P-Phenyleneethynylene-based comb-like oligomers: The synthesis and self-assembling property

Article abstract of DOI:10.1016/j.tet.2012.01.082

This paper describes the self-assembling property of three series of p-phenyleneethynylene based comb-like oligomers, which carry multiple peripheral side chains of different polarity. The new oligomers are prepared readily through the formation of the hydrazone bonds from the corresponding aldehyde and gallic acid-derived benzohydrazides. In polar solvents such as methanol and ethanol, the oligomers that bear n-decyl or 2-(2-(dioctylamino)-2-oxoethyl- amino)-2-oxoethoxyl unit (DOAOE) segments as the side chains are revealed to form vesicular structures, while the oligomers carrying hydrophilic oligo(ethyleneglycol) side chains do not. The structures of the vesicles are evidenced by SEM, AFM, TEM, and dye-encapsulation experiments. UV-vis absorption spectroscopic experiments suggest that the vesicles are generated through the stacking of the conjugated backbones, which is promoted by the solvophobic interaction of the peripheral side chains.

Full text of DOI:10.1016/j.tet.2012.01.082

Tetrahedron 68 (2012) 5303e5310
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
p-Phenyleneethynylene-based comb-like oligomers: the synthesis and
self-assembling property
*
*
Liu-Gang Wang, Tian-Guang Zhan, Xin Zhao , Xi-Kui Jiang, Zhan-Ting Li
State Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 18 August 2011
Received in revised form 24 October 2011
Accepted 26 October 2011
Available online 4 February 2012
This paper describes the self-assembling property of three series of p-phenyleneethynylene based comb-
like oligomers, which carry multiple peripheral side chains of different polarity. The new oligomers are
prepared readily through the formation of the hydrazone bonds from the corresponding aldehyde and
gallic acid-derived benzohydrazides. In polar solvents such as methanol and ethanol, the oligomers that
bear n-decyl or 2-(2-(dioctylamino)-2-oxoethyl-amino)-2-oxoethoxyl unit (DOAOE) segments as the side
chains are revealed to form vesicular structures, while the oligomers carrying hydrophilic oligo(ethyle-
neglycol) side chains do not. The structures of the vesicles are evidenced by SEM, AFM, TEM, and dye-
encapsulation experiments. UVevis absorption spectroscopic experiments suggest that the vesicles are
generated through the stacking of the conjugated backbones, which is promoted by the solvophobic
interaction of the peripheral side chains.
Keywords:
p-Phenyleneethynylene
Vesicle
Self-assembly
Comb-like
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
linear conjugated systems are quite limited,10 which might be partly
attributed to the fact that it is hard for rigid linear molecules to ar-
Conjugated systems have drawn considerable attention in the
past decade because of their unique physical properties associated
range into certain curve, which is a precondition for the formation of
hollow spherical structures. To reach this goal, peripheral sub-
stituents are usually required to attach to the rigid backbones of
linear conjugated systems, which not only provide solubility but
also serve to control the stacking angle and ordering. In this paper,
we describe the self-assembly behavior of three series of OPE de-
rivatives, i.e., Ta-1e4, Tb-1e4 and Tc-1e4. We report that only those
structures carrying peripheral side chains of low and medium po-
larity can self-assemble into vesicular structures and demonstrate
that the peripheral substituents play a crucial role in the construc-
tion of vesicular structures from linear conjugated molecules.
with the delocalization of
p-electrons within the backbones. Cur-
rently, numerous conjugated molecules have been created and
exploited as basic units for molecular electronics and photonics.1 In
this context, straight oligo-p-phenyleneethynylenes (OPEs) have
been investigated extensively for their applications in the fabrica-
tion of organic devices such as molecular wires and sensors.2 Due to
the intermolecular p-stacking interaction, this family of conjugated
molecules usually demonstrate strong aggregating tendency under
certain conditions, which makes them extremely attractive as
building blocks for the construction of functional supramolecular
architectures on the micro- and nanoscales. Among other mor-
phologies of assembled systems, vesicles, the microscopic capsules
that enclose a volume with a molecularly thin membrane, have
drawn great attention because of their potential applications in drug
and gene delivery,3 nano-reactors,4 and artificial cell membranes.5
To this end, vesicles assembled from conjugated systems should
be attractive for their potentials as novel functional soft materials
because the unique physical properties that these conjugated mol-
ecules offer should be maintained in the membranes of self-
assembled vesicles. Although vesicles formed from lipid mole-
cules,6 surfactants,7 block copolymers,8 and arylamides,9 have been
well-documented, examples of vesicular structures assembled from
* Corresponding authors. Tel.: þ86 21 54925023; fax: þ86 21 64166128; e-mail
addresses: xzhao@mail.sioc.ac.cn, xinzhao72@yahoo.com (X. Zhao), ztli@mail.sio-
c.ac.cn (Z.-T. Li).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2012.01.082

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L.-G. Wang et al. / Tetrahedron 68 (2012) 5303e5310
2. Results and discussion
2.1. Design and synthesis
The new compounds bear different side chains, including
hydrophobic decyl, hydrophilic oligo(ethyleneglycol), and am-
phiphilic 2-(2-(dioctylamino)-2-oxoethyl-amino)-2-oxoethoxyl
(DOAOE). The side chains were attached to the oligomeric p-
phenyleneethynylene backbones via forming a hydrazone bond
through a gallic acid as a linker to produce comb-like structures.
It was expected that a systematic investigation of their self-
assembling property would reveal the function of the side chains.
