Chiral polyamino alcohols and polyamino thiols for asymmetric heterogeneous catalysis

Article abstract of DOI:10.1016/j.tetasy.2006.06.041

A series of macroporous copolymer beads were synthesized by THE free radical suspension copolymerization of (S)-glycidylmethacrylate (GMA), (S)-thiiranylmethylmethacrylate (TMA), or (R,R)-phenylglycidylmethacrylate (Ph-GMA) with ethyleneglycol dimethacryl

Full text of DOI:10.1016/j.tetasy.2006.06.041

Tetrahedron: Asymmetry 17 (2006) 1944–1951
Chiral polyamino alcohols and polyamino thiols for
asymmetric heterogeneous catalysis
a
b
a,
*
´
Damien Herault, Christine Saluzzo and Marc Lemaire
a
`
Laboratoire de Catalyse et Synthese Organique, UMR 5622, UCBL, CPE, 43, Bd du 11 Novembre 1918,
69622 Villeurbanne Cedex, France
b
`
´ ´
Laboratoire de Synthese Organique, UMR 6011, Facultes des Sciences, Universite du Maine, Avenue Olivier Messiaen,
72085 Le Mans Cedex 09, France
Received 30 March 2006; revised 26 June 2006; accepted 28 June 2006
Abstract—A series of macroporous copolymer beads were synthesized by THE free radical suspension copolymerization of (S)-glycidyl-
methacrylate (GMA), (S)-thiiranylmethylmethacrylate (TMA), or (R,R)-phenylglycidylmethacrylate (Ph-GMA) with ethyleneglycol
dimethacrylate (EDMA) or divinylbenzene (DVB). This allowed for the evaluation of their chemical and physical properties (polymer
matrix nature or the structure of the heterocyclopropane) and their influence on the catalytic efficiency. These chiral polymers were sub-
sequently transformed into polyamino alcohol or polyamino thiol derivatives by the facile ring opening of the oxirane or thiirane group
with benzylamine and methylamine. Complexed with [RuCl2(p-cymene)]2, these derivatives were shown to be effective in the asymmetric
hydrogen transfer reduction of acetophenone. The best results (conversion: 94%, ee: 71%) were obtained with benzylamine grafted onto
poly(GMA-co-EDMA) (30/70 % wt/wt).
ꢀ 2006 Published by Elsevier Ltd.
1. Introduction
mation into polyamino alcohols by means of straightfor-
ward modification of the enantiopure epoxy groups with
chiral and homochiral amines.17 Ruthenium complexes
of these polyamino alcohols were used to catalyze the
asymmetric hydrogen transfer reduction of acetophe-
none.18,19 The best results, in terms of activity and enantio-
selectivity, were obtained with polyamino alcohols derived
from benzylamine and methylamine. We have recently
described the synthesis of aminoethanethiol trityl ether
ligands for ruthenium-catalyzed asymmetric transfer
hydrogenation obtaining enantioselectivities up to 85%.20
Herein, we report the synthesis of (S)-GMA, (S)-TMA,
and (R,R)-Ph-GMA monomers, as well as the copolymer-
ization of (S)-GMA with EDMA or DVB and that of (S)-
TMA or (R,R)-Ph-GMA with EDMA. The straightfor-
ward modification of the enantiopure heterocyclopropane
groups with either benzylamine or methylamine was per-
formed, in order to obtain polyamino alcohols or poly-
amino thiols, which were used as ruthenium ligands for
asymmetric heterogeneous catalytic hydrogen transfer of
acetophenone. The catalyst selectivity has been studied
as a function of the specific surface area, the structure
of the heterocyclopropane and the nature of the cross-
linking agent of the supported ligands.
The preparation of optically active polymers presents an
interesting challenge since it involves either asymmetric
polymerization1 or polymerization of an enantiopure
monomer.2 Over the last 30 years, Svec3 and Jovanovic4
have reported a series of articles relating to macroporous
copolymer beads based on glycidylmethacrylate (GMA)
and ethyleneglycoldimethacrylate (EDMA). These polymer
beads provide a wide range of applications due to the pres-
ence of the epoxy groups, which react readily with various
reagents. Thus epoxide derivatives have been used in ion
exchange chromatography,5–7 as ion exchange resins,8–10
as gas chromatography stationary phases,11 as gas sor-
bents,12,13 protecting groups,14 and enzyme immobilization
agents.15 More recently, Kuroda and Osawa16 prepared
poly(glycidylmethacrylate-co-divinylbenzene) as macro-
porous beads for highly adsorptive activity.
We have previously reported the synthesis of enantiopure
poly((S)-GMA-co-EDMA) and its subsequent transfor-
*
Corresponding author. Tel.: +33 4 72 43 14 07; fax: +33 4 72 43 14 08;
e-mail: marc.lemaire@univ-lyon1.fr
0957-4166/$ - see front matter ꢀ 2006 Published by Elsevier Ltd.
doi:10.1016/j.tetasy.2006.06.041

