Highly selective recognition of monosaccharide based on two-component system in aqueous solution

Article abstract of DOI:10.1016/j.tet.2011.03.025

A highly selective switch for d-fructose was formed by water-soluble conjugated polymer PP-S-BINOL and tetraboronic acid functionalized benzyl viologen ToBV. The two-component system showed a high selectivity and sensitivity only for d-fructose in familiar d-monosaccharides. The high selectivity of the sensing system for d-fructose may be depended on stable pyranose ester form of d-fructose with ToBV. A desirable linear response of the sensing system to low concentrations of d-fructose (<10.0 mM) was observed with 0.9936 linear dependent coefficient at pH 7.4.

Full text of DOI:10.1016/j.tet.2011.03.025

Tetrahedron 67 (2011) 3175e3180
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Highly selective recognition of monosaccharide based on two-component system
in aqueous solution
,
a
a
a
b,
Liheng Feng a , Yue Wang , Fei Liang , Ming Xu , Xiaoju Wang
*
*
a School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
b Institute of Molecular Science, Chemical Biology and Molecular Engineering, Laboratory of Education Ministry, Shanxi University, Taiyuan 030006, China
a r t i c l e i n f o
a b s t r a c t
Article history:
A highly selective switch for D-fructose was formed by water-soluble conjugated polymer PP-S-BINOL
Received 12 January 2011
Received in revised form 27 February 2011
Accepted 10 March 2011
and tetraboronic acid functionalized benzyl viologen ToBV. The two-component system showed a high
selectivity and sensitivity only for -fructose in familiar -monosaccharides. The high selectivity of the
sensing system for -fructose may be depended on stable pyranose ester form of -fructose with ToBV. A
-fructose (<10.0 mM) was
D
D
D
D
Available online 16 March 2011
desirable linear response of the sensing system to low concentrations of
D
observed with 0.9936 linear dependent coefficient at pH 7.4.
Keywords:
Ó 2011 Elsevier Ltd. All rights reserved.
D
-Monosaccharides
Selectivity
Viologen
Boronic acid
1. Introduction
co-workers.8 However, it is a pity that there are high sensitivities
and not obvious selectivity for
portance of fructose to the food and beverage industry, developing
a promising detection system for
-fructose is urgent.6b,7a,b Herein,
we now introduce a new strategy for highly selective recognition of
-fructose in aqueous solution. The sensing system is comprised of
water-soluble anionic polymer (PP-S-BINOL) and tetraboronic acid
functionalized benzyl viologen (ToBV). (Scheme 1 and Scheme 2)
Anionic conjugated polymer PP-S-BINOL is optic signal report
section and its fluorescence is modulated by electron transfer from
PP-S-BINOL to ToBV. Cationic viologen ToBV acts as both quencher
and receptor in the system. The electrostatic interaction between
PP-S-BINOL and ToBV through forming ground-state complex will
lead to a decrease in the fluorescence intensities of PP-S-BINOL. The
D-monosaccharides. Given the im-
D
-Monosaccharides are the most widespread nature saccharides
and play important roles in life processes.1 Owing to their wide
usages and special bioactivities, it is indispensable to develop ef-
D
ficient method for detection of
D-monosaccharides in aqueous so-
D
lution.2 Among various analytical methods, the detection based on
fluorescence is the most promising because it can offer the ad-
vantages of high sensitivity, real-time analysis, remote detection
capabilities, and multiple sensing modes.3 Regrettably, despite the
progress achieved in fluorescence-based recognition systems for
monosaccharides, no methods for D-monosaccharides with obvi-
ously high selectivity in aqueous solution have been reported.4
Although a few monosaccharide sensing systems based on fluo-
rescence with passable selectivity have been developed, the sig-
nificant drawbacks of the systems are lower sensitivity and
restricted detection media (only in organic or organic/water mixed
different binding capabilities between
D-monosaccharides and
ToBV by forming reversible boronates can weaken the interaction of
ToBV with PP-S-BINOL, which will result in the fluorescence re-
covery of PP-S-BINOL at different degree. Due to stronger binding
solvents).5 Due to most
D
-monosaccharides with only one kind of
functional group (hydroxyl), the highly selective recognition of
-monosaccharide is rather difficult for the method based on
fluorescence.6 Therefore, how to design and obtain highly selective
action of ToBV with
D-fructose and architectural space position of
D
boronic acid on ToBV, the recognition system is worth to expect
with high selectivity and sensitivity for D-fructose.
