Preparation of several BINOL-based polymeric ligands for the enantioselective addition of triethylaluminium to aromatic aldehydes

Article abstract of DOI:10.1016/j.tet.2015.12.076

The synthesis of several polystyrene-supported BINOL (1,1-binaphthol) ligands via radical polymerization is described. These BINOL-based polymeric ligands were applied to the enantioselective addition of triethylaluminium to aromatic aldehyde in the presence of titanium isopropoxide. The products were obtained with up to 93% enantiomeric excess (ee) in good to excellent yield. The ligands were easily recovered and reused without losing their catalytic activity as well as enantioselectivity.

Full text of DOI:10.1016/j.tet.2015.12.076

Accepted Manuscript
Preparation of several BINOL-based polymeric ligands for the enantioselective
addition of triethylaluminium to aromatic aldehydes
Dacai Liu, Kunbing Ouyang, Nianfa Yang
PII:
S0040-4020(15)30324-0
10.1016/j.tet.2015.12.076
TET 27402
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 20 November 2015
Revised Date: 15 December 2015
Accepted Date: 28 December 2015
Please cite this article as: Liu D, Ouyang K, Yang N, Preparation of several BINOL-based polymeric
ligands for the enantioselective addition of triethylaluminium to aromatic aldehydes, Tetrahedron (2016),
doi: 10.1016/j.tet.2015.12.076.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Preparation of several BINOL–based polymeric ligands
for the enantioselective addition of triethylaluminium
to aromatic aldehydes
Dacai Liu, Kunbing Ouyang *, Nianfa Yang *
OH
CHO
Poly-BINOL/Ti(O-i-Pr)4
Al
R
R
THF, 0 oC, 24 h
Up to 93% ee
Up to 96% yield

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Preparation of several BINOL-based polymeric ligands for the enantioselective
addition of triethylaluminium to aromatic aldehydes
Dacai Liu, Kunbing Ouyang*, Nianfa Yang*
Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, College of Chemistry, Xiangtan University, Hunan 411105,
PR China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
The synthesis of several polystyrene-supported BINOL (1,1-binaphthol) ligands via radical
polymerization is described. These BINOL-based polymeric ligands were applied to the
enantioselective addition of triethylaluminium to aromatic aldehyde in the presence of titanium
isopropoxide. The products were obtained with up to 93% enantiomeric excess (ee) in good to
excellent yield. The ligands were easily recovered and reused without losing their catalytic
activity as well as enantioselectivity.
Available online
2009 Elsevier Ltd. All rights reserved
.
Keywords:
polymeric
enantioselective addition
triethylaluminium
1. Introduction
chiral catalyst is attached to a polymer support due to the changes
in the microenvironment of the catalytic sites.8
Asymmetric catalysis is an area of utmost importance in
organic chemistry.1 Adaptation of small chiral molecule catalyst
to enantioselective synthesis has been well-studied in past
decades.2 In the contrast, the application of chiral polymeric
ligands remains rare. The inherent advantages of chiral polymeric
catalysts such as easy separation of product from reaction
mixture, readily recovery and reuse of the expensive chiral
catalyst 3 have made chiral polymeric ligands a promising area in
both green chemistry and combinatorial chemistry.4 In addition,
the employment of polymeric catalysts makes it possible to
conduct reactions in flow reactors or in flow membrane reactors
for large-scale production.5 Therefore, the development of
polymeric ligand for asymmetric catalysts has long been
attractive and of great significance.
We have been working on asymmetric syntheses based on
polymeric chiral catalysts for many years and have made
significant progress in many asymmetric reactions.9 However,
almost no polymeric ligands performed efficiently in the
asymmetric addition of triethylaluminium to aromatic aldehyde
in the past decades. Herein, we report the synthesis of several
chiral polymers bearing BINOL that exhibited high catalytic
activity and enantioselectivity in the addition of
triethylaluminium to aromatic aldehyde. The products were
obtained in good yields with high enantioselectivity. The
polymeric catalysts were also proven to be more efficient with
higher selectivity than its monomeric unit.
2. Results and discussion
Optically active 1,1'-binaphthol (BINOL) and its derivatives
are widely used in asymmetric reactions, such as asymmetric
alkylation, asymmetric hydrogenation, Diels-Alder reaction,
asymmetric epoxidation of α,β-unsaturated ketone, etc.6 Many
BINOL-based polymeric chiral ligands have been developed and
successfully applied as chiral catalyst in these model reactions.7
Traditional approach for the preparation of polymers involves the
development of a monomer and then anchored it to an achiral and
sterically irregular polymer backbone. Although many polymer-
supported catalysts have been obtained in this way, a significant
Four polymeric ligands were successfully synthesized from
commercially available (S)-BINOL as depicted in Scheme 1.
Chiral (S)-BINOL reacted with chloromethyl ether to give (S)-
2,2′-bis(methoxymethyloxy)-1,1′-binaphthalene 1.10 (S)-3-iodo-
2,2′-bis(methoxymethyl)-1,1′-binaphthalene
2
was easily
prepared from readily accessible 1 through a lithiation-iodination
sequence.11 The coupling of (S)-2 with 4-vinyphenyl boronic acid
was successfully carried out using Pd(PPh3)4 as catalyst in
dioxane to afford the monomer (S)-3-(4-vinyphenyl)-2,2′-
bis(methoxymethyl)-1,1′- binaphthalene (3) in good yield (93%).
drop of enantioselectivity is often observed when a monomeric
———
*Corresponding authors.
