Two modes of asymmetric polymerization of phenylacetylenes having an L -amino alcohol residue and two hydroxy groups

Article abstract of DOI:10.1002/pola.26346

Four novel chiral phenylacetylenes having an L-amino alcohol residue and two hydroxymethyl groups were synthesized and polymerized by an achiral catalyst ((nbd)Rh⁺[η⁶-(C₆H₅)B ^-(C₆H₅)₃]) or a chiral catalytic system ([Rh(nbd)Cl]₂/(S)- or (R)-phenylethylamine ((S)- or (R)-PEA)). The two resulting polymers having an L-valinol or L-phenylalaninol residue showed Cotton effects at wavelengths around 430 nm. This observation indicated that they had an excess of one-handed helical backbones. Positive and negative Cotton effects were observed only for the polymers having an L-valinol residue produced by using (R)- and (S)-PEA as a cocatalyst, respectively, although the monomer had the same chirality. Even when the achiral catalyst was used, the two resulting polymers having an L-valinol or L-phenylalaninol residue showed Cotton effects despite the long distance between the chiral groups and the main chain. We have found the first example of a new type of chiral monomer, that is, a chiral phenylacetylene monomer having an L-amino alcohol residue and two hydroxy groups that was suitable for both modes of asymmetric polymerization, that is, the helix-sense-selective polymerization (HSSP) with the chiral catalytic system and the asymmetric-induced polymerization (AIP) with the achiral catalyst. The other two monomers having L-alaninol and L-tyrosinol were found to be unsuitable to neither HSSP nor AIP because of their polymers' low solubility.

Full text of DOI:10.1002/pola.26346

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Two Modes of Asymmetric Polymerization of Phenylacetylenes Having an
L-Amino Alcohol Residue and Two Hydroxy Groups
Hongge Jia,1 Jun Li,2 Yu Zang,2 Toshiki Aoki,2,3,4 Masahiro Teraguchi,2,3,4 Takashi Kaneko2,3,4
1Department of Polymeric Material and Engineering, Qiqihar University, Wenhua Street 42, Qiqihar 161006, China
2Department of Chemistry and Chemical Engineering, Graduate School of Science and Technology, Niigata University, Ikarashi
2-8050, Nishi-Ku, Niigata 950-2181, Japan
3Center for Education and Research on Environmental Technology, Materials Engineering, Nanochemistry, Niigata University,
Ikarashi 2-8050, Nishi-Ku, Niigata 950-2181, Japan
4Center for Transdisciplinary Research, Niigata University, Ikarashi 2-8050, Nishi-Ku, Niigata 950-2181, Japan
Correspondence to: T. Aoki (E-mail: toshaoki@eng.niigata-u.ac.jp)
Received 20 May 2012; accepted 16 August 2012; published online
DOI: 10.1002/pola.26346
ABSTRACT: Four novel chiral phenylacetylenes having an L-amino
alcohol residue and two hydroxymethyl groups were synthesized
and polymerized by an achiral catalyst ((nbd)Rhþ[g6-
(C6H5)Bꢀ(C6H5)3]) or a chiral catalytic system ([Rh(nbd)Cl]2/(S)- or
(R)-phenylethylamine ((S)- or (R)-PEA)). The two resulting poly-
mers having an L-valinol or L-phenylalaninol residue showed Cot-
ton effects at wavelengths around 430 nm. This observation
indicated that they had an excess of one-handed helical back-
bones. Positive and negative Cotton effects were observed only
for the polymers having an L-valinol residue produced by using
(R)- and (S)-PEA as a cocatalyst, respectively, although the mono-
mer had the same chirality. Even when the achiral catalyst was
used, the two resulting polymers having an L-valinol or L-phenyla-
laninol residue showed Cotton effects despite the long distance
between the chiral groups and the main chain. We have found
the first example of a new type of chiral monomer, that is, a chiral
phenylacetylene monomer having an L-amino alcohol residue
and two hydroxy groups that was suitable for both modes of
asymmetric polymerization, that is, the helix-sense-selective
polymerization (HSSP) with the chiral catalytic system and the
asymmetric-induced polymerization (AIP) with the achiral cata-
lyst. The other two monomers having L-alaninol and L-tyrosinol
were found to be unsuitable to neither HSSP nor AIP because of
C
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their polymers’ low solubility.
2012 Wiley Periodicals, Inc.
J Polym Sci Part A: Polym Chem 000: 000–000, 2012
KEYWORDS: asymmetric polymerization; catalysts; chiral; conju-
gated polymers; initiators; L-amino alcohol; polyacetylenes
INTRODUCTION Conjugated polymers like polyacetylenes
have aroused interest because of their noteworthy physical
properties such as conductivity, organomagnetism, and opti-
cal nonlinear susceptibility. Recently, chiral polyacetylenes
have received much attention as the chiral structure can
enhance the unique properties and add new functions.1
similar to that of p-{L-(ꢀ)-menthoxycarbonyl}phenylacety-
lene.1 Similar results were also reported by other
researchers.3
To investigate the effects of position of the chiral groups in
the monomers on the induction of chirality in the main-chain
during polymerization, several oligosiloxanylphenylacetylenes
having one or two bulky chiral pinanyl groups at the 1-, 3-,
and/or 5-position of an oligosiloxane chain were polymer-
ized with a Rh complex to produce high-molecular-weight
polymers.2(g) The polymers with a chiral pinanyl group at
the 1-position of an oligosiloxanyl group showed high molar
ellipticity in the main-chain region in the CD spectra. On the
other hand, the polymers from monomers with a chiral
pinanyl group at the 3- or 5-position of an oligosiloxanyl
group showed almost no CD absorptions. Therefore, to real-
ize the AIP, the chiral group should be substituted at a posi-
tion close to the polymerizable group in the monomers. In
this AIP, the sign of the chirality of the formed main-chain
In 1993, the authors accidentally found an asymmetric-
induced polymerization (AIP) that induced a one-handed
helical chirality in the main-chain during polymerization of a
phenylacetylene having a bulky chiral L-menthoxycarbonyl
group.1(h) After this finding, the authors synthesized and poly-
merized many other phenylacetylenes and diphenylacetylenes
having a chiral substituent to check whether a main-chain
chirality was induced.2 As a result, many chiral monomers
were found to be suitable for the AIP. For example, the homo-
polymers of (ꢀ)-p-(dimethyl(10-pinanyl)silyl)phenylacety-
lene2(a) and (þ)-p-(10-pinanyloxycarbonyl)phenylacetylene2(g)
obtained with a Rh complex showed strong CD absorptions
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was strongly affected by the sign of the chirality of the chiral
group. Therefore, only two kinds of chiral polymers, that is,
the enantiomers, PD and ML (or PL and MD),4 could be
obtained from the enantiomeric monomers by AIP. In other
words, it was impossible to synthesize their diastereomers.
