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-[3,4- 127.4, 127.3, 100.9, 100.2, 99.61, 99.59, 99.5, 99.4, 99.2, 98.9,
O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O- 74.3, 73.5, 72.2, 72.1, 71.8, 71.6, 71.4, 70.9, 69.8, 69.0, 68.8,
(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl]-3,4-O-[(1′S,2′S)- 68.6, 68.2, 63.6, 63.4, 62.8, 62.6, 62.2, 62.1, 53.3, 48.2, 47.9,
1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-butyl- 47.8, 47.7, 47.6, 47.5, 31.9, 29.7, 29.6, 29.5, 29.3, 26.9, 26.8,
dibenzyl)-silyl-α-D-mannopyranoside
(10-2b). 1H
NMR 26.1, 22.6, 19.4, 19.2, 17.8, 17.77, 17.75, 17.71, 17.65, 17.54,
(400 MHz, CDCl3) δ: 7.74–7.15 (m, 24H), 5.31 (s, 1H), 4.90 (s, 14.0. MALDI-TOF-MS: m/z calcd 2282.4 [M + Na]+, found
1H), 4.62 (m, 2H), 4.63 (d, 1H), 4.33 (d, 1H), 4.04–3.85 (m, 2282.4 [M + Na]+.
12H), 3.64 (m, 1H), 3.51 (m, 4H), 3.43 (t, 4H), 3.24 (s, 3H), 3.22
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-{2-O-
(s, 3H), 3.15 (s, 3H), 3.11 (s, 3H), 1.55 (m, 4H), 1.31 (s, 3H), {2-O-[2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-
1.28 (s, 3H), 1.27 (s, 3H), 1.23 (s, 3H), 1.25 (s, 60H), 1.05 (s, 1′,2′-ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl]-
9H), 1.04 (s, 9H), 0.88 (t, 6H); 13C NMR (100 MHz, CDCl3) δ: 3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-
138.2, 136.5, 135.9, 135.8, 135.6, 135.5, 133.5, 133.4, 129.5, O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl}-3,4-O-[(1′S,2′S)-
129.4, 128.4, 128.1, 127.61, 127.58, 127.55, 127.52 127.49, 1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-
100.6, 100.1, 99.8, 99.7, 99.5, 99.1, 77.2, 73.6, 72.1, 71.9, 71.7, dibenzyl)-silyl-α-D-mannopyranosyl}-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-
70.9, 69.6, 69.2, 68.3, 63.4, 63.1, 62.5, 47.9, 47.8, 31.9, 29.7, 1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-manno-
29.6, 29.5, 29.3, 26.8, 22.7, 19.3, 19.2, 17.8, 17.7, 14.1. pyranoside (10-4a). 1H NMR (400 MHz, CDCl3) δ: 7.74–7.16
MALDI-TOF-MS: m/z calcd 1768.1 [M + Na]+, found 1768.2 (m, 44H), 5.43 (s, 1H), 5.22 (s, 1H), 5.15 (s, 1H), 4.89 (s, 1H),
[M + Na]+.
5.29 (s, 1H), 4.64 (d, 2H), 4.60 (s, 2H), 4.51–3.65 (m, 24H), 3.51
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-{2-O- (m, 4H), 3.42 (t, 4H), 3.26 (s, 3H), 3.25 (s, 3H), 3.11 (s, 6H),
[2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′- 3.10 (s, 3H), 2.93 (s, 3H), 2.79 (s, 3H), 2.71 (s, 3H), 2.13 (s, 3H),
ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl]- 1.56 (m, 4H), 1.29 (s, 3H), 1.24 (s, 3H), 1.22 (s, 3H), 1.14 (s,
3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]- 3H), 1.06 (s, 3H), 0.97 (s, 3H), 1.26 (s, 60H), 1.07 (s, 9H), 1.05
6-O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl}-3,4-O-[(1′ (s, 9H), 1.03 (s, 9H), 0.98 (s, 9H), 0.88 (t, 6H); 13C NMR
S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert- (100 MHz, CDCl3) δ: 169.9, 138.1, 136.5, 136.1, 135.8, 135.72,
butyl-dibenzyl)-silyl-α-D-mannopyranoside (10-3a). 1H NMR 135.7, 135.54, 135.45, 134.1, 134.2, 133.9, 133.7, 133.6, 133.56,
(400 MHz, CDCl3) δ: 7.81–7.21 (m, 34H), 5.32 (s, 1H), 5.31 (s, 133.43, 133.37, 129.4, 129.3, 129.2, 128.0, 127.6, 127.5, 127.4,
1H), 5.27 (s, 1H), 4.91 (s, 1H), 4.64 (m, 2H), 4.68 (d, 1H), 4.37 127.2, 100.1, 100.05, 99.9, 99.7, 99.5, 99.2, 99.16, 98.8, 98.0,
(d, 1H), 4.61–3.79 (2m, 17H), 3.70 (m, 1H), 3.55 (m, 4H), 3.51 73.8, 73.7, 73.5, 72.3, 72.2, 72.0, 71.8, 71.6, 70.9, 70.7, 68.9,
(t, 4H), 3.30 (s, 3H), 3.19 (s, 3H), 3.17 (s, 3H), 3.14 (s, 3H), 2.95 68.8, 68.5, 66.0, 63.6, 63.5, 62.9, 62.6, 62.5, 62.4, 62.1, 61.9,
(s, 3H), 2.05 (s, 3H), 1.58 (m, 4H), 1.32 (s, 9H), 1.29 (s, 60H), 48.1, 47.9, 47.8, 47.5, 47.47, 47.3, 31.9, 29.7, 29.6, 29.5, 29.3,
1.15 (s, 9H), 1.03 (s, 9H), 1.06 (s, 9H), 1.03 (s, 9H), 0.88 (t, 6H); 27.0, 26.8, 26.1, 22.7, 21.1, 19.5, 19.3, 19.2, 17.8, 17.7, 17.6,
13C NMR (100 MHz, CDCl3) δ: 170.0, 163.5, 138.0, 136.5, 136.0, 17.58, 17.5, 14.1. MALDI-TOF-MS: m/z calcd 2839.6 [M + Na]+,
135.7, 135.6, 135.5, 135.3, 134.3, 133.8, 133.7, 133.5, 133.3, found 2839.2 [M + Na]+.