D. He´rault et al. / Tetrahedron: Asymmetry 17 (2006) 1944–1951
1945
2. Results and discussion
the cross-linking agent and the steric hindrance. As re-
ported by Svec,24 the specific surface area could be con-
trolled during polymerization by changing the
concentration of the cross-linking agent.
2.1. Preparation of enantiopure monomers
In order to obtain enantiopure glycidylmethacrylate, the
hydrolytic kinetic resolution of saturated terminal epoxides
was attempted by using chiral cobalt-based salen as a cat-
alyst.21 In the presence of 0.5 mol % of [CoIII{(R,R)-salen}
(OAc)] complex, the (S)-GMA enantiomer was obtained
with an excellent enantioselectivity (greater than 99.5%)
and 45% yield (selectivity factor, S = 56) (Scheme 1).
The copolymerizations were carried out in a 500 mL glass
reactor equipped with a stirring anchor. The copolymeriza-
tion of (S)-GMA, (S)-TMA, or (R,R)-Ph-GMA with
EDMA were performed according to the procedures of
Svec3 and Jovanovic4 (inert phase: cyclohexanol and/or
dodecanol, initiator: AIBN, stabilizer: polyvinyl pyrroli-
done) (Scheme 4). Poly(GMA-co-DVB) 4 was prepared
following Osawa’s conditions16 using polyvinyl alcohol as
a stabilizer (Scheme 4). The preparation of poly(Ph-
GMA-co-EDMA) 3 was performed with 40/60 % wt/wt
Ph-GMA/EDMA. These proportions correspond to a
molar ratio of GMA/EDMA 30/70 % wt/wt. The copoly-
merization of (S)-TMA was carried out using only cyclo-
hexanol as the inert phase to increase the homogeneity of
the organic phase.
The synthesis of (2R,3R)-3-phenylglycidylmethacrylate
(Ph-GMA) was then carried out in 90% yield by esterifica-
tion of the commercially available (2R,3R)-phenylglycidol
with methacryloyl chloride (Scheme 2).22
O
O
Cl
O
O
The level of copolymerization was determined by elemental
analysis. As expected, polymer 2 (Table 1, entry 2), which
contains less cross-linking agents, leads to 4.92 mmol/g of
epoxy groups. For the same concentration of cross-linking
agent, polymers 1 and 4 (Table 1, entries 1 and 4), show
identical proportions in oxirane function (2.11 mmol/g).
With poly(Ph-GMA-co-EDMA) 3 (Table 1, entry 3), the
concentration of the epoxy groups was found to be
1.83 mmol/g. The poly(TMA-co-EDMA) 5 (Table 1, entry
5) contains 1.72 mmol/g of thiirane group.
HO
O
triethylamine
toluene, 100°C
Yield=90%
Scheme 2. Synthesis of enantiopure Ph-GMA.
Following Varela’s methodology,23 the enantiopure thiira-
nylmethylmethacrylate (TMA) was prepared from the (S)-
GMA in a quantitative yield (Scheme 3).
The specific surface area of these chiral copolymers was
measured by B.E.T.25 analysis (Table 1). As the cross-
linked copolymers were stable at high temperatures (Kofler
bench analysis), the measurements were realized after heat-
ing them at 240 ꢁC for 3 h in vacuo without observing any
noticeable deterioration. Porosity or specific surface area
analyses were already realized on poly(GMA/EDMA)16,24
and, as mentioned by Jovanovic,4 the specific surface area
depends on the ratio of GMA to EDMA. A decrease in the
2.2. Polymerization
The copolymerization of (S)-GMA with EDMA or DVB,
(R,R)-(Ph-GMA), and (S)-TMA with EDMA, were per-
formed using radical suspension copolymerization with
AIBN initiator. In order to optimize the ability of these
copolymers as polymer supported catalysts, we focused
our attention on the specific surface area, the nature of
H
H
N
N
O
0.5%
t-Bu
Co
t-Bu
O
O
O
O
OAc
t-Bu
t-Bu
O
O
O
+
OH
O
O
H2O, 0.55 eq
20°C
OH
ee> 99.5%
Yield= 45%
2,3-dihydroxypropyle
methacrylate (HPMA)
GMA
Scheme 1. Hydrolytic kinetic resolution of GMA.
S
O
O
O
2 eq
NH2
ee> 99.5%
Yield> 99.5%
H2N
MeOH, rt
O
O
S
Scheme 3. Synthesis of enantiopure TMA.

