Synthesis and self-assembly of 1-deoxyglucose derivatives as low molecular weight organogelators

Article abstract of DOI:10.3762/bjoc.7.31

Low molecular weight gelators are an important class of molecules. The supramolecular gels formed by carbohydrate derived low molecular weight gelators are interesting soft materials that show great potential for many applications. Previously, we have synthesized a series of methyl 4,6-O-benzylidene-α-D- glucopyranoside derivatives and found that several of them are good gelators for water, aqueous mixtures of DMSO, or aqueous mixtures of ethanol. The gelation efficiency of these glycolipid derivatives is dependent upon the structures of their acyl chains. In order to understand the influence of the anomeric position of the sugar headgroup towards self-assembly, we synthesized a series of 1-deoxyglucose analogs, and examined their gelation properties in several solvents. Several long chain esters, including diacetylene containing esters, and aryl esters exhibited gelation in ethanol, aqueous ethanol, or aqueous DMSO. The synthesis and characterization of these novel analogs are reported.

Full text of DOI:10.3762/bjoc.7.31

Synthesis and self-assembly of 1-deoxyglucose
derivatives as low molecular weight organogelators
Guijun Wang*1, Hao Yang1, Sherwin Cheuk1 and Sherman Coleman2
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2011, 7, 234–242.
1Department of Chemistry, University of New Orleans, New Orleans,
LA 70148, Phone: 504 280-1258, Fax: 504 280-6860 and 2Dillard
University, 2601 Gentilly Boulevard, New Orleans, Louisiana 70122
doi:10.3762/bjoc.7.31
Received: 13 July 2010
Accepted: 19 January 2011
Published: 21 February 2011
Email:
Guijun Wang* - gwang2@uno.edu
Guest Editor: J.-P. Desvergne
* Corresponding author
© 2011 Wang et al; licensee Beilstein-Institut.
License and terms: see end of document.
Keywords:
1,5-anhydroglucitol; carbohydrate; hydrogelator; organogelator;
self-assembly
Abstract
Low molecular weight gelators are an important class of molecules. The supramolecular gels formed by carbohydrate derived low
molecular weight gelators are interesting soft materials that show great potential for many applications. Previously, we have synthe-
sized a series of methyl 4,6-O-benzylidene-α-D-glucopyranoside derivatives and found that several of them are good gelators for
water, aqueous mixtures of DMSO, or aqueous mixtures of ethanol. The gelation efficiency of these glycolipid derivatives is depen-
dent upon the structures of their acyl chains. In order to understand the influence of the anomeric position of the sugar headgroup
towards self-assembly, we synthesized a series of 1-deoxyglucose analogs, and examined their gelation properties in several
solvents. Several long chain esters, including diacetylene containing esters, and aryl esters exhibited gelation in ethanol, aqueous
ethanol, or aqueous DMSO. The synthesis and characterization of these novel analogs are reported.
Introduction
In recent years, the field of low molecular weight gelators terials for drug delivery, enzyme immobilization, scaffolds for
(LMWGs) has received a great deal of attention. LMWGs are tissue engineering, etc. [10-14]. The structures of LMWGs span
an interesting class of small molecules that can form reversible a diverse range; carbohydrates have frequently been used in the
supramolecular gels in organic solvents or aqueous solutions synthesis of LMWGs because they are naturally abundant and
[1-9]. Non-covalent interactions such as hydrogen bonding, possess multiple chiral centers that can be selectively function-
hydrophobic interactions, and π–π stacking are the main driving alized [15-37]. Sugar-based supramolecular hydrogels are being
forces for the self-assembly of the gelators into 3-dimensional explored as biocompatible soft materials and as matrices for
networks. The resulting gels may find applications as soft ma- enzymes, DNA, and drug delivery systems [22-28]. Glucose, in
234

Beilstein J. Org. Chem. 2011, 7, 234–242.
particular, is a versatile building block for the preparation of Results and Discussion
various small molecule gelators [30-37], as it is relatively easy In order to better understand the importance of the anomeric
to obtain substituted products by selective functionalization of substituent of the sugar headgroup for self-assembly, we
the anomeric position and the 4- and 6-hydroxy groups. We synthesized a series of esters of the headgroup 8 by a one pot
have found that further derivatization of the glucose headgroup reaction of the acid chloride with the headgroup (Scheme 1). In
to form different glycolipids can result in organogelators [34- general, three products were obtained, which could be separated
37].