E-mail address: kbouyang@xtu.edu.cn; nfyang@xtu.etu.cn

2
Tetrahedron
Poly-4a, Poly-4b and Poly-4c were obtained by free radical
Almost all of the reported works on asymmetric addition of
ACCEPTED MANUSCRIPT
copolymerization of (S)-3 with styrene.
triethylaluminium (Et3Al) to aromatic aldehyde focused on small
molecular catalysts.15 The study of polymeric ligands remains
rare as mentioned above. As our continued interest in chiral
catalysts, we tried to apply the polymeric ligands in this
asymmetric addition reaction. Initially, we tested the reaction of
triethylaluminium and benzaldehyde as a model example. To
evaluate efficiency of the soluble polymeric ligands, the reactions
were carried out in the presence of the polymeric ligands (5
mol%), with Et3Al (3 equiv) and titanium tetraisopropoxide (1.4
equiv) in THF at 0 °C (Table 1). After 24 h, (S)-1-
phenylpropanol was obtained in moderate yields with moderate
selectivity. Poly-5a possessed the highest level of
enantioselective induction (61% ee) in 75% yield (Table 1, entry
1) among the three catalysts. Polymeric catalyst Poly-5b with a
lower loading of BINOL led to a decrease in both ee (57%) and
yield (72%) (Table 1, entry 2). The employment of Poly-5c
(Table 1, entry 3), which contained the lowest loading of BINOL,
gave similar result to that of Poly-5b. These results suggested
that the reaction was majorly promoted by the BINOL moiety on
the polymer chain. The chiral polymeric catalyst 6-substitued
BINOL Poly-10 gave lowest enantioselectivity (37%) and yield
(43%) (Table 1, entry 4) as expected. It can be inferred that the
substituent on the 6-position of BINOL would lead to a drop in
the catalytic activity of the ligand.
The purpose of copolymerization of (S)-3 with styrene was
to improve the solubility of the polymer in organic solvent so that
the catalytic reaction could be carried out in various solvents
such as toluene, CH2Cl2, THF and so on.12,3b In addition, a
component of the non-cross-linked copolymer backbones might
affect the catalytic activity and enantioselectivity.13 The
protecting groups were removed by treatment of acid to afford
Poly-5a (Mn = 1.05 × 104, PDI = Mw/Mn = 1.42), Poly-5b (Mn =
6.70 × 103, PDI = Mw/Mn = 1.47) and Poly-5c (Mn = 3.80 × 103,
PDI = Mw/Mn = 1.57). All of these polymers are well soluble in
solvents such as CH2Cl2, toluene, THF and ethyl acetate, and
could be readily precipitate by adding the solution to methanol.
By being precipitated in methanol for several times, the monomer
could be completely removed. The structure and purity of the
polymers were determined by 1H NMR spectra.
I
4-Vinyphenylboronic acid
n-BuLi, I2
OMOM
OMOM
OMOM
OMOM
Pd(PPh3)4, Na2CO3
Dioxane, reflux
-78 o
C
1
2
HCl
OMOM
OMOM
AIBN
Toluene, 85 oC
OMOM
OMOM
OH
OH
Table 1. Asymmetric reaction of Et3Al with benzaldehyde catalyzed
by various ligands
THF
3
4a - c
5a - c
a: 3/styene = 1/1 (mass ratio)
b: 3/styene = 1/2 (mass ratio)
c: 3/styene = 1/5 (mass ratio)
Entrya
Ligand
Poly-5a
Poly-5b
Poly-5c
Poly-10
Yield (%)b
eec (%)
61
57
56
1
2
3
4
75
72
70
43
Br
Br
Pd(PPh3)4 , Na2CO3
NaH, ClCH2OCH3
4-Vinyphenylborionic acid
Dioxane, reflux
OH
OH
OMOM
OMOM
THF, 0 o
C
37
a
Reactions were carried out with 5 mol% of catalyst, 1.0 mmol
6
7
benzaldehyde, 3.0 mmol Et3Al, 1.4 mmol Ti(O-i-Pr)4, in 5 mL THF
b
c
at 0 oC for 24 h. Isolated yield. Determined by HPLC using
AIBN
2.0 equiv styene
Chiralcel OD-H column.