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Organic & Biomolecular Chemistry
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-{2-O-
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-{2-O-
{2-O-[3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethyl- {2-O-{2-O-[3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-
ene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl]-3,4- ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl]-
O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O- 3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-
(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl}-3,4-O-[(1′S,2′S)- 6-O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl}-3,4-O-
1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-butyl- [(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-
dibenzyl)-silyl-α-D-mannopyranosyl}-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy- butyl-dibenzyl)-silyl-α-D-mannopyranosyl}-3,4-O-[(1′S,2′S)-1′,2′-
1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-dibenzyl)-silyl- dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-dibenzyl)-
α-D-mannopyranoside (10-4b). 1H NMR (400 MHz, CDCl3) δ: silyl-α-D-mannopyranosyl}-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-
7.81–7.14 (m, 44H), 5.42 (s, 1H), 5.21 (s, 1H), 5.18 (s, 1H), 4.88 dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-man-
(s, 1H), 4.63 (d, 2H), 4.61 (s, 2H), 4.39–3.67 (m, 24H), 3.51 (m, nopyranoside (10-5b). 1H NMR (400 MHz, CDCl3) δ: 7.81–7.14
4H), 3.43 (t, 4H), 3.24 (s, 3H), 3.22 (s, 3H), 3.12 (s, 3H), 3.08 (s, (m, 54H), 5.42 (s, 1H), 5.29 (s, 1H), 5.16 (s, 1H), 5.10 (s, 1H),
3H), 2.97 (s, 3H), 2.77 (s, 3H), 2.70 (s, 3H), 1.56 (m, 4H), 1.38 4.89 (s, 1H), 4.63 (d, 2H), 4.61 (s, 2H), 4.46–3.65 (m, 30H), 3.51
(s, 3H), 1.36 (s, 3H), 1.34 (s, 3H), 1.30 (s, 3H), 1.26 (s, 3H), 1.14 (m, 4H), 3.42 (t, 4H), 3.23–2.67 (m, 30H), 1.56 (m, 4H),
(s, 3H), 1.09 (s, 3H), 1.08 (s, 3H), 1.00 (s, 3H), 1.29(s, 60H), 1.06 1.38–0.95 (m, 135H), 0.88 (t, 6H); 13C NMR (100 MHz, CDCl3)
(s, 9H), 1.05 (s, 9H), 1.03 (s, 9H), 0.98 (s, 9H), 0.88 (t, 6H); 13C δ: 138.1, 136.6, 136.0, 135.9, 135.74, 135.67, 135.6, 135.49,
NMR (100 MHz, CDCl3) δ: 138.1, 136.5, 136.0, 135.8, 135.7, 135.45, 134.25, 134.2, 134.1, 133.9, 133.8, 133.60, 133.58,
135.67, 135.5, 135.4, 134.2, 134.1, 133.8, 133.76, 133.5, 133.4, 133.54, 133.49, 132.2, 131.9, 131.0, 130.9, 129.4, 129.3, 128.84,
132.2, 130.8, 129.4, 129.37, 129.3, 128.7, 127.9, 127.51, 127.46, 128.81, 128.0, 127.55, 127.51, 127.47, 127.42, 127.36, 100.3,
127.43, 127.39, 127.34, 127.27, 100.3, 100.2, 100.1, 99.6, 99.55, 100.25, 100.1, 99.6, 99.56, 99.5, 99.3, 99.23, 99.21, 99.17, 98.95,
99.52, 99.47, 99.3, 99.2, 99.15, 98.8, 73.7, 73.5, 73.3, 72.2, 72.1, 74.2, 74.1, 73.6, 73.4, 72.4, 72.2, 71.9, 71.6, 71.5, 70.9, 69.9,
71.9, 71.8, 71.6, 71.4, 70.9, 69.8, 69.0, 68.9, 68.7, 68.5, 68.1, 69.0, 68.9, 68.6, 68.5, 68.1, 63.7, 63.6, 63.0, 62.8, 62.5, 62.3,
63.6, 63.5, 62.8, 62.6, 62.5, 62.2, 62.0, 61.5, 48.1, 48.0, 47.9, 61.9, 61.5, 48.3, 48.0, 47.9, 47.8, 47.7, 47.6, 47.58, 47.4, 47.34,
47.7, 47.6, 47.5, 47.4, 47.3, 31.8, 29.6, 29.57, 29.56, 29.4, 29.3, 47.31, 31.9, 29.7, 29.6, 29.5, 29.3, 26.94, 26.90, 26.87, 26.8,
26.9, 26.8, 26.7, 26.1, 22.6, 19.3, 19.28, 19.14, 19.11, 17.8, 26.12, 26.1, 22.7, 19.4, 19.3, 19.19, 19.16, 17.9, 17.81, 17.78,
17.78, 17.7, 17.6, 17.56, 17.48, 14.0. MALDI-TOF-MS: m/z calcd 17.75, 17.7, 17.6, 17.55, 17.5, 14.1. MALDI-TOF-MS: m/z calcd
2796.6 [M + Na]+, found 2796.5 [M + Na]+.
3312.9 [M + Na]+, found 3313.4 [M + Na]+.