The key oligomeric aldehyde precursors were prepared through
repeated Sonogashira coupling reactions, which were followed by
the introduction of the peripheral side chains via the formation of
the hydrazone bonds. The synthetic routes for the aldehyde pre-
cursors are provided in Scheme 1. Thus, compound 1 was first
reacted with 2 to give dialdehyde 3 in 83% yield, while the reaction
of 2 with 4 afforded trialdehyde 5 in 57% yield. Using similar pro-
cedures, tetraaldehyde 10 was prepared in 76% yield by coupling 9
with 8, which was synthesized via the treatment of dialdehyde 4
with monoaldehyde 6 in the presence of PdCl2(PPh3)2 and CuI in
THF, followed by converting the resulting phenol into tri-
fluoromethanesulfonate. For the preparation of pentaaldehyde 14,
phenol 11 was first converted into trifluoromethanesulfonate 12,
which was then coupled with compound 9 to give dialdehyde 13
in 84% yield. After the removal of the TMS unit under the basic
condition, the resulting compound 14 was further coupled with 8
to generate pentaaldehyde 15 in 74% yield. For gallic acid hydra-
zides 20, 21, and 22 (Scheme 2), methyl gallate was reacted with n-
decylbromide, [2-[2-(2-methoxyethoxy)ethoxy]-ethoxy]tosylate,
and 2-(2-(dioctylamino)-2-oxoethyl-amino)-2-oxoethylchloride,
respectively, and the resulting products were further treated with
hydrazine to give the corresponding gallic acid hydrazides. Com-
pounds Ta-1e4, Tb-1e4, and Tc-1e4 were then prepared from the
condensation reactions of the aldehydes and hydrazides in
dichloromethane and methanol (Scheme 3).
Scheme 2.
Scheme 3.
2.2. Self-assembling property of Ta-1e4
The self-assembling behavior of the Ta series was first in-
vestigated using SEM, which revealed that they did not give rise to
ordered structures in n-hexane, chloroform or THF, although these
compounds were soluble in these solvents. The compounds were
nearly insoluble in polar methanol and ethanol at room tempera-
ture, but became soluble in ethanol upon heating. After being
cooled to room temperature, some precipitates could be observed
for the solutions of Ta-2e4. Therefore, clear supernatant ethanol
solutions of their as-prepared samples were drop-casted onto
freshly cleaved mica wafers. SEM images revealed that all the four
compounds gave rise to vesicles (Fig. 1). Compared to those formed
from Ta-2e4, significant fusion of the vesicles was observed for Ta-
1. The self-assembling behavior of the four compounds in the
ethanolechloroform binary solvent was also investigated. When
the content of chloroform was 20% (4:1, v/v), SEM did not show any
vesicular structures for the sample obtained from Ta-1, but oligo-
mers Ta-2e4 did form (Fig. S1). When the content of chloroform
was increased to 33%, only Ta-4 could assemble into well-defined
vesicles (Fig. S2). Under this condition, no vesicles could be ob-
served from compounds Ta-1 and Ta-2, and for Ta-3, only very few
spherical structures could be found and most of the aggregates
were irregular (Fig. S2). This result suggested that oligomers with
longer backbones had higher self-assembling ability. Introduction
of chloroform into ethanol decreased the polarity of the solvent and
weakened the stacking ability of the backbones and also decreased
Fig. 1. SEM images of (a) Ta-1 (1 mM), (b) Ta-2 (saturated, ca. 0.9 mM), (c) Ta-3 (sat-
urated, ca. 0.4 mM), and (d) Ta-4 (saturated, ca. 0.1 mM) on mica surface. The samples
were obtained by evaporation of their ethanol solutions.
Scheme 1.

L.-G. Wang et al. / Tetrahedron 68 (2012) 5303e5310
5305
the solvophobic interaction between the periphery alkyl chains and
solvent molecules. As a result, only oligomers with longer back-
bones could maintain enough strong stacking interactions to keep
the vesicular structures.
2.3. Self-assembling property of Tb-1e4
The self-assembling behavior of the Tb series was then in-
vestigated. In contrast to the Ta series, oligomers Tb-1e4 were
soluble in both less polar and polar solvents. However, SEM images
showed that, in all investigated solvents, including decalin, toluene,
dichloromethane, methanol, and ethanol, they did not give rise to
ordered aggregates.
2.4. Self-assembling property of Tc-1e4
Oligomers Tc-1e4 were also soluble in a wide range of solvents
of different polarity. Similar to the Ta series, SEM images showed
that they did not generate well-defined aggregates in decalin,
chloroform, or THF. However, in methanol or ethanol, spherical
entities were observed (Fig. 2).
Fig. 3. Tapping-mode AFM images and cross-section analysis of (a) Ta-2 (0.02 mM),
and (b) Tc-4 (0.03 mM), on silicon plate after the solvent (ethanol) was evaporated.
Fig. 4. High-resolution TEM images of (a) Ta-1 (0.1 mM), and (b) Ta-4 (0.1 mM) in
ethanolechloroform (4:1, v/v) and (c) Tc-4 (0.1 mM) in ethanol after the solvent was
evaporated.
oligomers of both the Ta and Tc series in ethanol. After one hea-
tingecooling cycle, the resulting solutions were dialyzed in ethanol
for 3 days to remove the dye in the solutions. Fluorescence images
of these samples after dialysis readily showed discrete red spheres,
suggesting rhodamine B was entrapped inside the spheres, which
not only supported their hollow feature but also indicated the as-
sembling structures were quite stable (Fig. 5).
Fig. 2. SEM images of (a) Tc-1, (b) Tc-2, (c) Tc-3, and (d) Tc-4 on mica surface. The
samples were obtained by evaporation of their ethanol solutions (0.5 mM).
2.5. AFM and TEM investigations
In order to obtain more evidences for the formation of vesicles
from the Ta and Tc series in polar solvents, tapping-model AFM and
high-resolution TEM studies were performed. The AFM images
further demonstrated the formation of spherical aggregates. Fur-
thermore, the cross-section analysis of typical spheres revealed
a flattened shape for the samples by demonstrating a large ratio of
diameter over height (22.5 for Ta-2 and 50.6 for Tc-4) (Fig. 3). The
flattened spheres might arise from the collapse of the vesicles after
evaporation of the solvent encapsulated in the inner part of the
spheres, suggesting a hollow nature for the spherical structures.11
The hollowness of the spheres was also evidenced by TEM
(Fig. 4). Clear contrast was observed between the periphery and
central part of the spherical aggregates, which is typically produced
by the projection of hollow sphere.12
2.6. Fluorescence microscopy investigation
Fig. 5. Fluorescence micrographs of rhodamine B-entrapped vesicles of (a) Ta-1, (b) Ta-
4, (c) Tc-2, and (d) Tc-4. The concentration was 0.5 mM (0.1 mM for Ta-4) in ethanol
and the scale bar for the fluorescent images was 10 mm.