OMOM
OMOM
OMOM
OMOM
Toluene
It is well known that the enantioselectivity of asymmetric
reactions are strongly affected by solvent, temperature, and the
amount of catalyst. To evaluate these effects, we investigated the
asymmetric reaction of Et3Al with benzaldehyde catalyzed by the
chiral polymeric ligand Poly-5a under various reaction
conditions, and compared the catalytic activity and
enantioselectivity with its monomeric unit. The results are
summarized in Table 2. We chose THF, DCM and toluene to
examine the solvent effects. The reaction carried out in toluene
led to the formation of (S)-1-phenylpropan-1-ol with only 33% ee
in 45% yield (Table 2, entry 2), while the reaction preformed in
DCM gained a slightly higher yield and ee (Table 2, entry 1). To
our delight, when THF was used as the solvent, the ee increased
to 61% in 75% yield (Table 2, entry 3). Ti(O-i-Pr)4 was proven to
be crucial to both ee and yield (Table 2, entries 3-7). The addition
of 3.0 eq. of Ti(O-i-Pr)4 afforded expected product in 90% yield
with up to 83% ee. Increasing the amount of Ti(O-i-Pr)4 to 4.0 eq.
resulted in a better yield with a slight drop of ee (Table 2, entry
7). Different amount of Et3Al was then screened (Table 2, entries
7-9). When 2.0 eq. of Et3Al was used, the yield was only 57%
(Table 2, entry 8). The yield rapidly increased to 98% when 4.0
eq. of Et3Al was employed while the ee dropped to 76% (Table 2,
8
9
HCl
THF, 0 o
OH
OH
MOM = CH2OCH3
C
10
Scheme 1. Synthesis of polymer 5a, 5b, 5c and 10
We were also interested in similar systems wherein the 4-
vinyphenyl was attached to the BINOL core at the 6 positions of
BINOL, which are sufficiently far apart from the catalytic active
center so that primary steric effect becomes an unimportant
factor. Poly-10 (Mn = 6.52 × 103, PDI = Mw/Mn = 1.46) was
synthesized in a similar way as presented in Scheme 1. (S)-6 and
(S)-7 were obtained for further use as reported.14 Later,
compound (S)-7 was subsequently coupled with 4-
vinyphenylborionic acid to give the 6-substituted monomer (S)-6-
(4-vinyphenyl)-2,2′-bis(methoxymethyl)-1,1′-binaphthalene (8).
The copolymerization of (S)-8 with styrene was carried out in
toluene using 2,2-azobisisobutyronitrile (AIBN) as initiator,
followed by deprotection of the group -CH2OCH3 to afford Poly-
10 in high yield (89%) with good solubility.
o
entry 9). When the reaction was carried out at 25 C, the desired
product was obtained in 78% yield with 75% ee. However, the
reaction system became more complex (Table 2, entry 10). When
o
the reaction temperature lowered to -15 C, the product was

3
ACCEPTED MANUSCRIPT
Table 2. Asymmetric reaction of Et3Al with benzaldehyde catalyzed by Poly-5a
Entry
1
Solvent
CH2Cl2
Toluene
THF
Et3Al/(eq.)
3.0
Ti(O-i-Pr)4(eq.)
T/(oC)
catalyst /(mol%)
Yield/(%)a
51
ee/(%)b
41
33
61
79
83
78
82
76
75
79
91
85
87
0
1.4
1.4
1.4
2.0
3.0
4.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
0
0
5
5
2
3.0
45
3
3.0
0
5
75
4
THF
3.0
0
5
82
6
THF
3.0
0
5
90
7
THF
3.0
0
5
95
8
THF
2.0
0
5
57
9
THF
4.0
0
5
98
10
11
12
13
14c
15
THF
3.0
25
-15
0
5
78
THF
3.0
5
80
THF
3.0
10
15
10
92
THF
3.0
0
87
THF
3.0
0
95
THF
3.0
0
0
85
a
b
c
Isolated yield.
Determined by HPLC using Chiralcel OD-H column.
The monomeric unit 12 was used as catalyst.
achieved in 80% yield with 79% ee (Table 2, entry 11). The yield
and selectivity of the product were found be sensitive to the
amount of catalyst. An increase in the catalyst loading from 5
Table 3. Enantioselective addition of Et3Al to various aromatic
aldehydes catalyzed by Poly-5a
o
mol% to 10 mol% at 0 C resulted in a large increase in the
enantioselectivity (91% ee) and a slight increase of yield (92%,
Table 2, entry 12). The product was obtained with a slight loss of
both the ee and yield when 15 mol% catalyst was used (Table 2,
entry 13). When the reaction was carried out without any ligand,
no enantioselectivity was observed (Table 2, entry 15). For
comparison with Poly-5a, the monomeric unit (S)-3-(4-
vinyphenyl)-1,1′-binaphthalene (12), which was synthesized via a
simple catalytic hydrogenation reaction (Scheme 2), was induced
to the model reaction. The product was obtained in 95% yield
with a slight loss of ee 87% (Table 2, entry 14). In consideration
of the unrecyclable nature of compound 12, the optimized
combination for the asymmetric addition of Et3Al to
benzaldehyde was realized: 10 mol% of Poly-5a, 1.0 mmol
aldehyde, 3.0 eq. of Et3Al 3.0 eq. of Ti(O-i-Pr)4, and THF as the
solvent, and the reaction was set at 0 °C for 24 h.