and water-soluble sensing system of D-monosaccharide is a chal-
lenge for chemists, biologists, and medical scientists.6b,7
Fortunately, boronic acid functionalized benzyl viologens for
sensing D-monosaccharides have been reported by Singaram and
2. Results and discussion
2.1. Synthesis
Polymer PP-S-BINOL was synthesized by six steps from the
commercially available p-hydroquinone and (S)-2,20-dimethoxy-
* Corresponding authors. Tel.: þ86 351 7011600; fax: þ86 351 7011688; e-mail
address: lhfeng@sxu.edu.cn (L. Feng).
0040-4020/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2011.03.025

3176
L. Feng et al. / Tetrahedron 67 (2011) 3175e3180
Br
OH
OH
OH
OH
+Na-O3S
O
Br
a
b
-
O
SO3 Na+
Br
Br
Monomer 1
O
B
O
O
Br
Br
OCH3
OCH3
c
e
OCH3
OCH3
OH
OH
OCH3
OCH3
d
B
O
Monomer 2
SO3 Na+
-
SO3 Na+
-
O
B
O
O
O
OCH3
OCH3
f
O
+
Br
Br
OCH3
OCH3
O
O
+Na-O3S
B
O
n
+Na-O3S
Polymer PP-S-BINOL
Monomer 2
Monomer 1
Scheme 1. (a) CH3COOH, Br2, room temperature 24 h, 45.8%; (b) 1,3-propanesultone, NaOH, dioxane/H2O, N2, room temperature 12 h, then 80e100 ꢀC 3 h, 68.4%; (c) CH3I, K2CO3,
acetone, reflux 36 h, N2, 89.2%; (d) Br2, CH2Cl2, 0 ꢀC, 5 h, 92.3%; (e) bis(pinacolato)diboron, Pd(dppf)Cl2, KOAc, DMSO, 80 ꢀC 6 h, N2, 51.4%; (f) Pd(PPh3)4, 1,4-dibromo-2,5-bis
(3-sulfonatopropoxy)benzene, Na2CO3, DMF/H2O, 80 ꢀC 48 h, N2, 51.6%.
Br
g
h
O
O
B
B
O
O
B
O
B
O
Br
Br
O
O
HO
B OH
Br
HO
j
i
B
HO
HO
OH
B
B
N
N
OH
OH
HO
OH
Br
Br
B
HO B
OH
Quencher/receptor ToBV
HO
B OH
Br
k
HO
B
N
N
HO
OH
OH
Br
Br
B
Quencher/receptor m-BBV
Scheme 2. (g) Bis(pinacolato)diboron, Pd(dppf)Cl2, KOAc, DMSO, 80 ꢀC 6 h, N2, 82.3%; (h) NBS, benzoyl peroxide, CCl4, reflux 7 h, N2, 74.5%; (i) sodium periodate, hydrochloric acid,
THF/H2O, 48 h, room temperature, 38.6%; (j) 4,40-bipyridine, DMF, 80 ꢀC 48 h, 47.8%; (k) 4,40-bipyridine, DMF, 70 ꢀC 48 h, 76.4%.