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-{2-O-
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-{2-O-
{2-O-{2-O-[2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl- {2-O-{2-O-{2-O-[2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-
1′,2′-ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl]- dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-manno-
3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O- pyranosyl]-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-
(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl}-3,4-O-[(1′S,2′S)- ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl}-3,4-
1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-butyl- O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-
dibenzyl)-silyl-α-D-mannopyranosyl}-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy- (tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl}-3,4-O-[(1′S,2′S)-
1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D- 1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-
mannopyranosyl}-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′- dibenzyl)-silyl-α-D-mannopyranosyl}-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-
ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranoside 1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-
(10-5a). 1H NMR (400 MHz, CDCl3) δ: 7.84–7.14 (m, 54H), mannopyranosyl}-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-
5.49 (s, 1H), 5.36 (s, 1H), 5.18 (s, 1H), 5.10 (s, 1H), 4.90 (s, 1H), 1′,2′-ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyrano-
5.30 (s, 1H), 4.62 (d, 2H), 4.55 (s, 2H), 4.34–3.67 (m, 30H), 3.51 side (10-6a). 1H NMR (600 MHz, CDCl3) δ: 7.83–7.11 (m, 64H),
(m, 4H), 3.42 (t, 4H), 3.32–2.69 (m, 30H), 2.12 (s, 3H), 1.56 (m, 5.51 (s, 1H), 5.34 (s, 1H), 5.16 (s, 1H), 5.15 (s, 1H), 5.08 (s, 1H),
4H), 1.38–0.97 (m, 135H), 0.88 (t, 6H); 13C NMR (100 MHz, 4.90 (s, 1H), 5.30 (s, 1H), 4.63 (d, 2H), 4.28 (s, 2H), 4.56–3.64
CDCl3) δ: 169.8, 138.1, 136.6, 136.1, 135.9, 135.8, 135.73, (m, 36H), 3.50 (m, 4H), 3.42 (t, 4H), 3.25–2.69 (m, 36H), 2.13
135.65, 135.63, 135.5, 135.48, 135.45, 135.4, 134.3, 134.2, (s, 3H), 1.56 (m, 4H), 1.35–0.96 (m, 150H), 0.88 (t, 6H); 13C
134.14, 134.1, 133.9, 133.7, 133.69, 133.59, 133.5, 133.47, NMR (150 MHz, CDCl3) δ: 170.1, 136.6, 136.2, 135.8, 135.8,
133.2, 132.3, 130.8, 129.5, 129.43, 129.39, 129.3, 128.0, 127.53, 135.7, 135.6, 135.5, 134.4, 134.3, 134.1, 134.1, 133.9, 133.7,
127.5, 127.46, 127.4, 127.2, 100.3, 100.2, 99.96, 99.8, 99.64, 133.6, 133.5, 131.1, 130.9, 129.4, 129.3, 128.9, 128.8, 128.0,
99.56, 99.5, 99.46, 99.2, 99.19, 99.15, 98.9, 98.7, 97.9, 74.2, 127.6, 127.5, 127.5, 127.4, 127.3, 100.4, 100.3, 100.1, 100.0,
74.0, 73.4, 72.3, 72.2, 72.0, 71.9, 71.8, 71.7, 71.6, 71.5, 70.9, 99.7, 99.7 (1JC–H = 172 Hz), 99.6, 99.5 (1JC–H = 173 Hz), 99.5
70.7, 69.0, 68.9, 68.8, 68.6, 66.1, 66.0, 63.7, 63.6, 63.0, 62.9, (1JC–H = 174 Hz), 99.5, 99.2 (1JC–H = 173 Hz), 99.1 (1JC–H = 173
62.7, 62.6, 62.5, 62.1, 62.0, 61.5, 48.2, 48.0, 47.9, 47.9, 47.7, Hz), 99.0 (1JC–H = 172 Hz), 97.8, 74.5, 74.3, 74.0, 73.2, 73.0,
47.5, 47.5, 47.4, 47.3, 47.3, 31.9, 29.7, 29.6, 29.5, 29.3, 26.9, 72.4, 72.2, 72.1, 72.0, 71.9, 71.7, 70.9, 70.8, 68.9, 68.8, 68.7,
26.9, 26.8, 26.8, 26.7, 22.6, 22.6, 19.5, 19.4, 19.3, 19.2, 19.2, 68.6, 68.5, 66.1, 63.7, 63.7, 63.0, 62.9, 62.8, 62.7, 62.5, 62.1,
19.2, 19.1, 17.8, 17.8, 17.7, 17.7, 17.6, 17.5, 14.1. 62.0, 61.6, 52.6, 48.3, 48.2, 47.9, 47.8, 47.7, 47.6, 47.5, 47.5,
MALDI-TOF-MS: m/z calcd 3355.9 [M + Na]+, found 3355.5 47.4, 31.9, 29.7, 29.6, 29.5, 29.3, 27.0, 26.9, 26.9, 26.8, 26.1,
[M + Na]+.
22.7, 21.2, 19.5, 19.4, 19.2, 19.2, 19.2, 17.9, 17.8, 17.7, 17.7,
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17.6, 17.6, 17.5, 14.1. MALDI-TOF-MS: m/z calcd 3869.1 [M + 3.44 (t, 4H), 3.27–3.16 (m, 18H), 2.13 (s, 3H), 2.12 (s, 3H), 2.11
Na]+, found 3869.5 [M + Na]+.