In 2003, the authors have also found a simple and novel syn-
thetic method for obtaining such a chiral polymer from an
achiral substituted acetylene monomer by using a chiral cata-
lytic system.5 In addition, the helical conformation was stable
in solution. This is the first example of helix-sense-selective
polymerization (HSSP) of substituted acetylenes, whose chiral
helicity is stable in solution without the aid of other chiral sub-
stituents or other small molecules. The authors polymerized
an achiral phenylacetylene having two hydroxyl groups and a
dodecyl group (DoDHPA) by using a chiral catalytic system
consisting of a rhodium dimeric complex, [Rh(nbd)Cl]2 (nbd ¼
2,5-norbornadiene), as a catalyst, and a chiral amine, (R)-1-
phenylethylamine ((R)-PEA), as a cocatalyst. The polymer
showed Cotton effects at wavelengths around 430 and 310
nm, where there are no UV absorptions of DoDHPA and (R)-
PEA.5(a, b) On the other hand, no HSSPs occurred in the case of
the corresponding monomers having no hydroxy groups.
Therefore, two hydroxy groups were found to be necessary to
realize the HSSP. In this polymerization, the sense of the main-
chain helicity was governed by the sign of the chirality of the
cocatalyst used. In this case also, only the pair of the enan-
tiomers (M and P)4 could be produced.
CHART 1 Chemical structures of the chiral monomers
(RDHPAs and VPA).
20
(c ¼ 2, H2O)), and L-tyrosine (Tyr, [a]D : ꢀ10.2ꢁ (c 4, 1
molLꢀ1 HCl)) purchased from Junsei Chemical Co., were used
as received.
Synthetic Procedures and Characterization of Monomers
(ADHPA, VDHPA, PDHPA, TDHPA, and VPA)
All the following reaction procedures were conducted under
dry nitrogen (Schemes 1–4).
These monomers described above were suitable only for the
AIP or the HSSP. There had been no monomers which were
suitable for both asymmetric polymerizations. Therefore, we
reported new monomers suitable to both modes of asym-
metric polymerization, that is, HSSP and AIP for the first
time. They were chiral hydrophobic phenylacetylene mono-
mers having an O-octylated amino alcohol residue.5(m)
1. L-Alaninol (Scheme 1) (1)6,8
A mixture of Ala (5.00 g, 56.1 mmol) in dry tetrahydro-
furan (THF) (40 mL) was added slowly to a mixture of
lithium aluminum ꢁhydride (3.20 g, 84.2 mmol) in dry
THF (40 mL) at 0 C. After the mixture was refluxed for
12 h, water (5 mL) was added slowly. The mixture was
filtered, and the solvent was removed. The crude prod-
uct was purified by vacuum distillation to give 1 as col-
orless liquid. Yield: 51.1% (2.11 g). Bp: 55 ꢁC (6.8
In this study, to develop new monomers which can be used
for both modes of asymmetric polymerizations, that is, AIP
and HSSP, novel chiral monomers RDHPAs (ADHPA, VDHPA,
PDHPA, and TDHPA, Chart 1) were designed and synthe-
sized. Monomers RDHPAs contain two hydroxy groups and a
chiral group, an L-amino alcohol residue, which was intro-
duced via a relatively long spacer. We previously reported
that VDHPA was suitable to both AIP and HSSP.6 In this arti-
cle, effects of the kind of amino alcohol residues in RDHPAs
on the two modes of asymmetric polymerizations will be
discussed.
20
1
mmHg). [a]D : þ8.5ꢁ (c 0.10, THF). H NMR (270 MHz,
CDCl3, d, ppm): 3.52 and 3.24 (2dd, 2H, CH2OH), 3.01
(m, 1H, NH2CH), 2.51 (b, 3H, NH2 and OH), 1.06 (d, 3H,
J ¼ 6.2 Hz, CH3).
2. L-Valinol (2) (Scheme 1)6,8
According to the literature procedure, 2 was prepared.
Yield: 57.5%. Bp: 42 ꢁC (0.32 mmHg). Appearance: col-
orless liquid. [a]D : þ11ꢁ (c ¼ 0.10, THF). 1H NMR
20
EXPERIMENTAL
(270 MHz, CDCl3, d, ppm): 3.60 and 3.25 (2dd, 2H,
CH2OH), 2.52 (m, 1H, NH2CH), 1.87 (b, 3H, NH2 and
OH), 1.55 (m, 1H, CH(CH3)2), 0.87 and 0.90 (2d, 6H, J ¼
3.4 Hz, CH(CH3)2).
Materials
All the solvents used for synthesis and polymerizations of
the monomers were distilled as usual. The polymerization
initiator, [Rh(nbd)Cl]2 (nbd ¼ 2,5-norbornadiene), purchased
from Aldrich Chemical Co., was used as received. According
to the literature procedures, (nbd)Rhþ[g6-(C6H5)Bꢀ(C6H5)3]
3. L-Phenylalaninol (3) (Scheme 1)6,8
A similar procedure as described for 1 was used. After
the reaction, the mixture was filtered, and the solution
was concentrated to give a solid residue. The crude
product was dissolved in ethyl acetate, and the solution
was washed with brine. The water layer was extracted
was prepared.7 L-Alanine (Ala, [a]D : þ14.3ꢁ ꢂþ15.2ꢁ (c 1,
20
20
6 molLꢀ1 HCl)), L-valine (Val, [a]D : þ27.6ꢁ ꢂþ28.7ꢁ (c 8, 6
molLꢀ1 HCl)), L-phenylalanine (Phe, [a]D : ꢀ33.5ꢁ ꢂꢀ35.0ꢁ
20
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SCHEME 1 Synthetic route to RDHPAs (ADHPA, VDHPA, PDHPA, and TDHPA).