L. Feng et al. / Tetrahedron 67 (2011) 3175e3180
3177
l,l0-dinaphthyl (S-BINOL).9 Water-soluble monomer 1, 1,4-dibromo-
2,5-bis(3-sulfonatopropoxy)benzene, was obtained by bromination
of p-hydroquinone and then reaction with 1,3-propanesultone in
strong alkali solution. Monomer 2, (S)-2,20-dimethoxy-6,60-bis
monosaccharides to the sensing system, no obvious fluorescence
changes of ToBV/PP-S-BINOL system were observed. To the best of
our knowledge, the selectivity of the sensing system for
was the highest ever recorded and the response ratio for
-glucose was about 85-fold increase in the present of 10 mM
monosaccharides. The high selectivity of the sensing system for
D
-fructose
D-fructose/
(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)1,10-naphthalene,
was
D
D
D
-
-
prepared through etherification, bromination, and then boronic
acid esterification under Pd(dppf)Cl2 catalysis. Lastly, the in-
teraction of the monomer 1 and monomer 2 gave polymer PP-S-
BINOL through Suzuki coupling reaction in 51.6%.
fructose may result from the meta-position of boronic acid groups in
the same benzyl ring of ToBV, which can provide suited binding
space for the pyranose form of fructose. This supposed binding way
was imitated by Chem3D (see Fig. S1). To confirm our guess, another
sensing system of N,N0-4,40-bis(benzyl-2-boronic acid)bipyridinium
dibromide (m-BBV, Scheme 2) with PP-S-BINOL was composed to
Quencher/receptor ToBV was synthesized by four steps from the
commercially available 1,3-dibromo-5-methylbenzene.10 Firstly,
the CeB coupling reaction between 1,3-dibromo-5-methylbenzene
and bis(pinacolato)diboron gave 3,5-bis-(4,4,5,5-tetramethyl-1,3,2-
dioxaboro-lane)toluene. Then 5-(bromomethyl)phenyl-1,3-dibor-
onic acid was obtained by bromination of NBS and deesterification
of sodium periodate. Lastly, N,N0-4,40-bis(benzyl-3,5-diboronic
acid)-bipyridinium dibromide (ToBV) was synthesized by quater-
nization of commercially available 4,40-dipyridyl and 5-(bromo-
methyl)phenyl-1,3-diboronic acid in 47.8%. (Scheme 2).
determine D-monosaccharides in pH 7.4 buffer solution (see Figs. S2
and S3). We found the fluorescence of PP-S-BINOL can be quenched
by m-BBV in pH 7.4 buffer solution. However, though the fluorescent
recoveries of PP-S-BINOL were all observed with the addition of any
D
-monosaccharides, no obvious differences of fluorescent changes
were observed, which indicated the m-BBV/PP-S-BINOL two-com-
ponent system did not have obvious selectivity for -mono-
saccharides. From the titration curves, it is believed that 1:2
boronate complex between ToBV and
-fructose was formed.8d Due
D
D
2.2. Fluorescence studies
to no considering the interaction of PP-S-BINOL and ToBV, the
binding constants of the system to monosaccharides were roughly
calculated. The results showed that the binding order of the sensing
Firstly, the quenching interaction of PP-S-BINOL and ToBV was
investigated by fluorescence spectra in detail. The fluorescent ti-
tration experiments showed that the fluorescence of PP-S-BINOL
can be effectively quenched by ToBV in pH 7.4 buffer solution
(Fig. 1). Obviously, ground-state complex between PP-S-BINOL and
ToBV was formed by electron transfer from PP-S-BINOL to ToBV,
resulting in a great reduction of PP-S-BINOL fluorescence in-
tensities. At lower concentrations of ToBV, the SterneVolmer plot
system to monosaccharides was
D
-fructose>
D-galactose>D-
ribosez
D
-xylosezD-arabinose>
D-mannitosez
D
-glucose.8
10
8
was linear and the static quenching constant (KSV
) was
2.37ꢁ104 Mꢂ1. At higher concentrations of ToBV, the SterneVolmer
plot was curved upward, which indicated a large sphere static
quenching had been produced by the electrostatic interaction be-
tween PP-S-BINOL and ToBV. The effectively quenching action be-
tween fluorescence dye and quencher through forming a complex
was very helpful for developing highly sensitive sensing systems of
saccharides.