Dye-encapsulation experiments were also conducted. Rhoda-
mine B (C¼2 mg mLꢀ1) was added into the solutions of the

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L.-G. Wang et al. / Tetrahedron 68 (2012) 5303e5310
Table 1
2.7. Self-assembling pattern
Summary of self-assembling property of the oligomers
UVevis absorption spectra of selected oligomers were recorded
to further investigate their self-assembling behavior in solution.
Compared to those in chloroform in which the aromatic stacking is
weak, the absorption of the solution of Ta-2 and Tc-3 in ethanol
decreased significantly (more than 30%), while Tb-3 exhibited al-
most the same absorption intensity as that in chloroform (Fig. 6).
The hypochromic effect displayed by Ta-2 and Tc-3 should be at-
tributed to the stacking of their oligo-p-phenyleneethynylene
backbones, which did not occur for Tb-3. The above high-resolution
TEM study also provided the wall thickness for the selected vesi-
cles. The wall thickness of the vesicles formed by Ta-2 in chlor-
oformeethanol (1:4 v/v) was estimated to be ca. 1.9 nm, while the
wall thickness of the vesicle formed by Tc-4 in ethanol was esti-
mated to be ca. 4.1 nm. Considering the low rotation barrier of the
single CeC bonds that connect the conjugated segments,13 the
gallic acid units with the side chains should distribute on both sides
of the oligo-p-phenyleneethynylene backbones. CPK modeling
showed that the widths (w) of oligomers Ta-2 and Tc-4 of this
conformation were ca. 2.2 and 3.5 nm, respectively. Therefore, their
vesicles might be formed through a monolayer stacking pattern, as
illustrated in Fig. 7.
Solvent
Ta-1
Ta-2
Ta-3
Ta-4
Tb-1e4
Tc-1e4
Hexane
Decaline
Chloroform
Tetrahydrofuran
Ethanol
Methanol
Ethanolechloroform
(4:1, v/v)
Ethanolechloroform
(2:1, v/v)
ꢁ
ꢁ
ꢁ
ꢁ
d
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
d
d
ꢁ
d
ꢁ
d
ꢁ
d
ꢁ
d
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
U
d
ꢁ
U
d
U
U
d
U
U
d
U
U
U
d
ꢁ
ꢁ
ꢁ
O
d
d
‘U’¼Vesicles, ‘ꢁ’¼irregular aggregates, ‘d’¼not applicable.
4. Experimental section
4.1. General methods
All reagents and chemicals were obtained from commercial
sources and used without further purification unless otherwise
noted. The solvents have been purified by standard procedures
before use. The 1H and 13C NMR spectra were recorded on Bruker
Avance 300 MHz or 400 MHz spectrometer in the indicated sol-
(a)
(b)
(c)
Fig. 6. UVevis spectra of (a) Ta-2 (5ꢁ10ꢀ6 M), (b) Tb-3 (7.5ꢁ10ꢀ6 M), and (c) Tc-3 (8ꢁ10ꢀ6 M) in chloroform (black) and ethanol (red).
Fig. 7. Tentative model for the formation of the vesicular structures from the oligomers (with Ta-2 and Tc-2 as examples).
3. Conclusion
vents. Chemical shifts are expressed in parts per million (d) using
residual proton resonances of the deuterated solvents as the in-
ternal standards. Because of the rotation and significant aggrega-
tion of the oligomers, the resolution of 1H and 13C NMR was of
extreme low for the oligomers with longer backbones, and no
satisfied spectra could be obtained for some oligomers. Therefore,
those oligomers could not be fully characterized. However, the
formation of the target compounds could be evidenced by their IR
spectra, which show no band of the CHO unit, as compared with
their precursors. Atomic force microscopy (AFM) measurements
were performed on a Nano scope IIIa MultiMode microscope;
transmission electron microscopy (TEM) images were recorded on
a JEOL JEM-2010 microscope working at 200 kV; scanning electron
Through the introduction of different peripheral side chains into
the backbones of oligo-p-phenyleneethynylenes, three series of
comb-like conjugated oligomers have been constructed. Although
the oligomers possess the identical backbones, the fact that only
the Ta and Tc series could self-assemble into vesicles revealed that
the peripheral substituents play a crucial role in promoting the
formation of the ordered aggregates for this family of rigid and
linear conjugated systems (Table 1). Currently, we are investigating
the aggregation of other comb-like aromatic systems that have side
chains of varying length to explore the possibility of forming other
kinds of aggregates like organogels.

L.-G. Wang et al. / Tetrahedron 68 (2012) 5303e5310
5307
microscopy (SEM) experiments were conducted on a JEOL JSM-
6390-LV microscope; a fluorescence microscope (Olympus IX51)
was used for fluorescence microscopy study. UVevis spectra were
recorded on a CARY 100 spectrometer.
J¼7.5 Hz, 1H), 8.14 (s, 1H), 8.19 (d, J¼2.1 Hz, 1H), 10.28 (s, 1H), 10.57
(s, 1H), 10.62 (s, 1H). 13C NMR (100 MHz, CDCl3):
87.8, 88.5, 94.1,
94.4, 123.0, 123.6, 124.0, 124.9, 125.6, 127.8, 128.7, 129.4, 131.2, 133.5,
133.7,133.8,133.9,136.0, 136.1,136.3,138.3,149.5,185.5,189.9,191.1.