A solution of 6 (1.72 g, 8.81 mmol), di(t-butyl)dicarbon-
ate (Boc2O, 2.12 g, 9.69 mmol), and triethylamine (2.5
mL) in methanol (10 mL) was stirred for 17 h at room
temperature. After the solution was concentrated, the
crude product was purified by silica-gel column chroma-
tography to give 7 as white solid. Yield: 77.3% (2.00 g).
Rf: 0.36 (chloroform:methanol:acetic acid ¼ 97:2:1).
with ethyl acetate. The organic layer was dried over
MgSO4 and concentrated to give 3 as yellow solid. Yield:
46.1%. [a]D : ꢀ28ꢁ (c ¼ 0.10, THF). 1H NMR (270
20
MHz, CDCl3, d, ppm): 7.34–7.17 (m, 5H, phenyl), 3.64
and 3.38 (2dd, 2H, CH2OH), 3.10 (m, 1H, NH2CH), 2.80
and 2.52 (2dd, 2H, PhCH2), 2.10 (b, 3H, NH2 and OH).
Because Tyr was insoluble in THF, L-tyrosinol (4,
Scheme 1) could not be prepared according to a similar
procedure as described for 1. As shown in Scheme 2, 4
was prepared as follows.
[a]D : 18ꢁ (c ¼ 2.0, methanol). 1H NMR (270 MHz,
20
CDCl3, d, ppm): 6.96 (d, 2H, J ¼ 8.6 Hz,
), 6.72 (d,
4.. L-Tyrosine methyl ester (6) (Scheme 2)9
A solution of Tyr (1.80 g, 9.94 mmol) in dry methanol
(5.0 mL) was added dropwise to a solution of SOCl2
2H, J ¼ 8.6 Hz, ), 4.97 (b, 1H, PhOH), 4.50 (m, 1H,
ꢁ
NHCH), 3.70 (s, 3H, OCH3), 3.00 and 2.98 (2dd, 2H,
PhCH2), 1.40 (s, 9H, C(CH3)3).
(2.6 mL) in dry methanol (5.0 mL) at ꢀ10 C. The solu-
tion was stirred for 48 h at room temperature. After the
solution was concentrated, the crude production was
purified by crystallization in methanol to give 6 as white
6.. L-N-t-butyloxycarbonyltyrosinol (8) (Scheme 2)6,8
A similar procedure as described for 1 was applied. Af-
ter the reaction, the mixture was filtered, and the solu-
tion was concentrated to give a solid residue. The crude
product was dissolved in ethyl acetate, and the solution
was washed with brine. The water layer was extracted
with ethyl acetate. The organic layer was dried over
MgSO4 and concentrated to give 8 as white solid. Yield:
20
solid. Yield: 88.7% (1.72 g). [a]D : 26ꢁ (c ¼ 2.0, metha-
nol). 1H NMR (270 MHz, CD3OD, d, ppm): 7.02 (d, 2H,
J ¼ 8.6 Hz,
), 6.73 (d, 2H, J ¼ 8.6 Hz,
),
4.19 (m, 1H, NH2CH,), 3.77 (s, 3H, OCH3), 3.10 and 3.00
(2dd, 2H, PhCH2).
20
69.6%. [a]D : ꢀ16ꢁ (c ¼ 2.0, methanol). 1H NMR (270
5. L-N-t-butyloxycarbonyltyrosine methyl ester (7) (Scheme
2)9
MHz, CDCl3, d, ppm): 7.03 (d, 2H, J ¼ 8.3 Hz,
),
SCHEME 2 Synthetic route to L-tyrosinol (4).
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SCHEME 3 Synthetic route to Compound 5.
According to the method we reported before, 5 was pre-
pared. Total yield (based on p-bromophenol): 25.0%.
Appearance: yellow liquid. Rf: 0.69 (ethyl acetate:hexane
¼ 2:1). H NMR (270 MHz, CDCl3, d, ppm): 10.04 (s, 1H,
6.73 (d, 2H, J ¼ 8.3 Hz,
), 4.71 (b, 1H, PhOH), 3.80
(m, 1H, NHCH), 3.64 and 3.50 (2dd, 2H, CH2OH), 2.72
(d, 2H, J ¼ 7.2 Hz, PhCH2), 1.40 (s, 9H, C(CH3)3).
1
7. L-Tyrosinol (4) (Scheme 2)9
CHO), 7.92 (d, 2H, J ¼ 8.3 Hz,
), 7.61 (d, 2H, J ¼
A solution of 8 (1.18 g, 4.45 mmol) and trifluoroacetic
acid (10 mL) in CH2Cl2 (10 mL) was stirred for 20 h at
room temperature. After NaHCO3 aqueous (1 molLꢀ1, 50
mL) was added, the mixture was extracted with brine
and CH2Cl2. The organic layer was dried over MgSO4
and concentrated. Then, the crude product was purified
by recrystallization in ethyl acetate to give 4 as yel-
8.3 Hz, ), 7.51 (s, 2H,
), 5.07 (s, 2H,
PhOCH2Ph), 4.67 (d, 4H, J ¼ 5.9 Hz, Ph(CH2OH)2), 1.88
(t, 2H, J ¼ 5.9 Hz, Ph(CH2OH)2), 0.24 (s, 9H, Si(CH3)3).