D-glucose
D-fructose
D-mannitose
D-arabinose
D-galactose
D-ribose
6
4
D-xylose
2
1.7
0
0
20
40
60
80
100
1.6
R2=0.9925
[Monosaccharides] mM
Fig. 2. The binding characteristics of PP-S-BINOL (2.84ꢁ10ꢂ3 g/L) and ToBV (0.674 g/L,
1.5
1.4
1.3
1.2
1.0ꢁ10ꢂ3 M) with different D-monosaccharides in pH 7.4 phosphate buffer solutions
(
lex¼320 nm; lem¼425 nm). The concentrations of monosaccharides were 10.0 mM,
40.0 mM, and 100.0 mM, respectively.
The sensitivity of the sensing system to
D-fructose was in-
vestigated by fluorescence spectra in pH 7.4 buffer solution (Fig. 3).
Upon introducing -fructose to the sensing system, an apparent
recovery of the fluorescence was observed by forming negatively
charged borate ester between ToBV and -fructose. The fluores-
cence recovery of PP-S-BINOL was dependent on the -fructose
concentration. The 11-fold increase of fluorescence intensity was
observed by adding 100 mM -fructose to PP-S-BINOL/ToBV sensing
system. Remarkably, we investigated a desirable linear response to
low concentrations of -fructose (<10.0 mM) at pH 7.4 (see Fig. S4).
Additionally, the desirable linear response of the sensing system to
-fructose was no obvious influence in the present of other
monosaccharides (see Figs. S5 and S6). It is well known that the
linear response of sensing system to -fructose was important for
practical detection in food safety field.
D
D
0
4
8
12
16
20
D
[ToBV] *10-6 M
Fig. 1. SterneVolmer plot of PP-S-BINOL (2.84ꢁ10ꢂ3 g/L) quenched by low concen-
D
tration of ToBV, measured in phosphate buffer solution pH 7.4
lem¼425 nm).
(lex¼320 nm;
D
Next, the selectivity of the two-component sensing system for
monosaccharides was determined in an aqueous solution at pH 7.4
(Fig. 2). As expected, we found the ToBV/PP-S-BINOL sensing system
D
-
D
D-
D
embodied dramatically high selectivity only for
common -monosaccharides. The rather large fluorescence re-
covery of PP-S-BINOL was observed by adding -fructose to the
sensing system. However, respectively introducing other
D-fructose in seven
D
Lastly, the ground-state complex (PP-S-BINOL/ToBV) formation
and the return to the uncomplex (PP-S-BINOL) led to the color
changes of solutions under 365 nm UVevis light (see Fig. S7). The
D
D-

3178
L. Feng et al. / Tetrahedron 67 (2011) 3175e3180
acquired on an Agilent 6510 Q-TOF LC/MS instrument (Agilent
Technologies, Palo Alto, CA) equipped with an electrospray ioni-
zation (ESI) source.
4000
3200
2400
1600
800
fluorescence
quenching
4.2. Fluorescent measurements for quenching and sensing
studies of D-monosaccharides
fluorescence recovery
upon introduction of
100 mM
fructose
All experiments of water were pure water. All of the working
solutions were buffered at pH 7.4ꢃ0.1 using a phosphate (the
mixture system of Na2HPO4 (0.2 M, 61.0 mL) and NaH2PO4 (0.2 M,
39.0 mL)) buffer solution. The stock solution (2.84 g/L, 1.0 mL) of PP-
S-BINOL was diluted in 1.0 L measuring flask with pH 7.4 buffer
solution to afford the working solution (2.84ꢁ10ꢂ3 g/L). The stock
solution (0.04 M) of ToBV was prepared by 0.2694 g ToBV in 10 mL
measuring flask. The stock solutions of monosaccharides were
1.0 M in 10 mL measuring flask. The standard stock solutions of
lower concentration were prepared by suitable dilution of the stock
solutions with pH 7.4 buffer solution.