1946
D. He´rault et al. / Tetrahedron: Asymmetry 17 (2006) 1944–1951
AIBN
O
O
O
O
polyvinylpyrrolidone
cyclohexanol/dodecanol : 91/9
+
O
O
O
O
water
O
O
70°C(2h) then 80°C(6h)
EDMA
(S)-GMA
poly((S)-GMA-co-EDMA) 1 and 2
AIBN
O
O
O
O
polyvinylpyrrolidone
cyclohexanol/dodecanol : 91/9
water
+
O
O
O
O
O
O
70°C(2h) then 80°C(6h)
EDMA
poly((R,R)-Ph-GMA-co-EDMA) 3
(R,R)-Ph-GMA
AIBN
O
O
polyvinyl alcohol
cyclohexanol/dodecanol : 91/9
+
+
O
O
O
O
water
70°C(2h) then 80°C(6h)
DVB
poly((S)-GMA-co-DVB) 4
(S)-GMA
AIBN
O
O
O
O
polyvinylpyrrolidone
cyclohexanol
O
S
O
O
O
water
S
70°C(2h) then 80°C(6h)
EDMA
(S)-TMA
poly((S)-TMA-co-EDMA) 5
Scheme 4. Free radical copolymerization.
Table 1. Copolymers containing heterocyclopropane functions
Entry Monomers (wt %)
Final polymer
f (mmol/g) B.E.T. surface (m2/g)
O
O
O
O
O
1
2
Poly((S)-GMA-co-EDMA) 1
2.11
4.92
100
50
O
O
O
O
O
O
(S)
(S)
O
O
(70)
(30)
(70)
O
Poly((S)-GMA-co-EDMA) 2
(30)
(60)
O
O
O
O
O
3
Poly((R,R)-Ph-GMA-co-EDMA) 3 1.83
35
O
O
O
(R)
(R)
O
(40)
4
5
Poly((S)-GMA-co-DVB) 4
Poly((S)-TMA-co-EDMA) 5
2.11
1.72
275
92
O
O
(S)
(S)
(70)
O
S
(30)
(30)
O
O
O
O
(70)
specific surface area was observed when the concentration
of EDMA decreased (Table 1, entries 1 and 2). The amount
of cross-linking agent affords to the rigidity of the copoly-
mer network and increases its specific surface area.
Although polymers 4 and 5 possess the same molar ratio
in cross-linking agent as polymer 1, their specific surface
areas are different. Using divinylbenzene as cross-linking
agent increases the specific surface area by 2.75 (Table 1,
entries 1 and 5). Compared to copolymer 1, copolymer 5
presents a similar specific surface area showing that the
nature of the heterocyclopropane has little influence on
it. Compared to copolymer 1, copolymer 3, which contains
phenyl groups presents a lower specific surface area
(35 m2/g). The highest specific surface area (275 m2/g)
was found for copolymer 4 using DVB as cross-linking
agent (Table 1, entry 4). As these copolymers have different
specific surface areas, we guess their activity would be
dependent upon this factor during their modification and
their use in heterogeneous catalysis (vide infra).
2.3. Grafting of amine on chiral copolymers
Polyamino alcohols 6, 7, 8, 9, 10, and 11 and polyamino
thiols 12 and 13 were prepared according to the procedure
reported by Lindsay and Sherrington,9 from oxirane-con-
taining polymers 1, 2, 3, 4, and thiirane-containing polymer
5, respectively, by heterocyclopropane ring opening with
benzylamine or methylamine (Scheme 5).