9. (þ)-4-[4-{(2-Hydroxy-1-methyl)ethylaminomethyl}benzy-
loxy]-3,5-bis(hydroxymethyl) phenylacetylene (ADHPA)
(Scheme 1)6,10,11
20
low solid. Yield: 79.0% (0.587 g). [a]D : ꢀ13ꢁ (c ¼
2.0, methanol). 1H NMR (270 MHz, CDCl3, d, ppm):
A solution of 5 (1.22 g, 3.32 mmol), 1 (0.248 g, 3.32
mmol) in dry methanol (30 mL) was stirred in the pres-
ence of molecular sieves 4 Å (3.0 g) for 24 h at room
temperature. Sodium tetrahydroborate (0.126 g, 3.32
mmol) was added, which was stirred for 36 h again. Af-
ter the solution was filtered, the solvent was removed.
The crude product was purified by silica-gel column
chromatography to give ADHPA as white solid. Yield:
7.06 (d, 2H, J ¼ 8.6 Hz,
), 6.77 (d, 2H, J ¼ 8.6
Hz, ), 6.56 (b, 1H, PhOH), 4.16 (m, 1H, NH2CH),
3.70 and 3.66 (2dd, 2H, CH2OH), 2.86 (d, 2H, J ¼ 7.2 Hz,
PhCH2).
8. 4-{4-Trimethylsilylethynyl-2,6-(bishydroxymethyl)-1-phe-
noxymethyl}benzaldehyde (5) (Scheme 3)5(a, b),6
50.0% (0.580 g). Rf: 0.10 (chloroform:methanol
¼
20
4:1). [a]D : 12ꢁ (c ¼ 0.10, THF). 1H NMR (270 MHz,
SCHEME 4 Synthetic route to VPA.
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CHCH2OH), 3.17 (s, 1H, HCBC), 2.68 (m, 2H, PhCH2CH),
1.91 (m, 1H, NHCH). IR (cmꢀ1, KBr): 3285, 2928,
2881, 2360, 1790, 1700, 1631, 1600, 1516, 1477,
1423, 1405, 1367, 1310, 1285, 1227, 1146, 1111, and
947.
DMSO-d6, d, ppm): 7.47 (s, 2H,
),7.38 (b, 4H,
), 5.20 (b, 3H, Ph(CH2OH)2 and CHCH2OH), 4.82
13. (ꢀ)-4-[4-{(2-hydroxy-1-isopropyl)ethylaminomethyl}ben-
zyloxy]phenylacetylene (VPA) (Scheme 4)6,10,11
According to the method we reported before, VPA was
prepared. Yield: 79.1%. Appearance: white solid. Rf: 0.30
(s, 2H, PhOCH2Ph), 4.52 (s, 4H, Ph(CH2OH)2), 4.08 (b,
1H, NH), 3.75 (2d, 2H, J ¼ 13 Hz, PhCH2NH), 3.27 (m,
2H, CHCH2OH), 3.16 (s, 1H, HCBC), 2.62 (m, 1H, NHCH),
0.94 (d, 3H, J ¼ 6.2 Hz, CHCH3). IR (cmꢀ1, KBr): 3263,
2967, 2926, 2855, 1728, 1630, 1599, 1516, 1456, 1420,
1362, 1346, 1293, 1269, 1209, 1141, 1106, 1067, 1050,
1029.
20
(chloroform:methanol ¼ 8:1). [a]D : ꢀ13ꢁ (c ¼ 0.10,
THF). 1H NMR (270 MHz, CDCl3, d, ppm): 7.42 (d, 2H,
J ¼ 8.7 Hz,
), 7.38 (b, 4H,
), 6.89 (d, 2H,
10. (ꢀ)-4-[4-{(2-Hydroxy-1-isopropyl)ethylaminomethyl}-
benzyloxy]-3,5-bis(hydroxymethyl)
phenylacetylene
(VDHPA) (Scheme 1).6,10,11
J ¼ 8.7 Hz,
), 5.03 (s, 2H, PhOCH2Ph), 3.80 (2d, 2H,
According to the method we reported before, VDHPA
was prepared. Yield: 64.0%. Appearance: white solid. Rf:
J ¼ 13 Hz, PhCH2NH), 3.63 and 3.38 (2dd, 2H, CH2OH),
2.98 (s, 1H, HCBC), 2.48(m, 1H, NHCH), 2.15 (b, 2H,
OH and NH), 1.87 (m, 1H, CH(CH3)2), 0.96 and 0.90
(2d, 6H, J ¼ 6.8 Hz, CH(CH3)2). IR (cmꢀ1, KBr): 3277,
3156, 2958, 2927, 2871, 2097, 1604, 158, 1506, and
1468.
20
0.29 (chloroform:methanol ¼ 4:1). [a]D : ꢀ71ꢁ (c ¼
0.50, THF). 1H NMR (270 MHz, CDCl3, d, ppm): 7.49 (s,
2H,
), 7.34 (b, 4H,
), 4.95 (s, 2H,
PhOCH2Ph), 4.57 (s, 4H, Ph(CH2OH)2), 3.79 (2d, J ¼ 13
Hz, 2H, PhCH2NH), 3.58 and 3.33 (2dd, 2H, CHCH2OH),
3.03 (s, 1H, HCBC), 2.44 (m, 1H, NHCH), 1.86 (m, 5H,
Ph(CH2OH)2, CHCH2OH, NH and CH(CH3)2), 0.97 and
0.90 (2d, 6H, J ¼ 6.8 Hz, CH(CH3)2). IR (cmꢀ1, KBr):
3246, 2954, 2874, 2104, 1608, 1459, 1364, 1291, 1205,
1135, and 1063.