0
350
400
450
500
550
Wavelength / nm
Fig. 3. Characteristic fluorescence response by introduction of quencher followed by
fructose to PP-S-BINOL solution (2.84ꢁ10ꢂ3 g/L) at pH 7.4. The concentration of ToBV
was 0.674 g/L (1.0ꢁ10ꢂ3 M) and final fructose concentration was 100 mM
(
lex¼320 nm; lem¼425 nm). The dashed line indicates unquenched fluorescence, the
bold line indicates fluorescence after introduction of quencher ToBV.
All spectra analysis studies were carried out at pH¼7.4 buffer
solution and the working solutions were placed in a quartz cuvette
with 1 cm path. The total volume of working solution was 2 mL. The
studies of fluorescence quenching and sensing monosaccharides
used titration experiments and the volume added did not exceed
3% of the total. After the mixture solution was shaken for 30 s, the
new spectra were measured. Fluorescence spectra were acquired
with a Hitachi F-4500 fluorescence spectrophotometer, the exci-
tation and emission slit widths were 5 nm and 10 nm, respectively.
The excitation wavelength was set in 320 nm according to experi-
mental requirements. All of the experiments were performed at
barometric pressure and room temperature. SterneVolmer static
quenching constants were calculated by fitting the data to F0/
F¼1þKsv[Q], where F0 was the initial unquenched fluorescence
intensity, F was the fluorescence intensity in the presence of
quencher, KSV was the static quenching constant, [Q] is the
quencher concentration.
blue solution of PP-S-BINOL turned into black solution with the
addition of ToBV, revealing the ground-state complex formation
(low-fluorescence). With the increase of D-fructose in the sensing
system, the quenched black solution gradually changed to darkblue
solution, which demonstrated the complex was less stable and had
been largely dissociated with a considerable recovery of the origi-
nal PP-S-BINOL.
3. Conclusions
We developed a highly selective and sensitive D-fructose sensing
system based on water-soluble PP-S-BINOL and tetraboronic acid
functionalized benzyl viologen ToBV. The high selectivity of the
sensing system for
form of -fructose and suitable boronic acid position of ToBV. The
response ratio for -fructose/ -glucose was about 85-fold increase
in the present of 10 mM -monosaccharides, respectively. Re-
markably, a desirable linear response of the sensing system to low
concentration of -fructose (<10.0 mM) was observed at pH 7.4. We
D-fructose may depend on stable pyranose ester
D
D
D
D
4.3. Synthesis
D
4.3.1. 2,5-Dibromobenzene-1,4-diol. A solution of 32.0 g (0.2 mol)
Br2 in 30 mL glacial acetic acid was generally added by dropping
funnel to a solution of 11.0 g (0.1 mol) p-hydroquinone in 60 mL
glacial acetic acid. The mixture was stirred for 24 h at room tem-
perature. The mixture solution was added 1 L water and the
resulting brown solid was filtered. The crude products were puri-
fied by recrystallization twice from water to yield product as white
needles (12.27 g, yield 45.8%), mp 177e178 ꢀC (lit. 177 ꢀC).
believe that these results can offer a new strategy for developing
highly selective monosaccharides sensors. Further studies of PP-S-
BINOL/ToBV sensing system for D-monosaccharides are currently
underway.
4. Experimental
4.1. General procedures
4.3.2. 1,4-Dibromo-2,5-bis(3-sulfonatopropoxy)benzene. A solution
Unless otherwise stated, all chemical reagents were obtained
from commercial suppliers and used without further purification.