(s, 3H), 1.57 (m, 4H), 1.26 (s, 78H), 1.02 (s, 9H), 0.88 (t, 6H);
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-acetyl- 13C NMR (100 MHz, CDCl3) δ: 170.7, 170.4, 170.2, 138.6, 136.0,
3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-α-D- 135.5, 135.4, 135.3, 134.2, 133.3, 129.5, 128.0, 127.7, 127.6,
mannopyranoside (11-1b). 1H NMR (400 MHz, CDCl3) δ: 127.5, 127.48, 127.4, 127.3, 100.2, 100.1, 100.08, 99.7, 99.67,
7.36–7.26 (m, 4H), 5.11 (s, 1H), 4.87 (s, 1H), 4.70 (s, 2H), 4.69 99.6, 98.3, 98.1, 97.0, 71.9, 71.7, 70.9, 70.7, 70.4, 70.3, 70.2,
(d, 1H), 4.48 (d, 1H), 4.17 (dd, 1H), 4.05 (t, 1H), 3.84–3.78 (m, 68.9, 66.1, 65.9, 65.1, 64.6, 63.3, 63.2, 62.9, 62.0, 48.0, 47.9,
3H), 3.71 (t, 1H), 3.53 (m, 4H), 3.44 (t, 4H), 3.26 (s, 3H), 3.25 (s, 47.9, 47.8, 47.75, 47.72, 31.9, 29.7, 29.6, 29.5, 29.3, 22.6, 21.1,
3H), 2.13 (s, 3H), 1.57 (m, 4H), 1.28 (s, 6H) 1.25 (s, 60H), 0.88 21.05, 19.4, 17.8, 17.7, 17.6, 14.1. MALDI-TOF-MS: m/z calcd
(t, 6H); 13C NMR (100 MHz, CDCl3) δ: 170.4, 138.7, 135.8, 1932.2 [M + Na]+, found 1932.2 [M + Na]+.
134.8, 129.5, 128.0, 127.8, 127.6, 100.1, 99.7, 97.6, 77.2, 71.8,
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-acetyl-
71.6, 71.0, 70.8, 70.5, 69.4, 66.0, 63.5, 61.3, 48.0, 47.8, 31.9, 3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-
31.8, 29.7, 29.6, 29.5, 29.3, 29.0, 26.1, 22.64, 22.6, 17.7, 17.6, {2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-
14.1. MALDI-TOF-MS: m/z calcd 1057.8 [M + Na]+, found ethylene]-6-O-{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-
1057.8 [M + Na]+.
dimethyl-1′,2′-ethylene]-α-D-mannopyranosyl}}-α-D-mannopyra-
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-acetyl- noside (11-3b). 1H NMR (400 MHz, CDCl3) δ: 7.34–7.27 (m,
3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O- 4H), 5.17 (s, 1H), 5.12 (s, 1H), 5.07 (s, 1H), 5.01 (s, 1H), 4.94 (s,
{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′- 1H), 4.83 (s, 1H), 4.69 (m, 2H), 4.45 (m, 2H), 4.18–3.76 (m,
ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl}-α-D- 15H), 3.70 (m, 1H), 3.51 (m, 4H), 3.44 (t, 4H), 3.28–3.15 (m,
mannopyranoside (11-2a). 1H NMR (400 MHz, CDCl3) δ: 18H), 2.15 (s, 3H), 2.14 (s, 3H), 2.12 (s, 3H), 1.57 (m, 4H), 1.25
7.75–7.30 (m, 14H), 5.13 (s, 1H), 5.08 (s, 1H), 4.98 (s, 1H), 4.83 (s, 78H), 0.88 (t, 6H); 13C NMR (100 MHz, CDCl3) δ: 170.6,
(s, 1H), 4.71 (m, 3H), 4.48 (d, 1H), 4.21–3.77 (m, 10H), 3.71 (m, 170.4, 169.9, 138.4, 135.8, 128.0, 127.6, 100.0, 100.0, 100.0,
1H), 3.53 (m, 4H), 3.44 (t, 4H), 3.24 (s, 3H), 3.21 (s, 3H), 3.15 99.6, 99.6, 99.5, 98.4, 98.2, 96.8, 71.7, 71.5, 70.8, 70.7, 70.5,
(s, 3H), 2.12 (s, 3H), 2.08 (s, 3H), 1.56 (m, 4H), 1.26 (s, 70.3, 70.2, 70.0, 68.8, 66.0, 65.7, 65.1, 64.8, 63.4, 63.2, 63.0,
72H),1.07 (s, 9H), 0.88 (t, 6H). 13C NMR (100 MHz, CDCl3) δ: 61.3, 47.9, 47.8, 47.7, 47.6, 31.8, 29.6, 29.5, 29.3, 29.2, 26.0,
170.6, 170.3, 138.6, 136.0, 135.9, 135.5, 134.2, 133.3, 129.5, 22.5, 21.0, 20.9, 17.6, 17.6, 17.5, 14.0. MALDI-TOF-MS: m/z
129.4, 128.2, 127.8, 127.5, 127.4, 100.1, 100.0, 99.7, 99.6, 98.0, calcd 1694.1 [M + Na]+, found 1693.9 [M + Na]+.
96.7, 77.2, 71.9, 71.6, 71.6, 71.0, 70.5, 70.4, 70.4, 68.7, 66.1,
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-acetyl-
66.1, 65.0, 63.4, 63.0, 62.1, 48.0, 47.9, 47.8, 47.7, 31.9, 29.7, 3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-
29.6, 29.5, 29.3, 26.8, 26.1, 22.7, 21.1, 21.0, 19.4, 17.8, 17.7, {2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-
17.6, 17.6, 14.1. MALDI-TOF-MS: m/z calcd 1614.0 [M + Na]+, ethylene]-6-O-{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-
found 1614.0 [M + Na]+.