by flash chromatography. Our previous results had shown that
esterification of headgroup 1 typically gave the 2-monoester as
Previously, we have systematically synthesized and studied the the major product, but when the headgroup 8 was used, the
self-assembling properties of a series of methyl 4,6-O-benzyli- selectivity of the acylation diminished significantly. The 2- and
dene-α-D-glucopyranoside (1) derivatives (Figure 1), including 3-esters were obtained in similar quantities and, in some cases,
esters and carbamates with different functional groups. Several the 3-ester was the major product. The difference in the acyla-
of these compounds proved to be effective gelators for organic tion selectivity was possibly because of the configurations of
solvents and aqueous solutions [34-37]. We found that the C-1 and C-2 positions. The α-methoxy group allows intramolec-
structures of the acyl chains of diester 2, and monoesters 3 and ular hydrogen bonding to the C-2 hydroxy to take place, which
4, are important for gelation. This result also indicates that the can make the 2-hydroxy group relatively more nucleophilic than
ester linked derivatives require more specific structures and the 3 position. In compound 8, there is no α-methoxy group
many substituents are not tolerated. Typically, monoesters with available for hydrogen bonding to the 2-hydroxy, so the 2- and
alkynyl groups containing 5–7 carbons (Figure 2, 5–7) are good 3-hydroxy groups were more or less equally nucleophilic [39].
gelators for water or aqueous ethanol mixtures. The monoesters The amount of diester was significantly less than the amounts of
presumably form an extended hydrogen bonding array between the 2- and 3-esters. Diester formation mirrors the synthesis of
the ring oxygen and the free hydroxy groups [36].
the diesters of compound 1.
For these compounds, the main forces that influence gelation The selection of the R groups used in this series was based on
include phenyl ring π–π interactions, hydrogen bonding, and our previous results [34-36]. We synthesized the terminal
hydrophobic interactions of the acyl chains, etc. To further acetylenes 9–11, saturated hydrocarbons 12–14, aryl deriva-
understand the structural influence of the anomeric position of tives 15,16, and two long chain diacetylene containing glyco-
the sugar headgroup on self-assembly, we synthesized analogs lipids 17,18. After we obtained these compounds, we then
using head group 8 [38] (Figure 2), in which the anomeric screened them for gelation in several solvents. These results are
methoxy group was replaced with a hydrogen atom and shown in Table 1.
contained a similar series of acyl chains to those in compounds
2–4. These can potentially lead to novel classes of organogela- From the gelation test results shown in Table 1, quite a few of
tors.
the diesters were good gelators for the solvents tested. In
Figure 1: Structures of three ester derivatives of compound 1.
Figure 2: Structures of ester analogs 5–7 and headgroup 8.
235

Beilstein J. Org. Chem. 2011, 7, 234–242.
Scheme 1: Synthesis of a series of esters 9A–18C.
Table 1: The gelation test results of the compounds synthesizeda.
Compound
Hexane
H2O
EtOH
EtOH:H2O (1:2)
DMSO:H2O (1:2)
9A
G 15
I
P
S
P
P
P
P
S
P
P
P
P
P
P
P
10A
11A
12A
13A
14A
15A
16A
17A
18A
G 20
I
P
S
S
S
I
I
S
P
P
P
P
P
P
P
P
S
P
S
P
S
P
G 5
P
G 5
G 20
P
I
S
P
G 7
G 3
P
9B
P
P
P
P
P
P
I
I
S
S
S
S
S
S
S
S
S
S
S
P
G 20
P
10B
11B
12B
13B
14B
15B
16B
17B
18B
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
G 4
P
P
I
P
P
P
P
P
P
P
9C
I
P
I
S
S
S
S
S
S
S
S
S
S
P
S
P
10C
11C
12C
13C
14C
15C
17C
18C
P
P
P
P
P
I
P
P
P
P
P
P
S
P
S
S
P
P
P
P
P
G 10
P
G 20
P
P
P
P
P
aAll concentrations are in mg/mL; G, gel at room temperature; the numbers after G are minimum gelation concentrations; P, precipitation; S, soluble at
~20 mg/mL; the ratio of solvents in parenthesis.