Entrya
R
Yield
(%)b
92
eec
(%)c
91
89
88
86
85
73
77
93
91
86
85
Config.d
1
Phenyl
S
S
S
S
S
S
S
S
S
S
S
2
2-Methoxyphenyl
3-Methoxyphenyl
4-Chlorophenyl
4-Bromophenyl
2-Phenylvinyl
3-Phenylpropyl
4-Phenylphenyl
1-Naphthyl
94
3
93
4
92
5
87
6
93
7
75
8
90
9
96
10
11
2- Naphthyl
95
9-Anthryl
94
a Reactions were carried out with 10 mol% of Poly-5a (as a BINOL
monomer), 1.0 mmol aldehyde, 3.0 mmol Et3Al, 3.0 mmol Ti(O-i-
Pr)4, in 5 mL THF at 0 oC for 24 h. b Isolated yield. c Determined by
Scheme 2 Synthesis of (S)-3-(4-ethyl)-2,2′-bis(methoxymethyl)-
1,1′- binaphthalene 12
d
HPLC using a Chiralcel OD-H column. Absolute configurations
With the optimized condition in hand, we examined the scope
of the enantioselective addition of aldehydes to study the
generality of the ligand Poly-5a. The results are summarized in
Table 3. As presented in Table 3, Poly-5a showed a satisfying
level of enantioselective for most aromatic aldehydes. The
position of the electron-donating -OCH3 substituent on the
aromatic ring (Table 3, entries 2 and 3) had little effect on the ee
of the product. Asymmetric Addition of the aryl aldehyde
proceeded with excellent enantioselectivity. The ethylation of 4-
phenylbenzaldehyde gave the highest ee 93% (Table 3, entry 8).
were determined by comparison with the sign of specific rotations
reported in the literature.16
Electron-withdrawing groups (Table 3, entries 4 and 5) resulted
in little differences in both the ee and yield. The reaction of 1-, 2-
naphthaldehyde and 9-anthracene resulted in excellent yield
(94%-96%) with good ee (85%-91%), respectively (Table 3,
entries 9-11). It was also noteworthy that the addition of
cinnamyl aldehyde or benzenepropanal also furnished the
corresponding alcohol smoothly with relatively lower ee 73%

4
Tetrahedron
and 77% (Table 3, entries 6 and 7). These observations
on silica gel (using 10 % ethyl acetate in toluene as eluent) to
ACCEPTED MANUSCRIPT
suggested that the ligand Poly-5a would not work efficiently in
the asymmetric addition of aliphatic aldehyde with Et3Al. In
summary, a series of secondary alcohols could be efficiently
prepared by asymmetric addition of the aldehyde in good yields
with high enantioselectivities in the presence of Poly-5a.
give 1.701
g
(93% yield) of (S)-3-(4-vinyphenyl)-2,2′-
bis(methoxymethoxy) -1,1′- binaphthalene (S-3) as a white solid.
m.p. 65.2 - 67.2 C. [
o
25
365
α]
= -486 (c = 1 mg/mL, THF). Elem.
Anal. Calcd. for C32H28O4: C 80.65, H 5.92; Found: C 80.62, H
5.94. IR：3052, 2823, 1939, 1621, 1131, 993 cm-1; H NMR
1
(400 MHz) δ 8.00 - 7.83 (m, 4H), 7.71 (d, J = 6.9 Hz, 2H), 7.60
(d, J = 8.7 Hz, 1H), 7.51 (d, J = 7.0 Hz, 2H), 7.44 – 7.34 (m, 2H),
7.26 (m, 4H), 6.78 (dd, J = 17.0, 11.2 Hz, 1H), 5.82 (d, J = 17.6
Hz, 1H), 5.29 (d, J = 10.8 Hz, 1H), 5.19 (d, J = 5.7 Hz, 1H), 5.08
(d, J = 6.5 Hz, 1H), 4.34 (d, J = 15.7 Hz, 2H), 3.23 (s, 3H), 2.29
(s, 3H). 13C NMR (100 MHz) δ 153.02, 151.17, 138.71, 136.60,
135.26, 134.21, 133.45, 131.12, 130.29, 129.92, 129.82, 129.77,
128.13, 127.92, 126.63, 126.51, 126.35, 126.27, 126.02, 125.93,
125.30, 124.22, 121.28, 116.84, 114.02, 98.81, 95.13, 56.04.
It is remarkable that the chiral ligand Poly-5a can be easily
separated and recycled. The recovered Poly-5a was used for the
asymmetric addition of Et3Al to benzaldehyde repeatedly (Table
4). The results show that ligand Poly-5a could be reused at least
four times without obvious loss of catalytic activity as well as
enantioselectivity.
Table 4 Asymmetric reaction of Et3Al with benzaldehyde catalyzed
by the recovered Poly-5a a
Synthesis of Poly-4a, Poly-4b and Poly-4c
Cycle
1
2
3
4
2,2′-Azobisisobutyronitrile (AIBN, 0.048 g, 5 mol%) and (S)-
3 (0.500 g) was added to a small dry Schlenk flask. The flask was
thoroughly purged with nitrogen for three times and then a
toluene solution of styrene (0.500 g in 2 mL) was added via
degassed syringes. The mixture was stirred for 36 h at 85 C.