Polymerizations
The AIP and the HSSP were performed by an achiral cata-
lyst, (nbd)Rhþ[g6-(C6H5)Bꢀ(C6H5)3] and a chiral catalytic
system, [Rh(nbd)Cl]2 (nbd ¼ 2,5-norbornadiene)/(R)- or (S)-
PEA, respectively.5,6
1. Polymerizations of VDHPA5,6
11.. (ꢀ)-4-[4-{(2-Hydroxy-1-benzyl)ethylaminomethyl}benzy-
loxy]-3,5-bis(hydroxymethyl) phenylacetylene (PDHPA)
(Scheme 1)6,10,11
A solution of [Rh(nbd)Cl]2 (0.24 mg, 0.52 lmol) and an
amine such as (R)-phenylethylamine (35 lL, 0.26 mmol)
in THF (0.65 mL) was added to a solution of monomer
VDHPA (50 mg, 0.13 mmol) in THF (0.65 mL). The reac-
tion solution was stirred at room temperature for 4 h.
The formed polymer was purified by precipitation of the
polymerization solution into a large amount of acetone
and dried in vacuum to give a red polymer. The other pol-
ymerizations of VDHPA were also conducted similarly by
using (nbd)Rhþ[g6-(C6H5)Bꢀ(C6H5)3]. For the other data
such as yield, Mw, and CD, see Table 1 and Figure 1.
2. Polymerizations of ADHPA5,6
A similar procedure as described for ADHPA was
applied. Yield: 67.0%. Appearance: white solid. Rf: 0.20
20
(chloroform:methanol ¼ 4:1). [a]D : ꢀ13ꢁ (c ¼ 0.10,
THF). 1H NMR (270 MHz, CDCl3, d, ppm): 7.49 (s, 2H,
), 7.40–7.14 (m, 9H, Phenyl), 4.93 (s, 2H,
PhOCH2Ph), 4.59 (s, 4H, Ph(CH2OH)2), 3.74 (2d, 2H, J ¼
13 Hz, PhCH2NH), 3.57 and 3.29 (2dd, 2H, CHCH2OH),
3.02 (s, 1H, HCBC), 2.90 (m, 1H, NHCH), 2.77 (dd, 2H,
PhCH2CH), 2.00 (b, 4H, Ph(CH2OH)2, CHCH2OH and NH).
IR (cmꢀ1, KBr): 3289, 3025, 2925, 2828, 2107, 1633,
1602, 1514, 1495, 1454, 1419, 1357, 1203, 1134, 1115,
1067, and 1036.
A similar procedure as described for polymerization of
VDHPA was applied. The formed polymer was purified by
precipitation of the polymerization solution into a large
amount of acetone and dried in vacuum to give a red
polymer. For the other data such as yields, Mw, and CD,
see Table 1.
12. (ꢀ)-4-[4-{2-Hydroxy-1-(4-hydroxybenzyl)ethylaminomethyl}
benzyloxy]-3,5-bis(hydroxymethyl) phenylacetylene (TDHPA)
(Scheme 1)6,10,11
3. Polymerizations of PDHPA5,6
A similar procedure as described for ADHPA was
applied. Yield: 71.0%. Appearance: white solid. Rf: 0.24
A similar procedure as described for polymerization of
VDHPA was applied. The formed polymer was purified by
precipitation of the polymerization solution into a large
amount of acetone and dried in vacuum to give a red
polymer. The other polymerization procedure was also
20
(chloroform:methanol ¼ 2:1). [a]D : ꢀ11ꢁ (c 0.1, THF).
1H NMR (270 MHz, DMSO-d6, d, ppm): 7.48 (s, 2H,
), 7.44–7.18 (m, 8H, Phenyl), 5.25 (b, 4H,
applied. For example,
a
solution of (nbd)Rhþ[g6-
(C6H5)Bꢀ(C6H5)3] (0.24 mg, 0.52 lmol) and monomer
PDHPA (50 mg, 0.12 mmol) in THF (1.17 mL) was stirred
at room temperature for 4 h. During polymerization, the
Ph(CH2OH)2, CHCH2OH and PhOH), 4.83 (s, 2H,
PhOCH2Ph), 4.55 (s, 4H, Ph(CH2OH)2), 4.10 (m, 1H, NH),
3.77 (2d, 2H, J ¼ 13 Hz, PhCH2NH), 3.37 (m, 2H,
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TABLE 1 Polymerizations of RDHPAs and VPA by Using Achiral or Chiral Catalytic Systemsa
No.
Chiral Monomer
Polymer
b
b
20
20
d
½aꢃD
½aꢃD
[h]310
Chiral
Yield Mw
c
Code
ADHPA 12
THF DMF Catalyst
Cocatalyst (%)
(ꢄ 104)c Mw=Mn
THF DMF
THF DMF
e
e
1
3.0
(nbd)Rhþ[g6ꢀ(C6H5)Bꢀ(C6H5)3] None
82.4
5.0
0.5
6.2
5.2
3.5
10.0
6.2
3.9
3.7
4.2
1.1
3.1
2.8
2.7
1.6
0.9
5.5
1.2
1.5
4.6
2.2
6.0
2.2
4.3
3.2
1.7
9.9
7.1
1.7
3.0
4.0
—
—
—
ꢀ85
ꢀ24
ꢀ18
—
—
—
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
e
e
e
e
2
[Rh(nbd)Cl]2
(R)-PEA
(S)-PEA
None
3
[Rh(nbd)Cl]2
(nbd)Rhþ[g6-(C6H5)Bꢀ(C6H5)3]
5.4
4
VDHPA ꢀ71 6.0
PDHPA ꢀ13 ꢀ15
TDHPA ꢀ11 ꢀ17
72.2
16.3
24.0
80.0
8.0
ꢀ11 ꢀ15
ꢀ3
5
[Rh(nbd)Cl]2
(R)-PEA
(S)-PEA
None
ꢀ28 ꢀ153 28
6
[Rh(nbd)Cl]2
(nbd)Rhþ[g6-(C6H5)Bꢀ(C6H5)3]
ꢀ12 ꢀ47
ꢀ28
e
7
—
—
—
—
—
—
ꢀ51
ꢀ85
ꢀ70
ꢀ159
ꢀ147
ꢀ130
32
20f
e
e
e
e
e
e
8
[Rh(nbd)Cl]2
(R)-PEA
(S)-PEA
None
—
e
9
[Rh(nbd)Cl]2
(nbd)Rhþ[g6-(C6H5)Bꢀ(C6H5)3]
6.0
—
e
10
11
12
13
14
15
a
74.0
4.0
—
e
[Rh(nbd)Cl]2
(R)-PEA
(S)-PEA
None
—
e
[Rh(nbd)Cl]2
(nbd)Rhþ[g6-(C6H5)Bꢀ(C6H5)3]
3.0
—
VPA
ꢀ13 10
71.9
15.5
12.3
ꢀ9
3
3
5
[Rh(nbd)Cl]2
(R)-PEA
(S)-PEA
d
ꢀ11 30
ꢀ20 35
[Rh(nbd)Cl]2
At room temperature in THF, [monomer] ¼ 0.1 molLꢀ1, [RDHPA]/[cata-
[h] ¼ ꢄ 10ꢀ3 (deg cm2)/dmol, c ¼ 1 mmolLꢀ1
Insoluble in THF.