236

Beilstein J. Org. Chem. 2011, 7, 234–242.
hexane, only the two short chain terminal acetylene compounds (Figure 3A, Figure 3B). Compound 9B showed tubular assem-
9A and 10A formed gels. Several diesters were effective gela- blies (Figure 3C) and more straight cylindrical tube or ribbons
tors for ethanol, including the benzoate 15A and the long chain (Figure 3D) at different areas. Compound 15B formed gels
diacetylene compounds 17A and 18A. The two diaryl esters more efficiently at 4 mg/mL in the ethanol/water mixture. The
15A and 16A were also able to form gels in aqueous DMSO morphology of the assembly showed uniform, long and narrow
solution. Compared to the diesters, the monoesters were not as fibers (Figure 3E, Figure 3F).
effective as organogelators; only the 2-pentynoate 9B was able
to gelate aqueous DMSO, and the 2-benzoate 15B was able to It is interesting to see that the gelation trends of the diester
form a gel in ethanol. The rest of the 2-monoesters did not derivatives of compound 8 are quite different compared to the
gelate any of the other solvents. For the 3-monoesters, com- corresponding compounds derived from headgroup 1. The gela-
pound 15C was able to form gels in aqueous DMSO and tion of the long chain diacetylene compounds were not affected
aqueous ethanol, but none of the other esters and solvents adversely by changing the headgroup. For the monoesters, the
formed gels.
deoxy sugar derivatives are somewhat less effective gelators in
comparison to the α-methoxy sugar derivatives. The terminal
The morphologies of several gels are shown in Figure 3. The alkynyl esters were among the most efficient gelators from the
hexane gel of compound 9A formed fibrous assemblies ester library derived from compound 1. The removal of the
Figure 3: Optical micrographs of the gels formed by compound 9A in hexane at 15 mg/mL (A, B), 9B in DMSO/water (1:2) at 20 mg/mL (C, D), and
15B in EtOH/H2O (1:2) at 4 mg/mL (E, F). The images were taken with gels containing solvents (not dried gels).
237

Beilstein J. Org. Chem. 2011, 7, 234–242.
methoxy group resulted in a sharp reduction in gelation, but found that the diesters are effective gelators for ethanol. Further
these compounds did exhibit some gelation ability. This obser- characterization of the gel formed by compound 18A in ethanol
vation indicated that the α-methoxy group is useful in the for- proved it to be a very efficient gelator, forming gels in ethanol
mation of a fibrillar network and may or may not be involved in at concentrations lower than 1 wt %/v. In addition, the gels can
the hydrogen bonding array. However, terminal alkynyl groups also be readily polymerized with a 6 W TLC illuminating UV
did show more promise than saturated hydrocarbons.
lamp (Figure 4) to give the typically blue colored product. The
glass vial is not UV transparent, therefore the polymerization
Polydiacetylenes have interesting optical and electronic only occurred from the top of the gel (Figure 4c). When a
properties, and diacetylene containing gels may have useful quartz tube was used as the container, the gel turned light blue
applications as advanced sensing materials [35,40,41]. The homogeneously after one min of exposure to UV light (254 nm)
morphologies of the self-assembled structures can be retained (Figure 4d). After three min of UV treatment, it produced a dark
by cross linking the diacetylene functional groups. Therefore, blue colored gel (Figure 4e). The blue gel also exhibited
we have also synthesized and studied several diacetylene interesting color transition properties upon heating (Figure 4f).
containing sugar lipids. Esterification of sugar headgroups with For a comparison of the two sugar headgroups, the lipid 19 [35]
diacetylene containing long chain carboxylic acids can give the was able gelate ethanol at 7 mg/mL, but it cannot be polymer-
desired diacetylene containing lipids. Previously we had used ized as easily with the 6 W UV lamp. This indicates that the two
headgroup 1 to synthesize a library of diacetylene containing diacetylene chains in 19 are not aligned favorably for polymer-
lipids, and found that many of them are effective gelators [35]. ization because of the presence of the methoxy group at the
Using the headgroup 8, we also synthesized six long chain anomeric position. The ethanol gels of compound 19 formed
diacetylene containing glycolipids 17A–17C and 18A–18C. We long rods or cylindrical tubules, which may require stronger UV
Figure 4: An ethanol gel formed by compound 18A at <10 mg/mL. a) A clear solution when heated above 70 °C; b) a stable gel after cooling to room
temperature; c) a blue gel after illuminating with UV lamp from the top of the vial in b; d) a light blue gel inside quartz tube after UV treatment for 1
min; e) a dark blue gel in quartz tube after UV treatment for 3 min; f) the blue gel in e) turned red after heating.