Solvents used were purified and dried by standard methods prior to
use. p-Hydroquinone, 1,3-propanesultone, 1,3-dibromo-5-methyl-
benzene, Pd(PPh3)4, Pd(dppf)Cl2, bis-(pinacolato)diboron, and (S)-
2,20-dihydroxy-l,l0-di-naphthyl were purchased from Aldrich
(Steinheim, Germany). N,N0-4,40-Bis(benzyl-2-boronic acid)bipyr-
idinium dibromide (m-BBV) was synthesized according to pre-
viously reported literature.10d pH measurements were carried out
on a Mettler Toledo MP 220 pH meter, 1H NMR and 13C NMR were
measured on a Bruker ARX400 spectrometer with chemical shifts
reported as parts per million (TMS as an internal standard). 11B
NMR spectra were recorded on a Bruker at 80 MHz and were
of 6.35 g (20.0 mmol) 2,5-dibromobenzene-1,4-diol, 2.0 g
(50.0 mmol) sodium hydroxide, and 200 mL water in a Erlenmeyer
flask was stirred under nitrogen. Then, a solution of 6.1 g
(50.0 mmol) 1,3-propanesultone in 40 mL dioxane was added to the
former solution at once. The resulting mixture was then stirred at
room temperature overnight, during which time a thick pink slurry
formed. The reaction mixture was then stirred at 80e100 ꢀC for
another 30 min and then cooled in a water/ice bath. The suspension
obtained was vacuum filtered, and the retained solid was washed
with cold water followed by acetone. The crude products were
purified by recrystallization twice from water to yield product as
white powder (7.61 g, yield 68.4%). 1H NMR (D2O, 400 MHz)
(s, 1H), 4.03 (dd, J¼6.0, 6.0 Hz, 4H), 3.05 (dd, J¼4.4, 5.6 Hz, 4H), 2.21
(m, 4H); 13C NMR (D2O, 100 MHz)
24.24, 47.91, 68.97, 111.03,
d 7.16
reported in ppm with respect to BF3$OEt2 (
d
¼0). Elemental analyses
d
were performed on a Vario EL elemental analysis instrument
(Elementar Co.). High-resolution mass spectra (HRMS) were
119.19, 149.42. Element Analysis for C12H14Br2Na2O8S2 (Mol. wt:
556.15) calcd: C 25.92; H 2.54; Br 28.73; S 11.53, found: C 25.89; H

L. Feng et al. / Tetrahedron 67 (2011) 3175e3180
3179
2.57; Br 28.69; S 11.58; HRMS-ESI for C12H14Br2Na2O8S2 (m/z)
533.51 [M-23].
Element Analysis for C34H30Na2O10S2 (Mol. wt monomeric unit:
708.72) calcd: C 57.62; H 4.27; S 9.04; Na 6.49, found: C 57.58; H
4.31; S 9.09; Na 6.55.
4.3.3. (S)-2,20-Dimethoxy-l,l0-dinaphthyl. A suspension of 25.0 g
(8.7 mmol) (S)-2,20-di-hydroxy-l,l0-dinaphthyl in 800 mL of ace-
tone was heated and stirred with maximum rotation to give
a homogeneous solution. To this solution stirred under N2 was
added 40.0 g (29.0 mmol) K2CO3 and 60.0 g (0.42 mol) CH3I, and
the mixture was refluxed for 24 h. An additional 20.0 g (0.14 mol)
portion of CH3I was added, and the mixture was refluxed for an
additional 12 h. The solvent was evaporated to leave a volume of
150 mL, which was cooled to 25 ꢀC, and 900 mL water was added
to the stirred suspension. The solid was collected, washed with
water, and dried under vacuum to give crude product. The crude
product was dissolved in 100 mL CH2Cl2 and heated. The solution
was poured into 500 mL petroleum ether and appeared as a pre-
cipitate. The precipitate was filtered off and dried in vacuo to give
desired product as a white powder that was used without further
purification in the next reaction. Mp 224e225 ꢀC (24.48 g, yield
89.2%).
4.3.7. 3,5-Bis-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)toluene. A mix
ture of 10.0 g (0.04 mol) 1,3-dibromo-5-methylbenzene, 22.4 g
(0.088 mol) diborane pinacol ester, 1.5 g (2.0 mmol) Pd(dppf)Cl2,
23.52 g (0.24 mmol) KOAc, and 80 mL DMSO was heated to 80 ꢀC for
4 h. After the mixture was cooled, 500 mL water was added, and the
mixture was extracted with ethyl acetate. The organic layer was
washed with brine, dried over Na2SO4, and the solvent was removed
by vacuum distillation. The crude product was purified by column
chromatography on silica gel with ethyl acetate/petroleum ether (1/
1
20) as the eluant to afford a white power (11.32 g, 82.3%). H NMR
(CDCl3, 400 MHz)
d
8.09 (s, 1H), 7.73 (s, 2H), 2.35 (s, 3H), 1.33 (s, 24H);
21.09, 24.89, 83.77, 136.32, 138.42;
13C NMR (CDCl3, 100 MHz)
d
HRMS-ESI for C19H30B2O4 (m/z) 345 [Mþ1], 344 [M], 189 [Mꢂ155].