dimethyl-1′,2′-ethylene]-6-O-{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-acetyl- dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-dibenzyl)-
3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O- silyl-α-D-mannopyranosyl}}}-α-D-mannopyranoside (11-4a). 1H
{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′- NMR (400 MHz, CDCl3) δ: 7.75–7.29 (m, 14H), 5.14 (d, 1H),
ethylene]-α-D-mannopyranosyl}-α-D-mannopyranoside (11-2b). 5.12 (d, 1H), 5.07 (d, 1H), 4.99 (s, 1H), 4.96 (s, 1H), 4.84 (s,
1H NMR (400 MHz, CDCl3) δ: 7.37–7.28 (m, 4H), 5.17 (s, 1H), 1H), 4.68 (s, 2H), 4.43 (d, 2H), 4.18–3.77 (m, 20H), 3.70 (m,
5.08 (s, 1H), 4.96 (s, 1H), 4.84 (s, 1H), 4.69 (m, 2H), 4.47 (m, 1H), 3.54 (m, 4H), 3.44 (t, 4H), 3.28–3.15 (m, 24H), 2.15 (s, 3H),
2H), 4.20–3.76 (m, 10H), 3.71 (m, 1H), 3.53 (m, 4H), 3.44 (t, 2.13 (s, 3H), 2.12 (s, 3H), 2.11 (s, 3H), 1.56 (m, 4H), 1.25 (s,
4H), 3.27 (s, 3H), 3.26 (s, 3H), 3.23 (s, 3H), 3.17 (s, 3H), 2.14 (s, 84H), 1.06 (s, 9H), 0.88 (t, 6H); 13C NMR (100 MHz, CDCl3) δ:
3H), 2.12 (s, 3H), 1.57 (m, 4H), 1.26 (s, 72H), 0.88 (t, 6H); 13C 170.7, 170.5, 170.3, 170.2, 138.5, 136.0, 135.4, 134.1, 133.2,
NMR (100 MHz, CDCl3) δ: 170.5, 169.9, 138.6, 135.8, 134.7, 129.5, 128.0, 127.7, 127.5, 127.4, 100.2, 100.1, 100.0, 99.8, 99.7,
128.0, 127.6, 100.1, 100.0, 99.7, 99.6, 98.5, 97.0, 77.1, 71.8, 99.6, 99.5, 98.4, 98.0, 97.0, 77.1, 71.8, 71.6, 70.9, 70.7, 70.5,
71.5, 70.9, 70.7, 70.4, 70.3, 70.1, 69.0, 66.0, 65.8, 65.2, 63.5, 70.4, 70.3, 70.2, 70.1, 68.9, 66.1, 66.0, 65.2, 64.7, 64.5, 63.2,
63.2, 61.4, 47.9, 47.8, 47.7, 47.6, 31.8, 29.6, 29.5, 29.4, 29.2, 63.0, 62.9, 62.0, 48.0, 47.9, 47.8, 47.8, 47.7, 31.9, 29.7, 29.6,
26.0, 22.6, 21.0, 20.9, 17.6, 17.6, 17.5, 14.0. MALDI-TOF-MS: 29.5, 29.3, 26.8, 26.1, 22.7, 21.1, 21.0, 21.0, 19.4, 17.8, 17.7,
m/z calcd 1375.9 [M + Na]+, found 1376.0 [M + Na]+.
17.6, 14.1. MALDI-TOF-MS: m/z calcd 2250.3 [M + Na]+, found
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-acetyl- 2250.3 [M + Na]+.
3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-acetyl-
{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′- 3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-
ethylene]-6-O-{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′- {2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-
dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-manno- ethylene]-6-O-{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-
pyranosyl}}-α-D-mannopyranoside (11-3a). 1H NMR (400 MHz, dimethyl-1′,2′-ethylene]-6-O-{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-
CDCl3) δ: 7.75–7.28 (m, 14H), 5.14 (dd, 1H), 5.13 (dd, 1H), 5.09 dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-α-D-mannopyranosyl}}}-
(dd, 1H), 5.00 (s, 1H), 4.97 (s, 1H), 4.85 (s, 1H), 4.70 (m, 2H), α-D-mannopyranoside (11-4b). 1H NMR (400 MHz, CDCl3) δ:
4.45 (m, 2H), 4.18–3.75 (m, 15H), 3.71 (m, 1H), 3.54 (m, 4H), 7.35–7.30 (m, 4H), 5.15 (d, 1H), 5.12 (d, 1H), 5.07 (d, 1H), 5.00
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(s, 1H), 4.96 (s, 1H), 4.95 (s, 1H), 4.84 (s, 1H), 4.70 (m, 2H), 135.5, 135.4, 134.2, 129.5, 129.4, 129.39, 128.2, 127.7, 127.6,
4.45 (m, 2H), 4.17–3.76 (m, 20H), 3.71 (m, 1H), 3.54 (m, 4H), 127.52, 127.5, 127.4, 127.3, 100.1, 99.9, 99.8, 99.6, 99.6, 99.6,
3.44 (t, 4H), 3.28–3.15 (m, 24H), 2.15 (s, 3H), 2.14 (s, 3H), 2.11 99.0, 98.3, 97.7, 77.2, 77.1, 74.7, 71.9, 71.8, 71.6, 71.5, 70.8,
(s, 3H), 2.04 (s, 3H), 1.56 (m, 4H), 1.26 (s, 84H), 0.88 (t, 6H); 70.4, 70.1, 68.7, 68.5, 66.3, 66.1, 66.1, 64.0, 62.8, 62.6, 61.9,
13C NMR (100 MHz, CDCl3) δ: 170.7, 170.5, 170.3, 170.0, 138.4, 61.8, 48.0, 47.9, 47.7, 47.7, 31.9, 29.7, 29.6, 29.5, 29.3, 26.8,
135.9, 128.0, 127.6, 100.1, 100.0, 100.0, 99.6, 99.6, 99.5, 98.4, 26.8, 26.1, 22.7, 21.1, 21.1, 19.4, 17.8, 17.8, 17.6, 17.5, 14.1.
98.3, 96.8, 71.8, 71.5, 70.8, 70.7, 70.6, 70.3, 70.2, 70.1, 70.0, MALDI-TOF-MS: m/z calcd 2128.3 [M + Na]+, found 2128.1
68.8, 66.0, 65.8, 65.7, 65.1, 64.9, 64.8, 63.5, 63.1, 63.0, 62.9, [M + Na]+.