238

Beilstein J. Org. Chem. 2011, 7, 234–242.
Figure 5: Optical micrographs under bright field (a, b) and scanning electron micrograph (c) of the gel formed by compound 18A in ethanol after
exposure to UV light for 3 min. Blue-purple fibers were observed in (a) and (b), and an entangled fibrous network was observed in (c).
energy to polymerize. The optical micrographs of 18A showed
fibrous assemblies composed of long intertwined thin fibers
(Figure 5). The topological cross-link of the diacetylenes
allowed the fibrous morphologies to be preserved.
We also carried out UV–vis studies to monitor the color tran-
sition of compound 18A as shown in Figure 6. The gel formed
by 18A in ethanol (10 mg/mL) was treated with a 6 W UV lamp
with 254 nm light for 1 min from the top of the uncovered plate.
The absorption of the gel was very strong and exceeded the
detection limit. The sample was split into two cells, and a small
amount of ethanol was added to avoid drying. The UV–vis
spectra showed two peaks at 646 nm (λmax) and 590 nm, which
is in agreement with the observed purple-blue color of the gel.
This plate was then treated with the same UV light for another 2
min. The absorption peaks became more intense, and no new
signals were observed (Figure 6A). The plate was covered with
a matching glass lid and then incubated in an incubator at 35,
40, 50, and 60 °C for 10–15 min. Below 50 °C, there was a
small red shift of the λmax, which increased with increasing
temperature. At 50 °C, the λmax shifted from 650 nm to 634 nm.
A short incubation at 60 °C also gave a similar spectrum but a
new broad absorption at 530 nm began to appear (Figure 6B).
The 530 nm absorption corresponds to the red phase of the gel.
After incubating at 60 °C for 90 min, only part of the gel turned
red, and the red signal at 530 nm increased significantly as
shown in Figure 6C. Upon heating briefly to a higher tempera-
ture with a heat gun, the gel turned completely red, and the
UV–vis spectrum (Figure 6D) showed two new strong peaks at
486 nm and 528 nm. After cooling the samples, part of the gel
turned back to blue whilst the remainder stayed red.
Figure 6: The UV–vis absorption spectra of the polymerized gel
formed by compound 18A in ethanol (10 mg/mL): A, at room tempera-
ture after 3 min UV irradiation (λmax = 650 nm); B, at 50 °C ( λmax =
634 nm); C, at 60 °C incubation for 90 min (λmax = 534 nm, other
From these observations, we can see that the side chain align-
ment of compound 18A is quite favorable in providing long
peaks are 582, 636 nm); D, after heating at above 60 °C till complete
color change to red (λmax = 486 nm together with 534 nm).
range order for the polymerization of the diacetylene groups.
Typically polydiacetylenes exhibit absorptions near 530 nm and
239

Beilstein J. Org. Chem. 2011, 7, 234–242.
630 nm depending on the side chain structures, and the color scope glass slide, and the gel was imaged directly under the
transition from blue to red has also been well studied [42,43]. microscope. The program used to acquire and store the photos
Our gelator 18A polymerized readily with a TLC UV lamp and was Corel Photo-Paint 7.
the cross linked gels only exhibited absorptions at longer wave-
lengths. The thermo induced color transition is probably due to Scanning electron microscopy. A piece of the gel was
an annealing effect of the blue-purple polydiacetylene gels into deposited on an aluminum sample holder and allowed to dry in
another stable conformation. The study indicated that the for- a desiccator. The dried gel sample was coated with a thin layer
mation of diacetylene gel is an effective method to obtain poly- of platinum (~100–150 Å) by a Denton Vacuum (model Desk
diacetylenes with interesting optical properties.