4.3.8. 3,5-Bis-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-1-
bromoemethylbenzene. A mixture of 10.32 g (30.0 mmol) 3,5-bis-
(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-toluene, 6.23 g(35.0 mmol)
NBS, 0.35g (1.4 mmol) benzoyl peroxide, and 250 mL CCl4 was refluxed
for 7 h under N2 atmosphere. The resulting solution was filtered while
it was cooled to room temperature. The filtrate was washed with
saturated sodium hyposulfite solution (3ꢁ100 mL) then brine
(2ꢁ100 mL), dried over Na2SO4, and concentrated by vacuum distil-
lation to afford yellow-white precipitate. The precipitate was recrys-
tallized with CCl4 to give white solid (9.46 g, 74.5%).
4.3.4. (S)-6,60-Dibromo-2,20-dimethoxy-1,10-binaphthyl. (S)-2,20-Di-
methoxy-1,10-binaphthyl 9.4 g (30.0 mmol) was dissolved in
500 mL CH2Cl2 and stirred at 0 ꢀC. 3.36 mL (66.0 mmol) Bromine
was added in one portion with stirring and a stream of nitrogen was
bubbled through the solution to remove the evolving HBr. The re-
action mixture was stirred for 5 h while the flask was allowed to
warm to room temperature. During this procedure, the product
precipitates as a white solid and was filtered off and dried in vacuo
to give desired product (9.52 g, 92.3%) as a white powder.
4.3.9. 5-(Bromomethyl)phenyl-1,3-diboronic acid. A mixture of
8.46 g (20.0 mmol) 3,5-bis-(4,4,5,5-tetramethyl-1,3,2-dioxabor-
olane)-1-bromoemethylbenzene, 12.84 g (60.0 mmol) sodium
periodate, and 50 mL THF/H2O (4/1) was stirred until homogeneous
at room temperature, and then 2 N HCl (0.2 mL) was added. After
48 h, the reaction mixture was extracted with ethyl acetate
(3ꢁ50 mL), and the combined organic extracts were washed with
water and brine, dried over Na2SO4, and concentrated in vacuo. The
crude product was recrystallized for two times with CCl4 to give
white solid (1.99 g, 38.6%).
4.3.5. (S)-2,20-Dimethoxy-6,60-bis-(4,4,5,5-tetramethyl-1,3,2-dioxa-
borolane)-1,10-naphtha-lene. A mixture with 9.44 g (20.0 mmol)
(S)-6,60-dibromo-2,20-dimethoxy-1,10-binaphthyl,
11.18
g
(44.0 mmol) bis(pinacolato)diboron, 0.58 g (8 mol %) Pd(dppf)Cl2,
and 11.78 g (0.12 mol) potassium acetate in 60 mL DMSO was
stirred at 80 ꢀC for 6 h under a nitrogen atmosphere. The reaction
mixture was cooled to room temperature, poured into the 200 mL
ice water, filtrated, and then purified by column chromatography
on silica gel with ethyl acetate/petroleum ether (1/15) as the eluant
to afford a white power (5.82 g, 51.4%). 1H NMR (CDCl3, 400 MHz)
4.3.10. N,N0-4,40-Bis(benzyl-3,5-diboronic acid)-bipyridinium di-
bromide (ToBV). To a solution of 1.94 g (7.5 mmol) 5-(bromomethyl)
phenyl-1,3-diboronic acid in 20 mL DMF was added 0.585 g
(3.75 mmol) 4,40-dipyridyl, and the reaction mixture was stirred at
80 ꢀC for 48 h under nitrogen. The orange precipitate was collected
by filtration, washed with DMF, acetone, then ether and dried un-
der a stream of nitrogen to yield ToBV (1.21 g, 47.8%). 1H NMR (D2O,
d
8.42 (s, 2H), 8.05 (d, J¼9.2 Hz, 2H), 7.58 (d, J¼8.8 Hz, 2H), 7.45 (d,
J¼8.8 Hz, 2H), 7.10 (d, J¼8.8 Hz, 2H), 3.76 (s, 6H), 1.38 (s, 24H); 13C
NMR (DMSOd6, 100 MHz)
d 24.89, 56.71, 83.70, 113.94, 119.31,
124.32, 128.60, 130.34, 130.85, 135.73, 136.52, 155.94; HRMS-ESI for
C34H40B2O6 (m/z) 567.40 [Mþ1], 566.24 [M], 565.16 [Mꢂ1].