61.4, 60.3, 47.9, 47.8, 47.8, 47.7, 47.6, 31.8, 29.6, 29.5, 29.4,
29.2, 26.0, 22.6, 21.0, 17.7, 17.5, 14.0. MALDI-TOF-MS: m/z {3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-
calcd 2012.2 [M + Na]+, found 2012.2 [M + Na]+.
(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl}-3,4-O-[(1′S,2′S)-
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2,6-di-O-
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2-O-acetyl- 1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-α-D-mannopyrano-
3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O- side (14). 1H NMR (400 MHz, CDCl3) δ: 7.75–7.14 (m, 30H),
{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′- 5.15 (s, 1H), 5.05 (s, 1H), 4.90 (s, 1H), 4.64 (m, 4H), 4.21–3.68
ethylene]-6-O-{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′- (m, 18H), 3.52 (m, 4H), 3.43 (t, 4H), 3.27–3.13 (m, 18H), 2.65
dimethyl-1′,2′-ethylene]-6-O-{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′- (s, 1H), 2.25 (s, 1H), 1.57 (m, 4H), 1.33–1.24 (m, 18H), 1.26 (s,
dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-{2-O-acetyl-3,4-O- 60H), 1.05 (s, 9H), 1.04 (s, 9H), 0.88 (t, 6H); 13C NMR
[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert- (100 MHz, CDCl3) δ: 138.4, 136.4, 136.0, 135.9, 135.6, 135.57,
butyl-dibenzyl)-silyl-α-D-mannopyranosyl}}}}-α-D-mannopyrano- 134.0, 133.6, 133.4, 129.5, 129.4, 129.39, 127.8, 127.66, 127.56,
side (11-5a). 1H NMR (600 MHz, CDCl3) δ: 7.74–7.27 (m, 14H), 127.5, 127.4, 127.41, 101.3, 100.5, 100.2, 100.1, 100.0, 99.8,
5.16–5.07 (m, 5H), 4.99–4.85 (m, 5H), 4.69–4.44 (m, 4H), 99.6, 99.5, 99.0, 77.2, 77.1, 76.0, 71.8, 71.7, 71.67, 71.2, 70.9,
4.18–3.74 (m, 25H), 3.70 (m, 1H), 3.54 (m, 4H), 3.44 (m, 4H), 69.7, 69.2, 69.1, 68.3, 68.29, 68.2, 63.3, 63.2, 63.0, 62.9, 62.7,
3.27–3.15 (m, 30H), 2.14–2.10 (m, 15H), 1.57 (m, 4H), 1.26 (m, 62.3, 48.0, 47.96, 47.9, 47.8, 47.6, 31.9, 29.7, 29.7, 29.5, 29.4,
90H), 1.06 (s, 9H), 0.88 (t, 6H); 13C NMR (150 MHz, CDCl3) δ: 26.9, 26.8, 26.78, 26.2, 22.7, 19.4, 19.3, 17.8, 17.7, 17.6, 14.1.
170.7, 170.5, 170.3, 170.2, 138.5, 136.0, 135.4, 134.1, 133.2, MALDI-TOF-MS: m/z calcd 2044.3 [M + Na]+, found 2044.3
129.5, 128.0, 127.7, 127.5, 127.4, 100.1, 100.1, 100.1, 99.7, 99.7, [M + Na]+.
99.6 (1JC–H = 173 Hz), 98.7 (1JC–H = 172 Hz), 98.5 (1JC–H = 173
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2,6-di-O-
Hz), 98.4, 98.0 (1JC–H = 174 Hz), 97.0 (1JC–H = 174 Hz), 71.9, {2-O-{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-
71.6, 70.9, 70.7, 70.6, 70.5, 70.4, 70.3, 70.2, 70.1, 70.0, 68.9, 1′,2′-ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl}-
66.1, 66.0, 65.9, 65.3, 65.0, 64.7, 64.6, 63.3, 63.2, 63.0, 63.0, 3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-6-O-
62.9, 62.0, 48.0, 48.0, 47.9, 47.8, 47.8, 47.8, 47.7, 47.7, 31.9, (tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl}-3,4-O-[(1′S,2′S)-
29.7, 29.6, 29.5, 29.3, 26.8, 26.1, 22.6, 21.1, 21.0, 19.4, 17.7, 1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-α-D-mannopyrano-
17.6, 17.6, 14.1. MALDI-TOF-MS: m/z calcd 2569.4 [M + Na]+, side (15). 1H NMR (400 MHz, CDCl3) δ: 7.73–7.15 (m, 39H),
found 2569.7 [M + Na]+.
5.26 (s, 1H), 5.23 (s, 1H), 5.25 (s, 1H), 5.23 (s, 1H), 5.18 (s, 1H),
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl
3,4-O- 4.82 (s, 1H), 4.73 (s, 1H), 4.61–4.27 (m, 4H), 4.51–3.57 (m,
[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-α-D-manno- 28H), 3.51 (m, 4H), 3.44 (t, 4H), 3.42–2.96 (m, 30H), 2.11 (s,
pyranoside (12). 1H NMR (400 MHz, CDCl3) δ: 7.73–7.34 (m, 6H), 1.55 (m, 4H), 1.27–0.95 (m, 30H) 1.25 (s, 60H), 1.08 (s,
4H), 4.91 (d, 1H), 4.70–4.64 (m, 4H), 4.34–3.64 (m, 6H), 3.71 9H), 1.05 (s, 9H), 0.99 (s, 9H), 0.88 (t, 6H); 13C NMR (100 MHz,
(m, 1H), 3.53 (m, 4H), 3.43 (t, 4H), 3.26 (s, 3H), 3.25 (s, 3H), CDCl3) δ: 169.9, 138.2, 136.2, 136.0, 135.8, 135.7, 135.5, 135.4,
1.57 (m, 4H), 1.31 (s, 3H), 1.29 (s, 3H), 1.26 (s, 60H), 0.88 (t, 134.5, 134.3, 134.2, 133.8, 133.6, 133.5, 133.3, 133.28, 129.5,
6H); 13C NMR (100 MHz, CDCl3) δ: 138.8, 136.1, 134.8, 129.6, 129.4, 128.0, 127.6, 127.5, 127.4, 127.35, 100.1, 100.0, 99.9,
128.2, 127.8, 127.7, 100.3, 99.9, 99.2, 71.8, 71.7, 71.0, 70.7, 99.73, 99.68, 99.6, 99.53 (1JC–H = 173 Hz), 99.5, 99.4 (1JC–H
=
69.8, 69.2, 68.1, 63.1, 61.4, 48.1, 47.9, 31.9, 29.7, 29.6, 29.5, 173 Hz), 99.3 (1JC–H = 173 Hz), 98.7, 98.6 (1JC–H = 174 Hz), 98.3
29.3, 26.5, 26.1, 22.7, 17.8, 17.7, 14.1. MALDI-TOF-MS: m/z (1JC–H = 175 Hz), 77.1, 74.9, 74.5, 74.0, 72.4, 72.0, 71.91, 71.86,
calcd 1015.8 [M + Na]+, found 1015.8 [M + Na]+.