After cooling to room temperature the polymer was precipitated
by addition to 50 mL methanol for several times. The precipitate
Yield (%) b
Ee (%) c
91
90
90
88
92
89
89
90
a Reactions were carried out with 10 mol% of recovered catalyst, 1.0
mmol benzaldehyde, 3.0 mmol Et3Al, 3.0 mmol Ti(O-i-Pr)4, in 5 mL
THF at 0 oC for 24 h. b Isolated yield. c Determined by HPLC using a
Chiralcel OD-H column.
o
was filtered and dried in vacuo at 40 °C for 4h to give 0.930 g of
25
365
(93% yield) Poly- 4a as a white powder. [
α]
= -411 (c = 1
3. Conclusions
mg/mL , THF). Mn = 1.20 × 104, PDI = Mw/Mn = 1.38. IR: 3086,
2919, 2343, 1651, 1414, 975 cm-1; H NMR (400 MHz) δ 7.94
1
In summary, four new chiral polymeric ligands have been
synthesized from commercial available BINOL and styrene. Its
activity in catalytic asymmetric addition of triethylaluminum to
aryl aldehyde was studied. The products were obtained with up to
93% ee and 96% yield. Meanwhile, Poly-5a exhibited good
activity even after being used four times. The development of
other asymmetric reactions using these polymeric ligands is
currently ongoing in our group.
(br), 7.86 (br), 7.22 (br), 6.56 (br), 5.10 (br), 4.22 (br), 3.20 (br),
2.13 (br), 1.44 (br). Poly-4b (95% yield) was prepared according
25
to the procedure mentioned above using 2.0 eq. styrene, [
α]
365 = -
378 (c = 1 mg/mLl, THF), Mn = 8.20 × 103, PDI = Mw/Mn = 1.40.
Poly-4c (93% yield) was prepared according to the procedure
25
mentioned above using 5.0 eq. styrene, [
α]
365 = -102 (c =1 mg/mL,
THF), Mn = 4.08 × 103, PDI = Mw/Mn = 1.48.
Synthesis of Poly-5a, Poly-5b and Poly-5c
4. Experimental
4 mL of concentrated hydrochloric acid was added to a THF
(50 mL) solution of Poly-4a (0.501 g) at 0°C. The mixture was
then stirred at room temperature for 24 h. The mixture was
extracted with CH2Cl2, the extractive was washed with saturated
NaHCO3 and then was poured into methanol to precipitate
polymer. The polymer was precipitated in 50 mL methanol twice.
General
1H NMR and 13C NMR spectra were performed on a Bruker
ARX 400 MHz spectrometer using deuterated chloroform as
solvent and tetramethylsilane (TMS) as the internal standard.
Optical rotation data were measured on a Perkin Elmer Model
341 LC Polarimeter at 365 nm. GPC analysis was performed
with a J ASCO-GPC system consisting of DG-1580-53 degasser,
PU-980 HPLC pump, UV-970 UV/Vis detector, RI-930 RI
detector and CO-2065-plus column oven (at 38oC) using two
connected Shodex GPC-KF-804L columns in THF (sample
concentration = 1 wt %; flow rate = 1.0 mL/min). The molecular
weight was calibrated with commercially available polystyrene.
All reagents were used as supplied commercially unless
otherwise noted. THF and toluene were distilled from sodium
under N2 before use.
The polymer was filtered and dried in vacuo at 40 °C for 4 h to
25
give 0.431 g (86% yield) of Poly-5a as a white powder. [
α]
365 = -
578 (c =1 mg/mL, THF). Mn = 1.05 × 104, PDI = Mw/Mn = 1.42.
IR: 3524, 2985, 2356, 1601, 1311, 999 cm-1; H NMR (400 MHz)
1
δ: 7.86 (br), 7.05 (br), 6.57 (br), 5.15 (br), 1.85 (br), 1.45 (br).
Similarity, Poly-5b and Poly-5c was prepared according to the
25
procedure mentioned above method. For Poly-5b: [
α]
365 = -415 (c
= 1 mg/mL, THF). Mn = 6.70 × 103, PDI = Mw/Mn = 1.47. For
Poly-5c: [
α]
365 = -134 (c = 1 mg/mL, THF). Mn = 3.80 × 103, PDI
25
= Mw/Mn = 1.57.
Synthesis of (S)-3-(4-vinyphenyl)-2,2′-bis(methoxymethyl)-
1,1′- binaphthalene (S-3)
Synthesis of (S)-6-(4-vinyphenyl)-2,2′-bis(methoxymethyl)-
1,1′- binaphthalene (S-8)
A mixture of (S)-3-iodo-2,2′-bis(methoxy(methoxy))-1,1′-
binaphthalene (2.001 g, 4.0 mmol), 4-vinyphenylborionic acid
(0.888 g, 6.0 mmol) and Pd(PPh3)4 (0.230 g, 0.2 mmol) in
aqueous 2 M Na2CO3 (5 mL) and 1,4-dioxane (30 mL) was
heated under reflux for 24 h under argon atmosphere. The
reaction mixture was poured into water and extracted with ethyl
acetate (2 × 20 mL). The combined organic layers were dried
over anhydrous magnesium sulfate (MgSO4) and concentrated in
vacuo. The residue was purified by flash column chromatography
A mixture of (S)-6-bromo-2,2′-bis(methoxymethoxy)-1,1′-
binaphthalene (2.260 g, 5.0 mmol), 4-vinyphenylborionic acid
(1.480 g, 10.0 mmol), and Pd(PPh3)4 (0.446 g, 0.4 mmol) in
aqueous 2 M Na2CO3 (5 mL) and 1,4-dioxane (30 mL) was
heated to reflux for 48 h under argon atmosphere. The reaction
mixture was poured into water and extracted with CH2Cl2 (2 × 20
mL). The combined organic layers were dried over anhydrous
magnesium sulfate (MgSO4) and concentrated in vacuo. The
residue was purified by flash column chromatography on silica

5
gel (using 10 % ethyl acetate in petroleum ether as eluent) to give
127.90, 126.60, 126.37, 126.18, 126.00, 125.20, 124.21, 121.47,
116.92, 98.71, 95.19, 56.01, 55.99, 28.73, 15.75.