II) at a reduced pressure of ~30 mTorr and a current of 45 mA
for 60 sec. The sample was analyzed using a JEOL JSM 5410
scanning electron microscope with an EDAX Detecting Unit
Conclusion
We have synthesized a series of 1-deoxy glucose derived esters, PV9757/05 ME (Model 204B+, active area = 10 mm2).
and screened their gelation in several solvents. In comparison
with the α-methoxy series with the same acyl chains, the deoxy Gelation testing. The compounds were typically tested for
sugar analogs, and the monoesters in particular, are less effec- gelation in a 1 dram glass vial. The diacetylene containing com-
tive gelators. It appears that the presence of the α-methoxy pounds were tested in brown vials to avoid polymerization. A
group assists in the formation of hydrogen bonds among the starting concentration of 20 mg/mL was used. The mixture was
compounds and with solvents. However, several diester deriva- heated and sonicated until the sample was fully dissolved. The
tives are effective gelators, and for both the diesters and the solution was then allowed to cool to room temperature for
monoesters, terminal acetylene and aromatic functional groups 15–20 min. If a gel is formed, then the vial is inverted; if no
seemed to facilitate gelation. Therefore, even though it was solvent flows while the gel is inverted, then it is called a stable
found to be less effective than the α-methoxy headgroup 1, the gel. If the gel falls apart during inversion and by gentle shaking,
deoxy sugar headgroup 8 can be used for the preparation of self then it is called an unstable gel or gel-like particulate. If a stable
assembling gelators when the hydrophobic tails are chosen judi- gel is formed, serial dilution is performed until the resulting gel
cially. For instance, long chain diacetylene containing diester is no longer stable. The concentration prior to formation of the
derivatives of 8 are effective gelators, and they can be polymer- unstable gel was recorded as the minimum gelation con-
ized using a TLC lamp more readily than the corresponding centration (MGC).
diesters of 1. The polymerized diacetylene gels were dark blue
with long wavelengths absorptions, these compounds may be UV–vis spectroscopy. The UV–vis spectra were recorded on a
useful as advanced stimuli responsive materials.
Bio-Tek PowerWave Microplate Spectrophotometer using a
96-well microplate (Corning’s UV transparent microplate
#3635). A sample (about 50–100 μL) of the gel of compound
18A in ethanol (10 mg/mL) was transferred into a cell of the
Experimental
General methods and materials
Materials and instrumentation. General chemicals and plate. The plate was covered with its matching lid when not
reagents were purchased from Aldrich, or VWR. The diacety- inside the plate holder. Heating was carried out using the
lene containing fatty acids were purchased from GFS chemi- internal incubator of the spectrophotometer (temperature range
cals. Optical microscope images were recorded with an 25–50 °C) and Max 4000 incubator (temperature range
Olympus BX60 microscope and CCD camera. The samples 25–60 °C) from Barnstead.
were prepared as thin slices of gels placed on a cleaned glass
General procedure for the synthesis of ester
slide, and the gels were imaged directly under the microscope.
NMR spectra were recorded using a 400 MHz Varian NMR derivatives of compound 8
spectrometer. High resolution mass spectrometry data were The three ester derivatives A, B, and C were synthesized in a
measured on the Q-Tof of the Mass Spectrometry lab at the one pot reaction by reacting the corresponding acid chloride
University of Illinois after the low resolution masses were (1.2 equiv) with headgroup 8 (1.0 equiv). Compound 8 was
confirmed. The ionization technique used was ESI (electro- prepared according to literature procedure [38]. If the acid chlo-
spray ionization). Melting points were measured using a Fisher- ride was not commercially available, it was prepared by
Jones melting point apparatus.
converting the corresponding terminal alkynyl carboxylic acid
(1.2 equiv) to the acyl chloride using excess oxalyl chloride
Optical microscopy. Optical micrographs were recorded with [35]. After confirming complete conversion to the acyl chloride,
an Olympus BX60 microscope and CCD camera. The sample hexane was used to co-distill and remove the excess oxalyl
was prepared as a small piece of gel placed on a clean micro- chloride. The acyl chloride was added to compound 8 (1 equiv)
240

Beilstein J. Org. Chem. 2011, 7, 234–242.
in DCM and 4 equiv of pyridine. The reaction mixture was left
stirring under an anhydrous atmosphere for 14–20 h. The crude
product was concentrated, extracted with DCM, washed with
water, then brine, and the combined organic phase dried over
anhydrous sodium sulfate. The crude product was isolated and
purified using a gradient solvent system (hexanes and acetone),
starting with 5% acetone. All yields reported are pure isolated
yields, and were calculated based on compound 8; the yields
were not optimized. The following sections include the charac-
terization data for three compounds, the rest are shown in the
Supporting Information section.
Supporting Information
Supporting Information File 1
Yields and characterization data for compounds 10A–10C
to 18A–18C.