71.6, 70.8, 70.6, 70.5, 69.0, 68.7, 68.4, 68.3, 66.6, 66.2, 66.1,
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2,6-di-O- 63.8, 63.5, 63.0, 62.8, 62.6, 62.7, 62.6, 62.2, 61.9, 61.8, 48.2,
{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′- 48.0, 47.9, 47.7, 47.6, 47.5, 31.9, 29.7, 29.6, 29.5, 29.3, 26.9,
ethylene]-6-O-(tert-butyl-dibenzyl)-silyl-α-D-mannopyranosyl}- 26.84, 26.79, 26.1, 22.7, 21.1, 19.6, 19.4, 19.3, 19.2, 17.8, 17.74,
3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-α-D- 17.69, 17.6, 17.57, 14.1. MALDI-TOF-MS: m/z calcd 3158.8
mannopyranoside (13). 1H NMR (400 MHz, CDCl3) δ: [M + Na]+, found 3158.9 [M + Na]+.
7.75–7.21 (m, 24H), 5.21 (dd, 1H), 5.03 (dd, 1H), 5.17 (s, 1H),
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2,6-di-O-
4.90 (s, 1H), 4.74 (s, 1H), 4.63 (m, 4H), 4.34–3.64 (m, 17H), {2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′-
3.51 (m, 4H), 3.43 (t, 4H), 3.24, 3.23–3.11 (m, 18H), 2.11 (s, ethylene]-α-D-mannopyranosyl}-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-
3H), 2.10 (s, 3H), 1.55 (m, 4H), 1.30–1.24 (m, 18H), 1.26 (s, 1′,2′-dimethyl-1′,2′-ethylene]-α-D-mannopyranoside
(16). 1H
60H), 1.07 (s, 9H), 1.05 (s, 9H), 0.88 (t, 6H); 13C NMR NMR (400 MHz, CDCl3) δ: 7.33–7.30 (m, 4H), 5.23 (dd, 1H),
(100 MHz, CDCl3) δ: 170.4, 169.9, 138.4, 136.2, 136.1, 136.0, 5.06 (dd, 1H), 5.07 (1 s, 1H), 5.03 (1 s, 1H), 4.89 (1 s, 1H), 4.46
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(m, 4H), 4.23–3.60 (m, 17H), 3.54 (m, 4H), 3.44 (t, 4H), 1H), 4.84 (d, J = 18.3 Hz, 1H), 4.75 (d, J = 2.6 Hz, 1H), 4.51 (d,
3.29–3.08 (m, 18H), 2.13 (s, 3H), 2.11 (s, 3H), 2.04 (s, 1H), 2.03 J = 13.3 Hz, 0.12H), 4.13 (m, 7H), 3.97 (m, 7H), 3.82 (m, 16H),
(s, 1H), 1.56 (m, 4H), 1.26 (s, 78H), 0.88 (t, 6H); 13C NMR 3.46 (d, J = 4.2 Hz, 2H), 3.24 (m, 30H), 2.89 (s, 3H), 1.29 (m,
(100 MHz, CDCl3) δ: 170.3, 169.8, 138.5, 135.97, 128.4, 127.7, 30H); 13C NMR (100 MHz, CDCl3) δ: 101.2, 100.4, 100.3, 100.2,
100.0, 99.9, 99.8, 99.6, 99.5, 99.5, 97.3, 97.1, 76.8, 71.8, 71.6, 100.0, 99.9, 99.7, 99.7, 99.6, 93.3, 80.1, 71.5, 71.1, 70.9, 70.7,
71.5, 70.8, 70.5, 70.2, 69.5, 68.6, 67.6, 66.0, 65.9, 65.5, 64.3, 70.4, 70.0, 69.7, 69.6, 69.5, 68.5, 68.4, 68.0, 65.8, 64.0, 62.8,
63.8, 63.6, 61.1, 60.9, 60.2, 47.9, 47.7, 47.6, 47.6, 31.8, 29.6, 62.6, 61.2, 61.1, 48.2, 48.1, 48.0, 47.9, 47.9, 47.8, 47.8, 47.6,
29.5, 29.4, 29.2, 26.0, 22.5, 20.95, 20.9, 17.6, 17.5, 17.5, 17.5, 47.4, 29.7, 29.6, 18.1, 17.8, 17.8, 17.8, 17.7, 17.7, 17.6, 17.6,
17.4, 14.0. MALDI-TOF-MS: m/z calcd 1652.0 [M + Na]+, found 17.3. HRMS (ESI) m/z calcd for C60H106NO36 [M + NH4]+:
1652.5 [M + Na]+.
1416.65, found: 1416.65.