MS (MALDI-TOF): m/z 511.0 [MþH]þ. HRMS (MALDI-TOF): calcd for
C26H14F3O6S [MþH]þ: 511.0474, found 511.0458.
d
4.2. Synthetic procedures and characterizations
4.2.1. Compound 3. To
a
mixture of compound
1
(326 mg,
4.2.5. Compound 10. Compound 10 was prepared in 76% yield as
a pale yellow solid from the reaction of compound 8 and compound
917 according to a procedure similar to that described for com-
pound 3. The crude product was dissolved in dichloromethane and
then the insoluble material was filtered. After removal of solvent,
the crude product was washed with a mixture of petroleum ether/
dichloromethane (v/v, 1:1) several times to remove impurities and
finally give compound 10. Mp 253e254 ꢂC. 1H NMR (300 MHz,
2.5 mmol), compound 214 (582 mg, 2.5 mmol), and PdCl2(PPh3)2
(37 mg, 0.05 mmol) in a flame-dried Schlenk tube were added THF
(15 mL) and Et3N (5 mL) under argon atmosphere and followed by
the addition of CuI (10 mg, 0.05 mmol) 10 min later. The mixture
was stirred at room temperature for 9 h and then water (20 mL)
and brine (20 mL) were added. After being extracted with ethyl
acetate (3ꢁ30 mL), the combined organic phase was washed with
brine and dried over sodium sulfate. Upon removal of the solvent
under reduced pressure, the resulting residue was purified by
column chromatography (petroleum ether/dichloromethane 1:1)
to give compound 3 as a pale yellow solid (487 mg, 83%). Mp
CDCl3):
d
7.52 (t, J¼6.9 Hz, 1H), 7.62e7.72 (m, 5H), 7.79 (d, J¼8.1 Hz,
2H), 7.84 (d, J¼7.5 Hz, 1H), 7.94 (d, J¼8.4 Hz, 1H), 7.98 (d, J¼8.1 Hz,
1H), 8.10 (s, 1H), 8.15 (s, 2H), 10.06 (s, 1H), 10.61 (s, 1H), 10.63 (s, 2H).
MS (EI): m/z 490 [M]þ. HRMS (MALDI-TOF): calcd for C34H19O4
[MþH]þ: 491.1281, found 491.1278. IR (KBr, cmꢀ1): 3056, 2837,
1691, 1588, 1499, 1389, 1250, 1194.
77e78 ꢂC. 1H NMR (300 MHz, CDCl3):
d
7.49 (t, J¼7.2 Hz, 1H),
7.54e7.64 (m, 2H), 7.67 (d, J¼7.5 Hz, 1H), 7.81 (d, J¼7.5 Hz, 1H), 7.90
(d, J¼7.5 Hz, 1H), 7.96 (d, J¼7.5 Hz, 1H), 8.07 (s, 1H), 10.03 (s, 1H),
10.63 (s, 1H). 13C NMR (100 MHz, CDCl3):
d
86.4, 94.5, 123.6, 126.0,
4.2.6. Compound 12. Compound 12 was prepared in 78% yield as
a pale yellow oil from the reaction of compound 1118 and tri-
fluoromethanesulfonic anhydride according to a procedure similar
127.6,129.1,129.3, 129.7,132.9,133.4,133.9,135.9,136.6,137.1,191.3,
191.3. MS (EI): m/z 234 [M]þ. HRMS (EI): calcd for C16H10O2 [M]þ:
234.0681, found 234.0687. IR (KBr, cmꢀ1): 3064, 2834, 2732, 2208,
1703, 1591, 1284, 1200.
to that described for compound 8. 1H NMR (300 MHz, CDCl3):
d 0.26
(s, 9H), 7.35 (d, J¼8.4 Hz, 1H), 7.74 (dd, J1¼8.4 Hz, J2¼1.8 Hz, 1H),
8.05 (d, J¼1.8 Hz, 1H), 10.22 (s, 1H). 13C NMR (100 MHz, CDCl3):
4.2.2. Compound 5. Compound 5 was prepared in 57% yield as
a pale yellow solid from the reaction of compound 2 and compound
415 according to a procedure similar to that described for com-
d
ꢀ0.3, 98.7, 101.4, 122.6, 124.7, 128.4, 134.2, 138.5, 148.9, 185.8. MS
(ESI): m/z 405.0 [MþMeOHþNa]þ. HRMS (ESI): calcd for
C13H13F3NaSSiO4 [MþNa]þ: 373.01481, found 373.01440.
pound 3. Mp 205e206 ꢂC. 1H NMR (300 MHz, CDCl3):
d 7.51 (t,
J¼6.9 Hz, 1H), 7.59e7.64 (m, 2H), 7.66e7.70 (m, 2H), 7.78 (dd,
J1¼7.8 Hz, J2¼1.8 Hz, 1H), 7.83 (d, J¼7.8 Hz, 1H), 7.93 (d, J¼7.8 Hz,
1H), 7.98 (d, J¼7.8 Hz, 1H), 8.09 (s, 1H), 8.13 (s, 1H), 10.05 (s, 1H),
4.2.7. Compound 13. Compound 13 was prepared in 84% yield as
a pale brown solid from the reaction of compound 9 and compound
12 according to a procedure similar to that described for compound
10.62 (s, 2H). 13C NMR (100 MHz, CDCl3):
d
86.1, 88.1, 94.3, 96.5,
3. 1H NMR (300 MHz, CDCl3):
d
0.26 (s, 9H), 7.54e7.67 (m, 3H), 7.80
(d, J¼6.6 Hz, 1H), 7.91 (d, J¼6.6 Hz, 1H), 8.03 (s, 1H), 8.06 (s, 1H),
10.04 (s, 1H), 10.57 (s, 1H). 13C NMR (100 MHz, CDCl3):
123.3, 123.4, 125.7 (d), 125.9, 127.7, 129.3, 129.4, 130.0, 130.8, 132.9,
133.4, 133.5, 133.9, 136.0, 136.2, 136.6, 137.1, 190.3, 191.1, 191.2. MS
(EI): m/z 362 [M]þ. HRMS (EI): calcd for C25H14O3[M]þ: 362.0943,
found 362.0948. IR (KBr, cmꢀ1): 3058, 2833, 2746, 1699, 1595, 1498,
1271, 1196.
d
ꢀ0.23, 86.2,
96.0, 98.3, 103.0, 123.4, 124.4, 125.3, 129.4, 129.9, 131.2, 132.9, 133.2,
135.7, 136.5, 136.6, 137.1, 190.5, 191.3. MS (EI): m/z 330 [M]þ. HRMS
(MALDI-TOF): calcd for C21H19SiO2 [MþH]þ: 331.1154, found
331.1149.