[http://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-7-31-S1.pdf]
Supporting Information File 2
1H and 13C NMR spectra of compounds 9A–18C.
[http://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-7-31-S2.pdf]
Synthesis of 4-pentynoates 9A, 9B, and 9C
Compound 9A. This product was isolated as a white crys-
talline solid in 9.1% yield. M.p. 97–98 °C. 1H NMR (400 MHz, Acknowledgements
CDCl3) δ (ppm) 7.39–7.46 (m, 2H), 7.29–7.37 (m, 3H), 5.49 (s, This research was supported by the National Science Founda-
1H), 5.37 (t, 1H, J = 9.5 Hz), 5.08 (ddd~dt, 1H, J = 5.9, 9.5, tion CHE#518283 and in part by the NSF REU program of
10.3 Hz), 4.33 (dd, 1H, J = 5.1, 10.3 Hz), 4.13 (dd, 1H, J = 5.9, AMRI at UNO for Mr. Sherman Coleman (2008 summer). We
11.4 Hz), 3.71 (t, 1H, J = 10.3 Hz), 3.64 (t, 1H, J = 9.5 Hz), also thank the assistance of Navneet Goyal and Kristopher
3.46 (dt, 1H, J = 5.1, 9.5 Hz), 3.40 (t, 1H, J = 11.0 Hz), Williams with the preparation of the manuscript.
2.51–2.59 (m, 4H), 2.43–2.50 (m, 4H), 1.99 (t, 1H, J = 2.6 Hz),
References
1. Terech, P.; Weiss, R. G. Chem. Rev. 1997, 97, 3133–3160.
1.89 (t, 1H, J = 2.6 Hz). 13C NMR (100 MHz, CDCl3) δ (ppm)
170.8, 170.7, 136.8, 129.0, 128.1, 126.1, 101.4, 82.2, 82.0, 78.6,
doi:10.1021/cr9700282
72.5, 71.4, 69.8, 69.3, 68.5, 67.3, 33.2, 33.1, 14.3, 14.2. HRMS
2. Abdallah, D. J.; Weiss, R. G. Adv. Mater. 2000, 12, 1237–1247.
ESI calcd for C23H24O7Na [M + Na+] 435.1420, found
doi:10.1002/1521-4095(200009)12:17<1237::AID-ADMA1237>3.0.CO;
435.1406.
2-B
3. Meléndez, R. E.; Carr, A. J.; Linton, B. R.; Hamilton, A. D.
Compound 9B. This product was isolated as a white crys-
talline solid in 14.6% yield. M.p. 100–101 °C. 1H NMR
(400 MHz, CDCl3) δ (ppm) 7.46–7.53 (m, 2H), 7.33–7.42 (m,
3H), 5.51 (s, 1H), 4.93 (ddd~dt, 1H, J = 5.9, 9.5, 10.3 Hz), 4.30
(dd, 1H, J = 4.8, 10.6 Hz), 4.09 (dd, 1H, J = 5.9, 11.0 Hz), 3.85
(t, 1H, J = 9.2 Hz), 3.67 (t, 1H, J = 10.3 Hz), 3.49 (t, 1H, J = 9.2
Hz), 3.35 (dt, 1H, J = 5.1, 9.9 Hz), 3.26 (dd~t, 1H, J = 10.6,
11.0 Hz), 2.54–2.64 (m, 2H), 2.45–2.54 (m, 2H), 2.01 (t, 1H, J
= 2.6 Hz). 13C NMR (100 MHz, CDCl3) δ (ppm) 171.1, 136.8,
129.2, 128.2, 126.2, 101.8, 82.2, 81.0, 72.4, 71.9, 70.9, 69.3,
68.5, 67.0, 33.1, 14.3. HRMS ESI calcd for C18H20O6Na [M +
Na+] 355.1158, found 355.1166.