4.3.6. PP-S-BINOL. To 100 mL three-neck flask, equipped with
mechanical stirrer was added 3.336 g (6.0 mmol) 1,4-dibromo-2,5-
bis(3-sulfonatopropoxy)benzene, 3.396 g (6.0 mmol) 2,20-dime-
thoxy-6,60-bis-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-1,10-naph
thalene, 60 mL dried DMF, and 0.224g (0.18 mol) Pd(PPh3)4 under
nitrogen. The mixture was stirred under nitrogen for 30 min, and
then 20 mL aqueous solution with 3.816 g (36.0 mmol) sodium
carbonate was generally added by dropping funnel. The reaction
was heated at 80 ꢀC for 48 h. The reaction turned black as Pd(0)
particles were liberated. The tan-violet filtrate was collected, pre-
cipitated into 1 L of acetone, and redissolved in deionized water.
The polymer was dialyzed using a membrane with a 3500 cutoff for
3 days. The final product, a dark yellow polymer, was obtained after
dried in vacuo at 110 ꢀC for 24 h (2.21 g, 51.6%). 1H NMR (DMSOd6,
400 MHz)
6H), 5.95 (s, 4H); 13C NMR (D2O, 100 MHz)
132.52, 136.58, 146.12, 149.68, 151.44; 11B NMR (80 MHz, D2O)
25.4; HRMS-ESI for C24H24B2Br2N2O4 (m/z) HRMS-ESI (m/z)
d
9.50 (d, J¼10.0 Hz, 4H), 8.76 (d, J¼7.2 Hz, 4H), 8.07 (s,
d
64.52, 99.98, 127.67,
d
513.24 [M-2Br].
Acknowledgements
We gratefully acknowledge the Natural Science Foundation of
China (20802042) and the Natural Science Foundation of Shanxi
province (2009021006-1).
Supplementary data
400 MHz)
d
8.22 (s, 2H), 8.15 (d, J¼7.6 Hz, 2H), 7.64 (d, J¼7.6 Hz, 2H),
1H NMR, 13C NMR, and ESI-MS of compounds and fluorescent
spectroscopy (PDF). Supplementary data related to this article can
be found online at doi:10.1016/j.tet.2011.03.025. These data include
MOL files and InChIKeys of the most important compounds de-
scribed in this article.
7.55 (d, J¼7.6 Hz, 2H), 7.16 (s, 2H), 7.04 (d, J¼7.2 Hz, 2H), 4.12 (broad,
4H), 3.77 (s, 6H), 2.58 (broad, 4H), 1.97 (broad, 4H); 13C NMR
(DMSOd6, 100 MHz)
d 25.82, 48.47, 56.74, 68.32, 114.82, 116.23,
118.64, 129.11, 129.87, 130.26, 132.80, 133.35, 150.24, 153.20, 155.25.

3180
L. Feng et al. / Tetrahedron 67 (2011) 3175e3180
6. (a) Tan, J.; Wang, H. F.; Yan, X. P. Anal. Chem. 2009, 81, 5273e5280; (b) Cao, Z.;
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