4.2.3. Compound 7. Compound 7 was prepared in 67% yield as
a pale yellow solid from the reaction of compound 4 and compound
616 according to a procedure similar to that described for com-
4.2.8. Compound 14. Compound 13 (317 mg, 0.96 mmol) was dis-
solved in dichloromethane (10 mL) and methanol (5 mL). Under
stirring, to this solution was added anhydrous potassium carbonate
(53 mg, 0.38 mmol). Stirring continued at room temperature for 3 h
and the solvent was removed with a rotavapor. Water (40 mL) was
added and the aqueous phase was then extracted with dichloro-
methane (3ꢁ35 mL). The combined organic phase was successively
washed with water (2ꢁ40 mL) and brine (40 mL), and dried over
magnesium sulfate. After removal of the solvent, the resulting
residue was purified by column chromatography (petroleum ether/
dichloromethane 1:5 to 1:2) to give compound 14 as a white solid
pound 3. Mp 233e234 ꢂC. 1H NMR (300 MHz, CDCl3):
d 7.05 (d,
J¼8.7 Hz, 1H), 7.51 (t, J¼7.8 Hz, 1H), 7.60e7.75 (m, 5H), 7.83 (d,
J¼1.5 Hz, 2H), 7.98 (d, J¼8.1 Hz, 1H), 8.12 (s, 1H), 9.93 (s, 1H), 10.60
(s, 1H), 10.62 (s, 1H), 11.24 (s, 1H). 13C NMR (100 MHz, CDCl3):
d 84.5,
88.0, 94.4, 96.6, 113.9, 118.6, 120.6, 123.0, 125.8, 126.3, 127.7, 129.3,
130.9, 133.3, 133.4, 133.9, 135.8, 136.0, 136.2, 137.3, 139.8, 162.2,
190.5, 191.2, 195.9. MS (ESI): m/z 377.1 [MꢀH]ꢀ. HRMS (MALDI-
TOF): calcd for C25H15O4 [MþH]þ: 379.0975, found 379.0965.
4.2.4. Compound 8. To
2.2 mmol) in dichloromethane (160 mL) and Et3N (30 mL) was
added slowly (ca. 40 min to complete) solution of tri-
a
solution of compound
7
(823 mg,
(208 mg, 84%). Mp 149e150 ꢂC. 1H NMR (300 MHz, CDCl3):
d 3.26 (s,
1H), 7.56e7.63 (m, 2H), 7.69 (d, J¼8.0 Hz, 1H), 7.81 (d, J¼7.7 Hz, 1H),
a
7.91 (d, J¼7.7 Hz, 1H), 8.06 (s, 2H), 10.04 (s, 1H), 10.58 (s, 1H). 13C
fluoromethanesulfonic anhydride in dichloromethane (30 mL). The
mixture was stirred at room temperature for 32 h and then the
resulting solid was filtered and the filtrate was dried over magne-
sium sulfate. After removal of the solvent under reduced pressure,
the resulting residue was purified by column chromatography
(dichloromethane) to give compound 8 as a pale yellow solid
NMR (100 MHz, CDCl3): d 80.5, 81.9, 86.0, 96.2, 123.2, 123.3, 125.8,
129.4,130.0,131.3,132.9,133.3,135.8,136.6,136.8,137.1,190.3,191.2.
MS (EI): m/z 258 [M]þ. HRMS (MALDI-TOF): calcd for C18H11O2
[MþH]þ: 259.0755, found 259.0754.
4.2.9. Compound 15. Compound 15 was prepared in 74% yield as
a pale yellow solid from the reaction of compound 8 and compound
14 according to a procedure similar to that described for compound
3. The crude product was purified by repeated washing and
(780 mg, 70%). Mp 176e177 ꢂC. 1H NMR (300 MHz, CDCl3):
d 7.47 (d,
J¼8.4 Hz, 1H), 7.52 (t, J¼7.8 Hz, 1H), 7.60e7.71 (m, 3H), 7.79 (dd,
J1¼7.8 Hz, J2¼2.1 Hz, 1H), 7.89 (dd, J1¼8.4 Hz, J2¼2.4 Hz, 1H), 7.98 (d,

5308
L.-G. Wang et al. / Tetrahedron 68 (2012) 5303e5310
centrifugation process. Mp >320 ꢂC. MS (EI): 618 [M]þ. HRMS
(MALDI-TOF): calcd for C43H22O5 [MþH]þ: 618.1469, found
618.1462. IR (KBr, cmꢀ1): 3055, 2837, 1691, 1588, 1501, 1389, 1249,
1186. No 1H and 13C NMR spectrum could be recorded for com-
pound 15 because of its extremely poor solubility.
70.8, 71.3, 71.5, 71.6, 71.7, 72.9, 73.6, 107.6, 129.2, 142.2, 153.8, 168.9.
MS (ESI): m/z 645.3 [MþNa]þ. HRMS (ESI): calcd for C28H50N2NaO13
[MþH]þ: 645.3205, found 645.3224. IR (KBr/cmꢀ1): 3319, 2876,
1638, 1578, 1492, 1341, 1245, 1135.
4.2.15. Compound 22. Compound 22 was prepared in 66% yield as
a sticky solid from the reaction of compound 19 and hydrazine
according to a procedure similar to that described for compound
4.2.10. Compound 17. A mixture of methyl gallate (16) (1.9 g,
10.4 mmol), decylbromide (8.9 g, 40.2 mmol), KI (2.11 g,12.8 mmol),
and anhydrous potassium carbonate (9.8 g, 70.8 mmol) in acetoni-
trile (40 mL) was heated under reflux for 24 h. After being cooled to
room temperature, the solvent was removed with a rotavapor.
To the resulting mixture, water (40 mL) was added and the
aqueous phase was extracted with dichloromethane (3ꢁ40 mL). The
combined organic phase was successively washed with water
(2ꢁ40 mL) and brine (40 mL), and dried over magnesium sulfate.