[4-(1,1′-Bis-octadecyl-O-isopropyl)-O-methyl]-benzyl 2,6-di-O-
2,6-Di-O-((6-O-α-D-mannopyranosyl)-α-D-mannopyranosyl)-
{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-1′,2′- D-mannopyranose (20). 1H NMR (600 MHz, D2O) δ: 5.32 (d, J =
ethylene]-6-O-{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′- 1.2 Hz, 1H), 4.92 (d, J = 1.3 Hz, 1H), 4.82 (m, 3H), 4.00 (m, 1H),
dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-diphenyl)-silyl-α-D-manno- 3.79 (m, 29H); 13C NMR (150 MHz, D2O) δ: 103.0, 100.4, 100.1,
pyranosyl}-α-D-mannopyranosyl}-3, 4-O-[(1′S,2′S)-1′,2′-dimethoxy- 99.9, 93.1, 80.7, 73.4, 73.4, 72.0, 71.6, 71.6, 71.5, 71.4, 71.3,
1′,2′-dimethyl-1′,2′-ethylene]-α-D-mannopyranoside
(17). 1H 70.7, 70.7, 67.5, 67.4, 67.4, 67.4, 67.2, 66.4, 66.3, 65.9, 61.7,
NMR (600 MHz, CDCl3) δ: 7.74–7.26 (m, 24H), 5.21–5.00 (m, 61.6. HRMS (ESI) m/z calcd for C30H52NaO26 [M + Na]+: 851.26,
4H), 5.20–4.85 (m, 5H), 4.71–4.40 (m, 4H), 4.25–3.75 (m, 26H), found: 851.26.
3.68 (m, 1H), 3.53 (m, 4H), 3.42 (m, 4H), 3.27–3.08 (m, 30H),
2.14–2.11 (m, 15H), 1.56 (m, 4H), 1.25 (m, 90H), 1.07 (s, 9H),
1.06 (s, 9H), 0.88 (t, 6H); 13C NMR (150 MHz, CDCl3) δ: 170.6,
170.2, 170.1, 170.7, 138.5, 136.2, 136.0, 136.0, 135.5, 135.5,
Acknowledgements
134.3, 134.2, 133.2, 129.5, 129.5, 128.5, 127.7, 127.6, 127.5, This study was financially supported by the National Basic
127.4, 100.1, 99.9, 99.9, 99.7, 99.7, 99.6 (1JC–H = 173 Hz), 99.6, Research Program of China (973 program, No. 2012CB822101),
98.9 (1JC–H = 172 Hz), 98.7, 98.5 (1JC–H = 173 Hz), 98.4 (1JC–H
=
the National Key Technology R&D Program “New Drug Inno-
173 Hz), 98.0 (1JC–H = 174 Hz), 77.1, 74.0, 71.9, 71.7, 71.6, 70.9, vation” of China (no. 2012ZX09502001-001) and NSFC (no.
70.8, 70.5, 70.5, 70.4, 70.3, 70.0, 68.9, 66.4, 66.1, 66.0, 65.8, 21232002), and the State Key Laboratory of Natural and Bio-
64.9, 64.7, 63.8, 63.2, 62.9, 62.8, 62.0, 53.4, 48.1, 48.0, 47.9, mimetic Drugs.
47.9, 47.8, 47.8, 47.7, 47.7, 31.9, 29.7, 29.6, 29.5, 29.4, 26.8,
26.1, 22.7, 21.2, 21.0, 21.0, 19.4, 17.8, 17.7, 17.7, 17.7, 17.6,
17.6, 17.5, 14.1. MALDI-TOF-MS: m/z calcd 2764.5 [M + Na]+,
Notes and references
found 2764.4 [M + Na] +.
2,6-Di-O-{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-1′,2′-dimethyl-
1′,2′-ethylene]-6-O-{2-O-acetyl-3,4-O-[(1′S,2′S)-1′,2′-dimethoxy-
1′,2′-dimethyl-1′,2′-ethylene]-6-O-(tert-butyl-diphenyl)-silyl-α-D-
mannopyranosyl}-α-D-mannopyranosyl}-3,4-O-[(1′S,2′S)-1′,2′-
dimethoxy-1′,2′-dimethyl-1′,2′-ethylene]-D-mannopyranose (18).
1H NMR (400 MHz, CDCl3) δ: 7.72–7.37 (m, 20H), 5.28 (d, J =
4.0 Hz, 0.77H, α-H1), 5.19 (dd, J = 9.6, 5.7 Hz, 2H), 4.93 (m,
5H), 4.80 (d, J = 3.8 Hz, 0.23H, β-H1), 4.14 (m, 9H), 3.86 (m,
16H), 3.23 (m, 30H), 2.11 (m, 12H), 1.26 (m, 31H), 1.06 (m,
19H); 13C NMR (100 MHz, CDCl3) δ: 170.8, 170.2, 169.9, 163.5,
136.0, 135.5, 134.3, 133.3, 129.5, 127.6, 127.5, 127.4, 100.7,
100.2, 99.9, 99.8, 99.8, 99.7, 99.6, 98.8, 97.9, 96.7, 93.9, 92.6,
92.0, 71.7, 71.7, 71.6, 71.1, 71.0, 70.9, 70.5, 70.5, 70.2, 69.5,
69.5, 67.4, 67.2, 66.5, 66.2, 65.9, 65.8, 65.6, 65.1, 64.3, 63.9,
62.9, 62.8, 62.8, 62.2, 62.0, 48.0, 48.0, 47.8, 39.0, 38.7, 34.1,
31.8, 29.7, 29.5, 27.9, 26.9, 26.8, 25.8, 25.0, 22.9, 22.6, 21.2,
20.3, 20.1, 19.4, 19.4, 19.2 17.8, 17.7, 14.9, 14.3, 14.1, 14.1,
11.9, 11.4.
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