.
e
f
lyst] ¼ 250, [VPA]/[catalyst] ¼ 100, [cocatalyst]/[catalyst] ¼ 500.
c ¼ 0.1 g dLꢀ1
.
In THF solution before reprecipitation.
b
c
Determined by GPC correlating polystyrene standard with DMF eluent.
solution had been homogeneous. The formed polymer
was purified by precipitation of the polymerization solu-
tion into a large amount of acetone and dried in vacuum
to give a red polymer. For the other data such as yield,
Mw, and CD, see Table 1 and Figure 3.
polymer. For the other data such as yield, Mw and CD, see
Table 1.
5. Polymerizations of VPA5,6
A similar procedure as described for polymerization of
VDHPA was applied. The formed polymer was purified by
precipitation of the polymerization solution into a large
amount of hexane and dried in vacuum to give a red poly-
mer. For the other data such as yield, Mw and CD, see Ta-
ble 1 and Figure 2.
4. Polymerizations of TDHPA5,6
A similar procedure as described for polymerization of
VDHPA was applied. The formed polymer was purified by
precipitation of the polymerization solution into a large
amount of acetone and dried in vacuum to give a red
FIGURE 1 CD and UV/vis spectra of poly(VDHPA) in THF pre-
pared by using (nbd)Rhþ[g6-(C6H5)Bꢀ(C6H5)3] and [Rh(nbd)Cl]2/
(R)- or (S)-PEA (Table 1, nos. 4–6).
FIGURE 2 CD and UV/vis spectra of poly(PDHPA) in THF pre-
pared by using (nbd)Rhþ[g6-(C6H5)Bꢀ(C6H5)3] (Table 1, no. 7).
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TABLE 2 Solubility of the Poly(RDHPA)s and Poly(VPA)a
polymer
CHCl3
THF
Methanol
DMF
DMSO
Acetone
Hexane
Poly(ADHPA)
Poly(VDHPA)
Poly(PDHPA)
Poly(TDHPA)
Poly(VPA)
a
ꢀ
ꢀ
ꢀ
ꢀ
þ
ꢀ
þþ
þ
þþ
þþ
þ
þþ
þ
þþ
þþ
þ
þþ
þ
þþ
þþ
þ
ꢀ
ꢀ
ꢀ
ꢀ
þ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
þ
þ
ꢀ
þþ
þþ: Soluble, þ: partly soluble, ꢀ: insoluble.
Measurements
presence of highly polar monomers (ADHPA and TDHPA)
than that in the presence of VDHPA and PDHPA, because
the amino groups of the monomers coordinated probably
with the rhodium. This speculation was supported by the
following result we reported. A chiral amino alcohol was
effective for the HSSP as a cocatalyst like (R)-PEA.5(c) How-
ever, the (nbd)Rhþ[g6-(C6H5)Bꢀ(C6H5)3] was hardly affected.
Therefore, the polymerization yields of all the monomers
were high (71.9%–82.4%) by using (nbd)Rhþ[g6-
(C6H5)Bꢀ(C6H5)3] and low (3.0%–24.0%) by using
[Rh(nbd)Cl]2/(R)- or (S)-PEA.
1H NMR (270 MHz) spectra were recorded on a JEOL LEO-
LEX-270 Spectrimeter. The average molecular weights (Mn
and Mw) were evaluated by gel permeation chromatography
using Hitachi 655A-11 liquid chromatograph instruments
(Polystyrene gel columns (Shodex GF-7M), DMF eluent, poly-
styrene calibration). CD spectra were recorded by using a
Jasco J-720WI spectropolarimeter with a Peltier controller
for temperatures at 20 ꢁC (a quartz cell of 1 mm path
length; sample concentration: 0.10–2.0 mM based on the
monomer unit). The specific rotations were recorded with
Polarimeter SEPA-200 (Horiba Co.). The infrared spectra
were recorded on FT/IR-4200 (JASCO Co.).
As shown in Table 2, all the five polymers were soluble in
polar solvents, such as methanol, DMF, and DMSO. The poly-
(VDHPA) and poly(PDHPA) were partly soluble in THF.
However, poly(ADHPA) and poly(TDHPA) were totally insol-
uble in THF. Therefore, it was found that the kind of amino
alcohol residues of the monomers affected yields, Mw, and
solubility of the resulting polymers. The polarity of poly-
(ADHPA) having L-alaninol residue with a methyl group is
higher than poly(VDHPA) containing L-valinol residue with
an isopropyl group. The polarity of poly(TDHPA) containing
L-tyrosinol residue with a hydroxylbenzyl group is higher
than poly(PDHPA) having L-phenylalaninol residue with a
benzyl group. Poly(ADHPA) and poly(TDHPA) are high polar,
and therefore, they were insoluble in low polar solvent like
THF and soluble in high polar solvents such as methanol,
DMF, and DMSO (Table 2). In summary, the low polar mono-
mers tended to give polymers with higher yields and Mws.