After removal of the solvent, the resulting residue was purified by
column chromatography (petroleum ether/dichloromethane 30:1)
to give compound 17 as a pale yellow oil (2.0 g, 85%). 1H NMR
20. 1H NMR (300 MHz, CDCl3):
d
0.81 (d, J¼5.0 Hz, 18H), 1.20 (s,
60H), 1.44e1.53 (m, 12H), 3.09e3.12 (m, 6H), 3.24 (d, J¼6.7 Hz, 6H),
4.06e4.12 (m, 8H), 4.61 (s, 4H), 4.72 (s, 2H), 7.24 (s, 2H), 7.59 (d,
J¼4.3 Hz, 2H), 8.37 (s, 1H), 9.49 (s, 1H). 13C NMR (100 MHz, CDCl3):
d
14.0, 22.6, 26.8, 26.9, 27.0, 27.6, 27.6, 28.7, 28.8, 29.1, 29.2, 29.2,
29.3, 29.3, 31.7, 40.7, 40.9, 46.1, 46.4, 47.0, 69.1, 72.7, 108.3, 129.1,
140.4, 150.6, 164.9, 166.9, 167.1, 168.3, 169.2. MS (ESI): m/z 1199.7
[MþH]þ. HRMS (ESI): calcd for C67H122N8NaO10 [MþH]þ:
1221.9176, found 1221.9231. IR (KBr/cmꢀ1): 3334, 2925, 2855, 1675,
1651, 1590, 1537, 1132.
(300 MHz, CDCl3)
d
0.88 (t, J¼6.4 Hz, 9H), 1.20e1.40 (m, 36H),
1.46e1.52 (m, 6H), 1.62e1.84 (m, 6H), 3.88 (s, 3H), 4.01 (t, J¼6.1 Hz,
4.2.16. Compound Ta-1. A mixture of compounds 3 and 20 in
methanol (10 mL) and dichloromethane (8 mL) was stirred at room
temperature for 3 days. After removal of the solvent, the resulting
residue was purified by column chromatography (dichloro-
methane/methanol 200:1 to 100:1) to give compound Ta-1 as
a pale yellow solid (201 mg, 85%). Mp 165e167 ꢂC. 1H NMR
6H), 7.25 (s, 2H). MS (ESI): 605.4 [MþH]þ.
4.2.11. Compound 18. Compound 18 was prepared in 99% yield as
a pale yellow oil from the reaction of compound 16 and [2-[2-(2-
methoxyethoxy)ethoxy]ethoxy]p-toluenesulfonate according to
a procedure similar to that described for compound 17. 1H NMR
(300 MHz, CDCl3):
d 0.82e0.90 (m, 18H), 1.15e1.80 (m, 96H),
(300 MHz, CDCl3):
d
3.36 (s, 9H), 3.53 (s, 8H), 3.63 (m, 12H), 3.70 (t,
3.55e4.14 (m, 12H), 6.61e7.09 (m, 6H), 7.18e9.40 (m, 8H),
12.92e13.20 (m, 2H). MS (MALDI-TOF): m/z 1430.1 [MþNa]þ. HRMS
(MALDI-TOF): calcd for C90H143N4O8 [MþH]þ: 1408.0893, found
1408.0900. Anal. Calcd for C90H142N4O8: C, 76.77; H, 10.16; N, 3.98.
Found: C, 76.68; H, 10.18; N, 3.88. IR (KBr/cmꢀ1): 3212, 3067, 2925,
2854, 2207, 1644, 1580, 1499, 1332.
J¼5.2 Hz, 6H), 3.78 (t, J¼4.9 Hz, 2H), 3.85 (m, 6H), 4.19 (t, J¼9.0 Hz,
6H), 7.27 (s, 2H). MS (ESI): m/z 645.3 [MþNa]þ.
4.2.12. Compound 19. Compound 19 was prepared in 90% yield as
a pale brown oil from the reaction of compound 16 and 2-(2-
(dioctylamino)-2-oxoethyl-amino)-2-oxoethylchloride9a according
to a procedure similar to that described for compound 17. 1H NMR
4.2.17. Compound Tb-1. Compound Tb-1 was prepared in 82% yield
as a pale yellow oil from the reaction of compounds 3 and 21
according to a procedure similar to that described for compound
(300 MHz, CDCl3):
d
0.87 (t, J¼4.0 Hz, 18H), 1.25 (s, 60H), 1.51 (s,
12H), 3.12e3.17 (m, 6H), 3.26e3.30 (m, 6H), 3.87 (s, 3H), 4.09 (d,
J¼3.9 Hz, 4H), 4.18 (d, J¼3.9 Hz, 2H), 4.68 (s, 4H), 4.81 (s, 2H), 7.33
Ta-1. 1H NMR (300 MHz, CD3OD):
d 3.20e3.28 (m, 18H), 3.35e3.78
(s, 2H), 7.69 (s, 2H), 8.42 (s, 1H). 13C NMR (100 MHz, CDCl3):
d
13.7,
(m, 60H), 4.03e4.19 (m, 12H), 7.17e7.24 (m, 4H), 7.29e7.41 (m, 4H),
7.46e7.55 (m, 2H), 8.04 (d, J¼6.9 Hz, 1H), 8.22 (1H), 8.37 (s, 1H),
22.2, 22.3 (d), 26.5, 26.6, 26.7, 27.3, 28.4, 28.5, 28.8, 28.9 (d), 29.0
(d), 31.4 (d), 31.5 (d), 40.5, 40.7, 45.8, 46.6, 46.7, 52.0, 68.3, 72.4,
109.0, 125.7, 141.2, 150.2, 165.4, 166.3, 166.9, 167.2, 168.6. MS (ESI):
m/z 1200.2 [MþH]þ, 1222.2 [MþNa]þ. HRMS (ESI): calcd for
C68H122N6NaO11 [MþH]þ: 1221.9064, found 1221.9054.
9.29 (1H). 13C NMR (100 MHz, CD3OD):
d 59.1, 70.0, 70.2, 70.6, 70.7,
71.3, 71.4, 71.4, 71.5 (d), 71.6, 71.7 (d), 72.9 (q), 73.6, 73.8, 87.8, 95.2,
108.2, 108.4, 124.5, 124.6, 126.5, 128.4, 128.9, 130.1, 130.4, 131.3,
134.3, 134.9, 135.6, 136.4, 142.8, 143.1, 148.8, 150.4, 153.8, 153.9,
166.7(d). MS (MALDI): m/z 1465.7 [MþNa]þ. HRMS (MALDI-TOF):
calcd for C72H107N4O26 [MþH]þ: 1443.7166, found 1443. 7168. IR
(KBr/cmꢀ1): 3210, 2926, 2876, 1645, 1581, 1499, 1311, 1120.