Struct. Bonding 2000, 96, 31–61. doi:10.1007/3-540-46591-X_2
4. Estroff, L. A.; Hamilton, A. D. Chem. Rev. 2004, 104, 1201–1218.
doi:10.1021/cr0302049
5. Gronwald, O.; Snip, E.; Shinkai, S. Curr. Opin. Colloid Interface Sci.
2002, 7, 148–156. doi:10.1016/S1359-0294(02)00016-X
6. George, M.; Weiss, R. G. Acc. Chem. Res. 2006, 39, 489–497.
doi:10.1021/ar0500923
7. Carretti, E.; Bonini, M.; Dei, L.; Berrie, B. H.; Angelova, L. V.;
Baglioni, P.; Weiss, R. G. Acc. Chem. Res. 2010, 43, 751–760.
doi:10.1021/ar900282h
8. Yang, Z.; Liang, G.; Xu, B. Acc. Chem. Res. 2008, 41, 315–326.
doi:10.1021/ar7001914
9. Yang, Z.; Liang, G.; Xu, B. Soft Matter 2007, 3, 515–520.
doi:10.1039/b700138j
10.Shah, C.; Patel, R.; Mazumder, R.; Bhattacharya, S.; Mazumder, A.;
Gupta, R. N. Pharma Rev. 2009, 7, 164–166.
Compound 9C. This product was isolated as a white crys-
talline solid in 23.0% yield. M.p. 148–150 °C. 1H NMR
(400 MHz, CDCl3) δ (ppm) 7.40–7.47 (m, 2H), 7.28–7.36 (m,
3H), 5.46 (s, 1H), 5.16 (dd~t, 1H, J = 9.2, 9.5 Hz), 4.30 (dd, 1H,
J = 5.1, 10.6 Hz), 4.07 (dd, 1H, J = 5.9, 11.4 Hz), 3.86 (m, 1H),
3.67 (dd~t, 1H, J = 10.1 Hz), 3.56 (dd~t, 1H, J = 9.3 Hz, 1H),
3.34–3.47 (m, 2H), 2.54–2.64 (m, 2H), 2.42–2.52 (m, 2H), 1.88
(m, 1H). 13C NMR (100 MHz, CDCl3) δ (ppm) 172.0, 136.9,
128.9, 128.1, 126.0, 101.2, 82.3, 78.7, 76.6, 71.2, 70.6, 69.14,
69.09, 68.7, 33.3, 14.3. HRMS calcd for C18H20O7Na [M +
Na+] 355.1158, found 355.1147.
11.Zhao, F.; Ma, M. L.; Xu, B. Chem. Soc. Rev. 2009, 38, 883–891.
doi:10.1039/b806410p
12.Fujita, N.; Mukhopadhyay, P.; Shinkai, S. Annu. Rev. Nano Res. 2006,
1, 385–428. doi:10.1142/9789812772374_0009
13.Vintiloiu, A.; Leroux, J.-C. J. Controlled Release 2008, 125, 179–192.
doi:10.1016/j.jconrel.2007.09.014
14.Nonappa, N.; Maitra, U. Org. Biomol. Chem. 2008, 6, 657–669.
doi:10.1039/B714475J
15.Hafkamp, R. J. H.; Feiters, M. C.; Nolte, R. J. M. J. Org. Chem. 1999,
64, 412–426. doi:10.1021/jo981158t
16.Ajayaghosh, A.; Praveen, V. K.; Vijayakumar, C. Chem. Soc. Rev.
2008, 37, 109–122. doi:10.1039/b704456a
241

Beilstein J. Org. Chem. 2011, 7, 234–242.
17.Vemula, P. K.; John, G. Acc. Chem. Res, 2008, 41, 769–782.
doi:10.1021/ar7002682
43.Schott, M. J. Phys. Chem. B 2006, 110, 15864–15868.
doi:10.1021/jp0638437
18.John, G.; Vemula, P. K. Soft Matter 2006, 2, 909–914.
doi:10.1039/b609422h
19.Ghosh, R.; Chakraborty, A.; Maiti, D. K.; Puranik, V. G. Org. Lett. 2006,
8, 1061–1064. doi:10.1021/ol052963e
License and Terms
20.Friggeri, A.; Gronwald, O.; Van Bommel, K. J. C.; Shinkai, S.;
Reinhoudt, D. N. J. Am. Chem. Soc. 2002, 124, 10754–10758.
doi:10.1021/ja012585i
This is an Open Access article under the terms of the
Creative Commons Attribution License
(http://creativecommons.org/licenses/by/2.0), which
permits unrestricted use, distribution, and reproduction in
any medium, provided the original work is properly cited.
21.Chakraborty, T. K.; Jayaprakash, S.; Srinivasu, P.;
Madhavendra, S. S.; Ravi Sankar, A.; Kunwar, A. C. Tetrahedron 2002,
58, 2853–2859. doi:10.1016/S0040-4020(02)00158-8
22.Koshi, Y.; Nakata, E.; Yamane, H.; Hamachi, I. J. Am. Chem. Soc.