RESULTS AND DISCUSSION
Effect of the Kind of Amino Alcohol Residues on Yields
and Mw of Polymerizations and Solubility of the
Resulting Polymers
The monomers (ADHPA, VDHPA, PDHPA, TDHPA, and VPA;
Chart 1) were polymerized by using an achiral catalyst
(nbd)Rhþ[g6-(C6H5)Bꢀ(C6H5)3] and a chiral catalytic system
[Rh(nbd)Cl]2/(R)- or (S)-PEA, and the results are summar-
ized in Table 1.
VDHPA containing L-valinol residue was polymerized by
using [Rh(nbd)Cl]2/(R)- or (S)-PEA as a chiral catalytic sys-
tem to give polymers in 16.3% and 24.0% yields with 10.0
and 6.2 ꢄ 104 of Mw, respectively (Table 1, nos. 5 and 6).12
Polymerizations of ADHPA, PDHPA, and TDHPA by using
[Rh(nbd)Cl]2/(R)- or (S)-PEA as a catalytic system gave poly-
mers in lower yields (3.0%–8.0%) with a lower molecular
weight (2.8ꢀ6.2 ꢄ 104) (Table 1, nos. 2, 3, 8, 9, 11, and 12).12
The polymerizations of all the five chiral monomers
(RDHPAs and VPA) were also performed by using an achiral
catalyst (nbd)Rhþ[g6-(C6H5)Bꢀ(C6H5)3] without the chiral
cocatalyst to give polymers in high yields (71.9%–82.4%),
which were much higher than those in polymerizations by
using [Rh(nbd)Cl]2/(R)- or (S)-PEA as a catalytic system
(Yields: 3.0%–24.0%, Table 1). The molecular weights of
poly(VDHPA) and poly(PDHPA) were higher (3.5 and 3.9 ꢄ
104 in Table 1, nos. 4 and 7) than those of poly(ADHPA) and
poly(TDHPA) (0.5 and 1.1 ꢄ 104 in Table 1, nos. 1 and 10).
The differences may be because the amino groups of the
monomers decreased the stability of Rh-PEA complex as an
active species of the asymmetric polymerization. Stability of
the active species may be weakened more strongly in the
Achievement of AIP of the Chiral Monomers Using an
Achiral Catalytic System
We performed polymerization of RDHPAs using an achiral
catalyst (nbd)Rhþ[g6-(C6H5)Bꢀ(C6H5)3] without chiral cocata-
lysts to give polymers in high yields (Table 1, nos. 1, 4, 7,
and 10). The resulting poly(VDHPA) showed Cotton effects
at wavelengths assignable to the main chain (Table 1, no. 4,
Fig. 1), indicating that the polymer adopted a one-handed
helical conformation. The intensity of the CD absorptions
was relatively weak because the chiral groups were located
at a position far from the main chain.2(g) Poly(PDHPA)
obtained by using the achiral catalyst also showed CD
absorption at wavelengths assignable to the main chain (Ta-
ble 1, no. 7 and Fig. 2). The CD spectra of poly(VDHPA) and
poly(PDHPA) were measured in THF and chloroform. How-
ever, the other two poly(RDHPA)s, that is, poly(ADHPA) and
poly(TDHPA) were insoluble in THF and chloroform, and
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the polymerizations of chiral acetylenes reported,1–3 the chir-
alities of the main-chain and the chiralities of the monomer
substituent were not independent. Therefore, only their
enantiomers (ML or PL)4 could be synthesized. However, as
chiral VDHPA was suitable for the HSSP, the diastereomers
(ML and PL)4 can be obtained from the chiral monomer
VDHPA.
The [h] value of the point of intersection of the two CD
peaks of the both polymers obtained by using (R)- and (S)-
PEA was not zero but a positive value at 297 nm, and there-
fore, both the peaks were not completely mirror images of
each other (Fig. 1, nos. 5 and 6). This may be because poly-
(VDHPA) contains chiral amino alcohol residues, which can
affect the main-chain chirality. In addition, the chiral valinol
residue can coordinate with rhodium to affect the chiral
induction.5(c)
FIGURE 3 CD spectra of poly(VDHPA) in THF and DMF with
various ratio prepared by using [Rh(nbd)Cl]2/(S)-PEA (Table 1,
no. 6).
The CD spectra of the other three poly(RDHPA)s, that is,
poly(ADHPA), poly(PDHPA), and poly(TDHPA) could not be
detected, because those were insoluble in THF and chloro-
form. In addition, these polymers did not show CD absorp-
tions in polar solvents such as methanol, DMF, and DMSO,
because hydrogen bonds could not form in the solvents.
Therefore, they were not suitable to HSSP.
soluble in polar solvents such as methanol, DMF, and DMSO,
where they did not show CD absorptions. This was because
intramolecular hydrogen bonds between hydroxyl groups of
polyphenylacetylenes, which can maintain the one-handed
helical conformation of the polymers, could not form in these
polar solvents.5(a, b) In fact, all poly(RDHPA)s could not form
stable one-handed helical conformations in polar solvents,
such as methanol, DMF, and DMSO. The CD absorption of
poly(VDHPA) decreased and disappeared with adding DMF
to the solution of the polymers in THF (Fig. 3). In summary,
the one-handed helical polymers of VDHPA and PDHPA, that
is, relatively low polar monomer, were obtained by AIP with
an achiral catalyst.
In conclusion, only VDHPA of these four monomers
(RDHPAs) was suitable to both the HSSP by using the chiral
catalytic system and the AIP by using the achiral catalytic
system (Table 3). In other words, it polymerized in two
modes.