4.2.13. Compound 20. A mixture of compound 17 (5.3 g, 8.8 mmol)
and hydrazine monohydrate (20 mL) in methanol (20 mL) and THF
(35 mL) was heated under reflux for 6 h and then cooled to room
temperature. The organic solvent was removed with a rotavapor. To
the resulting mixture, water (20 mL) was added and the aqueous
phase was extracted with dichloromethane (4ꢁ40 mL). The com-
bined organic phase was washed with brine (4ꢁ50 mL), and dried
over magnesium sulfate. After removal of the solvent, the resulting
residue was purified by column chromatography (dichloro-
methane/methanol 50:1 to 30:1) to give compound 20 as a pale
4.2.18. Compound Tc-1. A mixture of compound
3 (20 mg,
0.08 mmol) and 22 (215 mg, 0.18 mmol) in methanol (5 mL) and
chloroform (20 mL) was heated under reflux for 3 days and then
cooled to room temperature. After removal of the solvent, the
resulting residue was purified by column chromatography
(dichloromethane/methanol 35:1) to give compound Ta-1 as a pale
yellow solid (211 mg, 95%). Mp 64e66 ꢂC. 1H NMR (400 MHz,
yellow oil (4.2 g, 79%). 1H NMR (300 MHz, CDCl3)
d
0.88 (t, J¼6.6 Hz,
CDCl3): d 0.80e0.88 (m, 36H), 1.05e1.61 (m, 144H), 2.96e3.34 (m,
9H), 1.26 (s, 34H), 1.46 (s, 6H), 1.60e1.76 (m, 6H), 3.98 (t, J¼6.4 Hz,
6H), 4.09 (s, 2H), 6.92 (s, 2H), 7.35 (s, 1H). MS (ESI): m/z 605.6
[MþH]þ. IR (KBr/cmꢀ1): 3306, 2924, 2854, 1634, 1581, 1495, 1470,
1344, 1237, 1116.
24H), 4.00e4.20 (m, 12H),4.65e4.85 (m, 12H), 7.31e8.07 (m, 9H),
8.28e8.61 (m, 4H), 9.22 (s, 1H), 11.34e11.65 (2H). MS (MALDI-TOF):
2618.9 [MþNa]þ. HRMS (MALDI-TOF): calcd for C150H250N16O20Na
[MþNa]þ: 2618.8958, found 2618.8970. IR (KBr/cmꢀ1): 3352, 2926,
2855, 1651, 1589, 1376, 1333, 1132, 758.
4.2.14. Compound 21. Compound 21 was prepared in 88% yield as
a pale yellow oil from the reaction of compound 18 and hydrazine
according to a procedure similar to that described for compound
4.2.19. Compound Ta-2. Compound Ta-2 was prepared in 96% yield
as a pale yellow solid from the reaction of compounds 5 and 20
according to a procedure similar to that described for compound
20. 1H NMR (300 MHz, CDCl3):
d
3.33 (s, 6H), 3.34 (s, 3H), 3.51e3.53
(m, 6H), 3.64 (m, 18H), 3.78 (m, 6H), 4.09 (s, 2H), 4.15e4.18 (m, 6H),
7.07 (s, 2H), 8.09 (s, 1H). 13C NMR (100 MHz, CDCl3):
59.1, 70.0,
Ta-1. Mp 241e245 ꢂC. 1H NMR (400 MHz, CDCl3):
d
0.80e0.92 (m,
d
27H), 1.03e1.82 (m, 144H), 3.52e4.16 (m, 18H), 6.56e7.06 (m, 5H),

L.-G. Wang et al. / Tetrahedron 68 (2012) 5303e5310
5309
7.08e7.61 (m, 9H), 7.72e8.58 (m, 4H), 9.38e9.60 (m, 2H),
12.99e13.51 (m, 3H). MS (MALDI-TOF): m/z 2122.3 [MþH]þ. HRMS
(MALDI-TOF): calcd for C136H212N6O12Na [MþNa]þ: 2144.6056,
found 2144.6146. Anal. Calcd for C136H212N6O12: C, 76.93; H, 10.06;
N, 3.96. Found: C, 76.80; H, 10.18; N, 3.90. IR (KBr/cmꢀ1): 3184,
2924, 2853, 1645, 1580, 1499, 1333, 1229, 1115.
21 according to a procedure similar to that described for compound
Tc-1. 1H NMR (300 MHz, CDCl3):
3.17e4.47 (m, 225H), 6.74e9.66
(m, 32H), 12.51e13.83 (m, 5H). MS (MALDI-TOF): m/z 3664.8
[MþNa]þ. HRMS (MALDI-TOF): calcd for C183H262N10O65Na
[MþNa]þ: 3662.7396, found 3662.7398. IR (KBr/cmꢀ1): 3181, 2919,
2875, 2200, 1645, 1580, 1497, 1331, 1118.
d
4.2.20. Compound Tb-2. Compound Tb-2 was prepared in 91%
yield as a pale yellow oil from the reaction of compounds 5 and 21
according to a procedure similar to that described for compound
4.2.27. Compound Tc-4. Compound Tc-4 was prepared in 98% yield
as a pale yellow solid from the reaction of compounds 15 and 22
according to a procedure similar to that described for compound
Ta-1. 1H NMR (300 MHz, CD3OD):
d
3.24e4.36 (m, 135H),
Tc-1. Mp 114e118 ꢂC. 1H NMR (400 MHz, CDCl3)
d 0.83e0.86 (m,
6.77e8.94 (m, 18H), 9.16e9.57 (m, 2H), 12.55e13.38 (m, 3H). MS
(MALDI-TOF): m/z 2198.0 [MþNa]þ. HRMS (MALDI-TOF): calcd for
C109H158N6O39Na [MþNa]þ: 2198.0457, found 2198.0495. IR (KBr/
cmꢀ1): 3185, 2926, 2876, 2207, 1645, 1581, 1498, 1331, 1122.