ACCEPTED MANUSCRIPT
1.400
g
(59
%
yield) of (S)-6-(4-vinyphenyl)-2,2′-
bis(methoxymethoxy)-1,1′-binaphthalene (S-8) as
a
white
o
25
Synthesis of (S)-3-(4-vinyphenyl) -1,1′- binaphthalene (S-12)
powder. m.p. 85.1 - 86.9 C. [α]
= -351 (c = 1 mg/mL, THF).
365
Elem. Anal. Calcd. for C32H28O4: C 80.65, H 5.92; Found: C
5 mL of concentrated hydrochloric acid was added to a
solution of (S)-10 (0.501 g) in THF (20 mL) at 0°C. The mixture
was stirred at room temperature for 6 h and the reaction was
quenched with water. Then the mixture was extracted with ethyl
acetate (2 × 20 mL). The combined organic layers were dried
over anhydrous magnesium sulfate (MgSO4) and concentrated in
vacuo. The residue was purified by flash column chromatography
on silica gel (using 20 % ethyl acetate in petroleum ether as
1
80.64, H 5.95. IR: 2903, 2819, 2354, 1620, 1239, 1012 cm-1; H
NMR (400 MHz) δ 8.09 (s, 1H), 7.99 (dd, J = 15.8, 9.0 Hz, 2H),
7.89 (d, J = 8.1 Hz, 1H), 7.67-7.57 (m, 4H), 7.49 (d, J = 8.0 Hz,
3H), 7.36 (t, J = 7.2 Hz, 1H), 7.26-7.19 (m, 3H), 6.76 (dd, J =
17.5, 10.9 Hz, 1H), 5.79 (d, J = 17.6 Hz, 1H), 5.27 (d, J = 10.9
Hz, 1H), 5.10 (d, J = 6.7 Hz, 2H), 5.02-4.97 (m, 2H), 3.18 (s, 3H)
3.16 (s, 3H). 13C NMR (100 MHz) δ 152.96, 152.82, 140.45,
136.54, 136.28, 134.14, 133.41, 130.22, 130.01, 129.84, 129.59,
128.05, 127.35, 126.82, 126.49, 126.30, 125.86, 125.66, 125.63,
124.23, 121.25, 121.25, 117.77, 117.38, 113.92, 95.26, 95.22,
55.95.
eluent) to afford 0.371 g (90% yield) of pure (S)-3-(4-vinyphenyl)
25
365
-1,1′- binaphthalene (S-12) as a yellow bubble. [
α]
= -678 (c =
1 mg/mL, THF). Elem. Anal. Calcd. for C28H22O2: C 86.13, H
5.68; Found: C 86.15, H 5.65. IR: 3494, 2957, 2360, 1609, 1120,
744 cm-1; 1H NMR (400 MHz) δ 8.06-7.95 (m, 2H), 7.90 (t, J =
7.1 Hz, 2H), 7.65 (d, J = 7.9 Hz, 2H), 7.47-7.19 (m, 8H), 7.15 (d,
J = 8.3 Hz, 1H), 5.30 (s, 1H), 5.12 (s, 1H), 2.73 (q, J = 7.5 Hz,
2H), 1.30 (t, J = 7.6 Hz, 3H). 13C NMR (100 MHz) δ 152.73,
150.52, 144.06, 134.83, 133.60, 133.05, 131.35, 130.85, 129.69,
129.60, 128.50, 128.21, 127.48, 127.38, 124.50, 124.43, 124.34,
124.07, 117.91, 111.96, 111.81, 28.81, 15.73.