Role of the Two Hydroxyl Groups of Monomers
(RDHPAs)
We also synthesized and polymerized the corresponding chi-
ral monomer (VPA) of VDHPA lacking hydroxymethyl groups
(Chart 1). Poly(VPA) prepared by the achiral catalyst showed
CD absorption bands at wavelengths assignable to the main
chain (Table 1, no. 13 and Fig. 4). AIP of VPA was also
achieved. Poly(VPA)s prepared by the chiral catalytic system
(Table 1, nos. 14 and 15) and the achiral catalyst (Table 1,
no. 13) showed similar Cotton effects at wavelengths around
382 and 327 nm in chloroform (Fig. 4). The two polymers of
VPA prepared by using (R)-PEA and (S)-PEA showed almost
the same CD bands (Fig. 4, nos. 14 and 15), although PEAs
having opposite signs of configuration were used as a
It is noteworthy that VDHPA and PDHPA were suitable for
the AIP despite the relatively long distance between the chi-
ral groups and the main chain. These may be because this
spacer between the chiral group and the polymerizable
group was relatively rigid, at least more rigid than those
composed of a siloxane chain we described in the Introduc-
tion section and reported before.2(g)
Achievement of HSSP of the Chiral Monomer Using a
Chiral Catalytic System
The monomer (VDHPA) was also polymerized by using
[Rh(nbd)Cl]2 catalyst in the presence of a chiral amine coca-
talyst, (R)- or (S)-PEA, to give polymers having a moderate
molecular weight in moderate yields (Table 1, nos. 5 and 6).
As shown in Figure 1, the resulting poly(VDHPA) showed
absorption bands in CD at wavelengths around 430 and 306
nm, which are assigned to the one-handed helical main chain
and the chiral position between pendant groups, respectively.
These findings indicated the presence of an excess of a one-
handed helical polyacetylene backbone.
TABLE 3 Suitability of RDHPAs and VPA for Asymmetric
Polymerizationsa
Monomer
HSSPb
AIPc
ADHPA
VDHPA
PDHPA
TDHPA
VPA
ꢀ
þ
ꢀ
ꢀ
ꢀ
ꢀ
þ
þ
ꢀ
þ
In addition, positive and negative Cotton effects were
observed for the polymers obtained using (R)-PEA and (S)-
PEA, respectively (Table 1 and Fig. 1, nos. 5 and 6). There-
fore, the handedness of the main chain was controlled not
by the chiral substituents but by the chiral cocatalyst. For all
a
þ: Suitable, ꢀ: unsuitable.
b
HSSP: Helix-sense-selective polymerization.
AIP: Asymmetric-induced polymerization.
c
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FIGURE 4 CD and UV/vis spectra of poly(VPA)s in chloroform
prepared by using and
(nbd)Rhþ[g6-(C6H5)Bꢀ(C6H5)3]
[Rh(nbd)Cl]2/(R)- or (S)-PEA (Table 1, nos. 13–15).
FIGURE 6 CD spectra of poly(VPA) versus various tempera-
tures in chloroform prepared by using [Rh(nbd)Cl]2/(R)-PEA
(Table 1, no. 14).
cocatalyst. Therefore, the chirality of the main chain of poly-
(VPA) was controlled only by the chiral valinol residues.
This means VPA was not suitable for the HSSP. Therefore,
the two hydroxy groups were necessary to realize HSSP and
not necessary to AIP.
between two hydroxyl groups of the achiral monomer
units.5(a,b)
In conclusion, the two hydroxyl groups played an important
role on both the asymmetric polymerization and the stability
of one-handed helical conformation.
Cotton effects of poly(VDHPA) containing two hydroxyl
groups hardly decreased as the measuring temperature was
raised from 0 to 60 ꢁC (Fig. 5). On the other hand, CD
absorptions of poly(VPA) without hydroxyl groups decreased
largely as the measuring temperature was raised from 0 to
CONCLUSIONS
We have synthesized a novel four chiral phenylacetylenes
having an L-amino alcohol residue and two hydroxymethyl
groups. The monomer VDHPA only was suitable for both the
HSSP with a chiral catalytic system and the AIP with an
achiral catalyst. This means the possibility of synthesis of
four chiral polymers, the diastereomers (PL, ML, PD, and
MD) form the chiral monomer from the chiral monomer.4 It
was found that the kind of amino alcohol residues of the
monomers affected asymmetric polymerization and solubility
of the resulting polymers. The two hydroxy groups in the
monomer were necessary to realize the HSSP of VDHPA.
The two hydroxyl groups played an important role on both
the asymmetric polymerization and the stability of one-
handed helical conformation.
ꢁ
60 C (Fig. 6). These results indicated that the helical confor-
mation of poly(VDHPA) was more stable than that of poly-
(VPA). We can conclude that two hydroxyl groups of VDHPA
played a very important role in the stability of helical struc-
ture by intramolecular hydrogen bonds. It is similar as our
previous study, the chiral helical conformation of poly-
(DoDHPA) was stabilized by intramolecular hydrogen bonds
ACKNOWLEDGMENTS
Partial financial support through a Grant-in-Aid for Scientific
Research (B) (Nos. 16350061 and 19350054) from the Japan
Society for the Promotion of Science, and a Grant-in-Aid for
Scientific Research in a Priority Area ‘‘Super-Hierarchical
Structures’’ (Nos. 18039011 and 19022009) from the Ministry
of Education, Culture, Sports, Science, and Technology, Japan,
through an Asahi Glass Foundation, through the Iketani Science
and Technology Foundation, and through a Grant for Promotion
of Niigata University Research Projects is gratefully acknowl-
edged. The work was also supported by the National Natural
Science Foundation of China (51103076), Natural Science
Foundation of Heilongjiang Province, China (LC2011C12),
Overseas Scholars Foundation of Education Department of Hei-
longjiang Province, China (1251H012), and the Research
FIGURE 5 CD spectra of poly(VDHPA) versus various tempera-
tures in THF prepared by using [Rh(nbd)Cl]2/(S)-PEA (Table 1,
no. 6).
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F.; Masuda, T. Macromolecules 2003, 36, 3932–3937; (k) Gao,
G.; Sanda, F.; Masuda, T. Macromolecules 2003, 36, 3938–3943;
(l) Sanda, F.; Araki, H.; Masuda, T. Macromolecules 2004, 37,
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Foundation for Young Teachers (2010K-Z03) from Qiqihar
University, China.
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