2006, 128, 10413–10422. doi:10.1021/ja0613963
23.Kiyonaka, S.; Sada, K.; Yoshimura, I.; Shinkai, S.; Kato, N.; Hamachi, I.
Nat. Mater. 2004, 3, 58–64. doi:10.1038/nmat1034
24.Yang, Z.; Liang, G.; Ma, M.; Abbah, A. S.; Lu, W. W.; Xu, B.
Chem. Commun. 2007, 843–845. doi:10.1039/b616563j
25.Vemula, P. K.; Li, J.; John, G. J. Am. Chem. Soc. 2006, 128,
8932–8938. doi:10.1021/ja062650u
The license is subject to the Beilstein Journal of Organic
Chemistry terms and conditions:
(http://www.beilstein-journals.org/bjoc)
The definitive version of this article is the electronic one
which can be found at:
26.Jung, J. H.; Amaike, M.; Nakashima, K.; Shinkai, S.
J. Chem. Soc., Perkin Trans. 2 2001, 1938–1943.
doi:10.1039/B104190H
doi:10.3762/bjoc.7.31
27.Bhat, S.; Maitra, U. Tetrahedron 2007, 63, 7309–7320.
doi:10.1016/j.tet.2007.03.118
28.Suzuki, M.; Owa, S.; Shirai, H.; Hanabusa, K. Tetrahedron 2007, 63,
7302–7308. doi:10.1016/j.tet.2007.02.065
29.Goyal, N.; Cheuk, S.; Wang, G. Tetrahedron 2010, 66, 5962–5971.
doi:10.1016/j.tet.2010.05.071
30.Bielejewski, M.; Łapiński, A.; Luboradzki, R.; Tritt-Goc, J. Langmuir
2009, 25, 8274–8279. doi:10.1021/la900467d
31.Kobayashi, H.; Friggeri, A.; Koumoto, K.; Amaike, M.; Shinkai, S.;
Reinhoudt, D. N. Org. Lett. 2002, 4, 1423–1426.
doi:10.1021/ol025519+
32.Luboradzki, R.; Gronwald, O.; Ikeda, A.; Shinkai, S. Chem. Lett. 2000,
29, 1148–1149. doi:10.1246/cl.2000.1148
33.Jung, J. H.; John, G.; Masuda, M.; Yoshida, K.; Shinkai, S.; Shimizu, T.
Langmuir 2001, 17, 7229–7232. doi:10.1021/la0109516
34.Wang, G.; Cheuk, S.; Williams, K.; Sharma, V.; Dakessian, L.;
Thorton, Z. Carbohydr. Res. 2006, 341, 705–716.
doi:10.1016/j.carres.2006.01.023
35.Nie, X.; Wang, G. J. Org. Chem. 2006, 71, 4734–4741.
doi:10.1021/jo052317t
36.Cheuk, S.; Stevens, E. D.; Wang, G. Carbohydr. Res. 2009, 344,
417–425. doi:10.1016/j.carres.2008.12.006
37.Wang, G.; Cheuk, S.; Yang, H.; Goyal, N.; Reddy, P. V. N.;
Hopkinson, B. Langmuir 2009, 25, 8696–8705. doi:10.1021/la804337g
38.Nie, X.; Wang, G. J. Org. Chem. 2005, 70, 8687–8692.
doi:10.1021/jo0507901
39.Wang, G.; Ella-Menye, J.-R.; St. Martin, M.; Yang, H.; Williams, K.
Org. Lett. 2008, 10, 4203–4206. doi:10.1021/ol801316f
40.Dautel, O. J.; Robitzer, M.; Lère-Porte, J.-P.; Serein-Spirau, F.;
Moreau, J. J. E. J. Am. Chem. Soc. 2006, 128, 16213–16223.
doi:10.1021/ja065434u
41.Sada, K.; Takeuchi, M.; Fujita, N.; Numata, M.; Shinkai, S.
Chem. Soc. Rev. 2007, 36, 415–435. doi:10.1039/b603555h
42.Fujita, N.; Sakamoto, Y.; Shirakawa, M.; Ojima, M.; Fujii, A.; Ozaki, M.;
Shinkai, S. J. Am. Chem. Soc. 2007, 129, 4134–4135.
doi:10.1021/ja069307+
242