Synthesis of Poly-9
To a toluene solution of 6 (0.303 g) was added AIBN (0.029
g) and styrene (0.601 g). The solution was purged with argon
thoroughly for three times. Polymerization continued for 48 h at
85°C. After cooling to room temperature the polymer was
precipitated by pouring into 50 mL methanol to obtain
precipitate. The obtained precipitate was precipitated in methanol
for several times. Then the precipitate was filtered and dried in
A
typical
asymmetric
addition
reaction
of
triethylaluminium with aldehydes catalyzed Poly-5a
vacuo at 40°C for 4 h to give 0.765 g (85% yield) of Poly-9 as a
25
white powder. [α] = -242 (c = 1 mg/mL, THF). Mn = 7.95 ×
365
Titanium tetraisopropoxide (1.0 mL, 3.0 mmol) was added to
a solution of Poly-5a (86.5 mg, 0.1 mmol as a BINOL monomer)
in THF (5 mL) at room temperature under argon atmosphere. The
mixture was stirred for 15 min at room temperature. Then
triethylaluminium (3 mL, 1M in hexane, 3.0 mmol) was added to
this mixture at 0 oC. The mixture was stirred at room temperature
for another 15 min. After that benzaldehyde (1 mL, 1.0 mmol)
was added to this mixture at 0 oC. After being stirred for 24 h, the
reaction mixture was quenched with aqueous 3 M HCl and
extracted with ethyl acetate twice. The combined organic layer
were washed with aqueous 5% NaHCO3, dried over MgSO4 and
concentrated in vacuo. The residue was added into 20 mL of
methanol. Then, the mixture was filtrated. The filtrated cake
was recovered for recycling. The filtrate was evaporated in
vacuo and residue was purified by column chromatography on
silica gel to afford the pure product. The structure of all products
were confirmed by comparison of characterization data to
reported literature.16
103, PDI = Mw/Mn = 1.35. IR: 3010, 2921, 2348, 1603, 1489,
1012 cm-1 1H NMR (400 MHz) δ 7.98 (br), 7.6 (br), 7.22 (br),
;
6.57 (br), 5.05 (br), 3.16 (br), 1.85 (br), 1.42 (br).
Synthesis of Poly-10
4 mL of concentrated hydrochloric acid was added to a THF
(in 50 mL) solution of Poly-9 (0.503 g) at 0 °C. The mixture was
then stirred at room temperature for 24 h. The mixture was
extracted with CH2Cl2. The extractive was washed with saturated
NaHCO3 and precipitated into 50 mL methanol twice. The
precipitate was filtered and dried in vacuo at 40 °C for 4 h to give
25
365
0.445 g of (89 % yield) Poly-10 as a white powder. [
α]
= -299
(c =1 mg/mL, THF). Mn = 6.52 × 103, PDI = Mw/Mn = 1.46. IR:
3523, 3022, 2921, 2354, 1501, 1006 cm-1; H NMR (400 MHz) δ
1
7.95 (br), 7.38 (br), 7.05 (br), 6.58 (br), 5.08 (br), 1.84 (br), 1.42
(br).
Synthesis of (S)-3-(4-vinyphenyl)-2,2′-bis(methoxymethyl)-
1,1′- binaphthalene (S-11)
Recovery experiment of Poly-5a
The recovered filtrated cake (1.0 g) was ground into powder
and redissolved in 10 mL THF. The mixture was filtrated, the
filtrate was poured into 100 mL methanol. The precipitate was
washed with methanol several times and dried in vacuo at 40 °C
for 4 h to obtain the recovered Poly-5a, yield 95%. The recovered
Poly-5a was used for the asymmetric addition experiment again
to study the catalytic activity.
A mixture of (S)-3 (0.301 g) and 10 mol% Pd-C catalyst
(0.021 g) in 10 mL THF was add to a small autoclave. The
mixture was filled with hydrogen (0.3 MPa). The reaction
continued for 24 h at 110 C. After being cooled to room
temperature, the mixture was filtrated and the filtrate was
evaporated in vacuo to afford the pure product 0.291 g (98%
o
yield) of (S)-3-(4-vinyphenyl)-2,2′-bis(methoxymethyl)-1,1′-
binaphthalene (11) as a white crystal. m.p. 79.3-81.1 oC. [
α]
365 = -
Determination of alcohol enantiomeric excesses
25
436(c = 1 mg/mL, THF). Elem. Anal. Calcd. for C32H30O4: C
80.31, H 6.32; Found: C 80.29, H 6.33. IR: 3046, 2944, 2354,
The ee of the product was determined by chiral HPLC analysis
using a chiral stationary phase column (Chiralcel OD-H).
1
1716, 1233, 1000 cm-1; H NMR (400 MHz) δ 7.97-7.85 (m, 4H),
7.62 (dd, J = 18.1, 8.3 Hz, 3H), 7.37 (dd, J = 13.3, 5.5 Hz, 2H),
7.32-7.21 (m, 6H), 5.17 (d, J = 6.7 Hz, 1H), 5.07 (d, J = 6.8 Hz,
1H), 4.35 (d, J = 5.5 Hz, 1H), 4.30 (d, J = 5.6 Hz, 1H), 3.22 (s,
3H), 2.74 – 2.68 (m, 2H), 2.28 (s, 3H), 1.28 (t, J = 7.5 Hz, 3H).