90H), 1.10e1.55 (m, 360H), 3.00e3.27 (m, 60H), 4.02e4.16 (m,
30H), 4.76e4.85 (m, 30H), 7.36e7.40 (m, 12H), 7.52e7.76 (m, 20H),
8.14 (s, 1H), 8.39e8.56 (m, 9H), 9.25e9.30 (m, 3H), 11.36e11.90 (m,
5H). IR (KBr/cmꢀ1): 3351, 2926, 2855, 2200, 1648, 1588, 1527, 1429,
1335, 1134.
4.2.21. Compound Tc-2. Compound Tc-2 was prepared in 90% yield
as a pale yellow sticky solid from the reaction of compounds 5 and
22 according to a procedure similar to that described for compound
Acknowledgements
Tc-1. Mp 74e76 ꢂC. 1H NMR (300 MHz, CDCl3):
d 0.78e0.87 (m,
We thank MOST (2007CB808001), NSFC (20732007, 20921091,
20872167, 20974118, 20972180), and STCSM (09XD1405300,
10PJ1412200) for financial support.
54H), 0.98e1.61 (m, 216H), 2.94e3.34 (m, 36H), 3.98e4.22 (m,
18H), 4.62e4.94 (m, 18H), 7.30e8.12 (m, 21H), 8.32e8.65 (m, 6H),
9.25 (s, 2H), 11.28e11.90 (m, 3H). MS (MALDI-TOF): m/z 3927.9
[MþNa]þ. HRMS (MALDI-TOF): calcd for C226H374N24O30Na
[MþNa]þ: 3927.8370, found 3927.8430. IR (KBr/cmꢀ1): 3351, 2956,
2855, 2207, 1679, 1651, 1589, 1428, 1336, 1134.
Supplementary data
Supplementary data related to this article can be found in the
online version, at doi:10.1016/j.tet.2012.01.082 .
4.2.22. Compound Ta-3. Compound Ta-3 was prepared quantita-
tively as a pale yellow solid from the reaction of compounds 10 and
20 according to a procedure similar to that described for compound
References and notes
Tc-1. Mp 252e256 ꢂC. 1H NMR (300 MHz, CDCl3):
d 0.79e0.96 (m,
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36H), 1.01e1.91 (m, 192H), 3.47e4.27 (m, 24H), 6.43e9.95 (m, 26H),
12.81e13.79 (m, 4H). MS (MALDI-TOF): m/z 2859.2 [MþNa]þ. HRMS
(MALDI-TOF): calcd for C182H282N8O16Na [MþNa]þ: 2859.1391,
found 2859.1317. IR (KBr/cmꢀ1): 3178, 2924, 2854, 1647, 1578, 1498,
1332, 1229, 1116.
4.2.23. Compound Tb-3. Compound Tb-3 was prepared in 90%
yield as a pale yellow oil from the reaction of compounds 10 and
21 according to a procedure similar to that described for com-
pound Tc-1. 1H NMR (300 MHz, CDCl3):
d 3.18e4.41 (m, 180H),
6.78e9.66 (m, 26H), 12.54e13.66 (m, 4H). MS (MALDI-TOF): m/z
2930.4 [MþNa]þ. HRMS (MALDI-TOF): calcd for C146H210N8O62Na
[MþNa]þ: 2930.3926, found 2930.3964. IR (KBr/cmꢀ1): 3521, 3183,
2874, 2207, 1645, 1581, 1331, 1120, 949.
5. (a) Stoenescu, R.; Meier, W. Chem. Commun. 2002, 3016e3017; (b) Graff, A.;
Sauer, M.; Gelder, P. V.; Meier, W. Proc. Natl. Acad. Sci. U.S.A. 2002, 99,
5064e5068.
4.2.24. Compound Tc-3. Compound Tc-3 was prepared quantita-
tively as a pale yellow solid from the reaction of compounds 10 and
22 according to a procedure similar to that described for compound
6. (a) Menger, F. M.; Gabrielson, K. D. Angew. Chem., Int. Ed. Engl. 1995, 34,
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Saily, V. M. J.; Parry, M. J.; Luciani, P.; Mancini, G.; Alakoskela, J.-M. I.; Kinnunen,
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Thomas, G. B.; Danoff, E. J.; English, D. S.; DeShong, P. Soft Matter 2008, 4,
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Tc-1. Mp 97e101 ꢂC. 1H NMR (300 MHz, CDCl3):
d 0.77e0.92 (m,
72H), 0.96e1.63 (m, 288H), 2.91e3.35 (m, 48H), 3.93e4.23 (m, 24H),
4.63e4.94 (m, 24H), 7.31e9.35 (m, 34H), 11.22e11.94 (m, 4H). MS
(MALDI-TOF): m/z 5236.1 [MþNa]þ. Anal. Calcd for C302H498N32O40
:
C, 69.52; H, 9.62; N, 8.59. Found: C, 69.04; H, 9.85; N, 8.35. IR (KBr/
cmꢀ1): 3347, 2954, 2926, 2855, 1655, 1429, 1375, 1335, 1133.
4.2.25. Compound Ta-4. Compound Ta-4 was prepared quantita-
tively as a pale yellow solid from the reaction of compounds 15 and
20 according to a procedure similar to that described for compound
Tc-1. Mp 255e259 ꢂC. MS (MALDI): m/z 3551.1 [MþH]þ. Anal. Calcd
for C288H352N10O20: C, 77.07; H, 9.98; N, 3.94. Found: C, 77.08; H,
9.99; N, 3.85. IR (KBr/cmꢀ1): 3179, 2924, 2854, 2200, 1647, 1578,
1333, 1116.
9. (a) Cai, W.; Wang, G.-T.; Xu, Y.-X.; Jiang, X.-K.; Li, Z.-T. J. Am. Chem. Soc. 2008,
130, 6936e6937; (b) You, L.-Y.; Jiang, X.-K.; Li, Z.-T. Tetrahedron 2009, 65,
9494e9504; (c) Xu, Y.-X.; Wang, G.-T.; Zhao, X.; Jiang, X.-K.; Li, Z.-T. Langmuir
2009, 25, 2684e2688; (d) Xu, Y.-X.; Wang, G.-T.; Zhao, X.; Jiang, X.-K.; Li, Z.-T.
Soft Matter 2010, 6, 1246e1252.
4.2.26. Compound Tb-4. Compound Tb-4 was prepared in 89%
yield as a yellow-green oil from the reaction of compounds 15 and

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