13C NMR (100 MHz) δ 153.04, 151.25, 143.40, 136.47, 135.65,
134.26, 133.32, 131.15, 130.32, 129.84, 129.71, 129.68, 128.07,
For 1-Phenyl-1-propanol: n-hexane/isopropanol = 99/1, f = 0.8
mL/min, tR = 10.335 min, tS = 13.723 min. For 1-(2-
Methoxyphenyl)-1-propanol: n-hexane/isopropanol = 98/2, f =
0.8 mL/min, tR = 10.505 min, tS = 9.007 min. For 1-(3-
Methoxyphenyl)-1-propanol: n-hexane/isopropanol= 99/1, f = 1
mL/min, tR = 18.693 min, tS = 21.602 min. For 1-(4-
Chlorophenyl)-1-propanol: n-hexane/isopropanol = 99.8/0.2, f =

6
Tetrahedron
ACCEPTED MANUSCRIPT
4. (a) Dickerson, T.J.; Reed, N. N.; Reed, K. D. Janda, Chem. Rev.
0.7 mL/min, tR = 14.587 min, tS = 24.387 min. For 1-(4-
2002, 102, 3325-3544; (b) Fan, Q. H.; Li, Y. M.; Chan, A. S. C.
Chem. Rev. 2002, 102, 3385-3446
Bromo)-1-propanol: n-hexane/isopropanol = 99.8/0.2, f = 1
mL/min, tR = 9.380 min, tS = 10.590 min. For 1-Phenyl-1-penten-
3-ol: n-hexane/isopropanol = 90/10, f = 1.0 mL/min, tR = 10.432
5. An, W. K.; Han, M. Y.; Wang, C. A.; Yu, S. M.; Zhang, Y.; Bai,
S.; Wang, W. Chem. Eur. J. 2014, 20, 11019-11028.
min, tS
hexane/isopropanol = 90/10, f = 1.0 mL/min, tR = 4.468 min, tS =
7.115 min. For 1-(4-Phenylphenyl)-1-propanol: n-
hexane/isopropanol = 99.5/0.5, f = 0.5 mL/min, tR = 70.11 min, tS
63.532 min. For 1-(1-Naphthyl)-1-propanol: n-
hexane/isopropanol = 90/10, f = 1.0 mL/min, tR = 18.898 min, tS
11.665 min. For 1-(2-Naphthyl)-1-propanol: n-
hexane/isopropanol = 98/2, f = 0.8 mL/min, tR = 28.120 min, tS =
22.698 min. For 1-(9-Anthracy)-1-propanol: n-
=
16.580 min. For 1-Phenyl-3-pentanol: n-
6. Chen, Y.; Yekta, S.; Yudin, A. K. Chem. Rev. 2003, 103, 3155-
3211.
7. (a) Fan, Q. H.; Ren, C. Y.; Yeung, C. H.; Hu, W. H.; Chan, A. S.
C. J. Am. Chem. Soc. 1999, 121, 7407-7408. (b) Jayaprakash, D.;
Sasai, H.; Tetrahedron: Asymmetry 2001, 12, 2589-2595. (c)
Jayaprakash, D.; Kobayashi, Y.; Arai, T.; Hu, Q. H.; Zheng, X. F;
Pu, L.; Sasai, H. J. Mol. Catal. A: Chem. 2003, 196, 145-149. (d)
Arai, T.; Hu, Q. H.; Zheng, X. F; Pu, L.; Sasai, H. Org. Lett. 2000.
26. 4261-4263.
=
=
8. (a)Yu, H. B.; Hu, Q. S.; Pu, L. Tetrahedron Lett. 2000, 41, 1681-
1685. (b) L. Pu, Chem. Rev. 1998, 98, 2405-2494.
hexane/isopropanol = 99/1, f = 0.6 mL/min, tR = 35.621 min, tS =
51.842min.
9. (a) Zhang, A. L.; Yu, Z. D.; Yang, L. W.; Yang, N. F.
Tetrahedron: Asymmetry 2015, 26, 173-179. (b) Zhang, A. L.; Yu,
Z. D.; Yang, L. W.; Yang, N. F.; Peng, D. J. Mol. Catal. A: Chem.
2015, 398, 407-412. (c) Cheng, Y. H.; Qin, G. C.; Yang, L. W.;
Yang, N. F. Chin. J. Chem. 2015, 33, 436-466. (d) Huang, C.W.;
Yang, N. F.; Zhang, A. L.; Yang, L. W. Polymer 2012, 53, 3514-
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10. Recsei, C.; McErlean, C. S. P. Tetrahedron 2012, 68, 464-480.
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Gau, H. M.; You, J. S. Chem. Eur. J. 2008, 14, 2223-2231.
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Acknowledgments
We are grateful to the National Science Foundation of China
(21172186) and the Higher Education Doctoral Science
Foundation of China (No. 20134301110004) for financial support
of this work.
Supplementary data
13. Yamada, Y. M. A.; Ichinohe, M.; Takahashi, H.; Ikegami, S.
Tetrahedron Lett. 2002, 43, 3431-3434.
14. Liu, G. H.; Tang, W. J.; Fan, Q. H. Tetrahedron 2003, 59, 8603-
8611.
Supplementary data (1H NMR , 13C NMR and IR spectra of
the new compounds) associated with this article can be found in
the online version, at http://dx.doi.org/.
15. (a)Fernández-Mateos, E.; Maciá, B.; Yus. M. Tetrahedron:
Asymmetry 2012, 23, 789-794. (b)Biswas, K.; Prieto, O.;
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