D. He´rault et al. / Tetrahedron: Asymmetry 17 (2006) 1944–1951
1947
We chose the widely used asymmetric hydrogen transfer
reduction, which is attractive because it avoids the use of
pressurized hydrogen, which requires special equipment.
Supported ligands are often employed and have been shown
to efficiently induce enantioselectivity and can be reused.29
O
O
HNR1R2
R
R
O
O
T, solvent
E
HE
NR1R2
E=O, S
Scheme 5. Grafting of amines onto chiral copolymers.
Ruthenium complexes of polyamino alcohols 6–11 and
polyamino thiols 12–13 were prepared in situ using
[RuCl2(p-cymene)]2 as the precursor and were then in-
volved in the hydrogen transfer reduction of acetophenone
(Scheme 6). The reaction was performed under argon, with
a ratio of acetophenone/Ru/ligand/t-BuOK of 20/1/4/5
and using isopropanol as a hydrogen donor. The results
are summarized in Table 3.
In the case of EDMA copolymers, we assumed that the
radical polymerization was complete enough to minimize
the presence of unreacted unsaturated ester groups. There-
fore, we assumed the amine reacted only with the hetero-
cyclopropane function. Moreover under these conditions,
the regioselective attack at the less hindered position of
the heterocyclopropane is favored.26 Pericas27 analyzed
by 13C NMR the regioselectivity of the aminolysis of the
supported phenylglycidyl ether and observed selective at-
tack at the benzyl position.
(Ru(p-cymene)Cl2)2
O
OH
t-BuOK, i-PrOH
L*
The level of functionalization of these polyamino alcohols
and polyamino thiols was determined by elemental analysis
of the nitrogen content (Table 6). A difference was ob-
served between the grafting of benzylamine and that of
methylamine. The levels of functionalization of benzyl-
amine were, respectively, 85%, 49%, and 78% for polymers
1, 3, and 5 (Table 2, entries 1, 4, and 8), while the levels of
functionalization of methylamine are, respectively, 43%,
29%, and 55% (Table 2, entries 2, 5, and 7). Benzylamine
grafting onto polymer 2, which contains more oxirane
groups than polymer 1 (Table 2, entries 1 and 3), is more
efficient although the specific surface area is smaller (Table
1, entry 2). Moreover, polymer 4, having the highest
specific surface area (cross-linking agent: DVB), was mod-
ified by benzylamine with a yield of 77%. Grafting the
amines onto polymer 3 was less efficient than onto polymer
1, due to the less hindered epoxide group (Table 2, entries
1, 2, 4, and 5). Polymer 5, containing the thiirane group,
attained a lower level of functionalization with benzyl-
amine than polymer 1 (Table 2, entries 1 and 8), but was
more reactive with methylamine (Table 2, entries 2 and 7).
r.t.
O
R
O
L* =
E = O, S
HE
NR1R2
Scheme 6. Hydrogen transfer reduction of acetophenone.
The ligands derived from benzylamine (Table 3, entries 1,
3, and 6) gave the best conversions and the best enantio-
meric excesses (ees) compared to those modified with
methylamine (Table 3, entries 2, 4, and 5). Nevertheless,
ligand 7 (Table 3, entry 2) derived from methylamine was
faster in converting the acetophenone. The hindrance of
the phenyl group (Table 3, entries 3 and 4) decreased the
activity and enantioselectivity of the ligand during the
reduction. Less than 5% of the acetophenone was con-
verted with ligand 10. The enantioselectivity induced by
both ligands 9 and 10 was lower than with the other
ligands. This could be due to the presence of two asymmetric
centers. The asymmetric alcohol or thiol function seemed
to self-direct the enantioselectivity. The presence of the
other asymmetric center unfavorably affected the enantio-
selectivity of the reaction. Finally, introduction of a thiol
group instead of the alcohol did not give better conversions
and ees (Table 3, entries 5 and 6).
Table 2. Functionalization ratio of epoxy polymers
Entry Initial polymer Nucleophile
Conversion Final polymer
(f0 in mmol/g)a
(%)b
(f in mmol/g)c
1
2
3
4
5
6
7
8
1 (2.11)
1 (2.11)
2 (4.92)
3 (1.83)
3 (1.83)
4 (2.11)
5 (1.94)
5 (1.94)
Benzylamine 85
6 (1.46)
7 (0.85)
8 (2.90)
9 (0.65)
10 (0.51)
11 (1.28)
12 (0.90)
13 (1.11)
Methylamine 43
Benzylamine 92
Benzylamine 49
Methylamine 29
Benzylamine 77
Methylamine 55
Benzylamine 78
Comparing the results of the benzylamine copolymer deriv-
atives 6, 8, and 11, differences in reactivity and enantio-
selectivity were observed (Table 4). Since copolymer 11
presents a higher specific surface area than copolymer 6,
with copolymer 11, the conversion of acetophenone was
only 58% and the ee 44%, while with copolymer 6, the con-
version was 94% and the ee 71%. A marked decrease in
activity from 94% to 51% and lowered selectivity from
71% to 57% (Table 4, entries 1 and 2) were observed,
respectively, for copolymers 6 and 8 when the concentra-
tion of EDMA, the cross-linking agent, was decreased
(i.e., for less macroporous beads). In fact, in order to ob-
tain highly efficient heterogeneous catalysts, it appears
that, if the ligand structure is important, surface area and
texture seem to be of equal importance.
a f0 = mmol of heterocyclopropane function/g of polymer.
b Conversion = (%Nfound/%Ncalcd) · 100.
c f = (f0/(1 + f0Mamine)) · (%Nfound/%Ncalcd).
2.4. Asymmetric hydrogen transfer reduction of
acetophenone
Enantiopure amino alcohols and amino thiols, used as
ligands for transition metals, are precious tools for the
introduction of chirality in asymmetric catalysis of C–C,
C–O, and C–H bond forming reactions.20,28

1948
D. He´rault et al. / Tetrahedron: Asymmetry 17 (2006) 1944–1951
Table 3. Ruthenium-catalyzed transfer hydrogenation of acetophenone: influence of the ligand
Entry
1
Ligand
Time (h)
3
Conversion (%)
94
ee (%) (configuration of phenylethanol)
O
71 (R)
(S)
(S)
O
O
N
H
HO
HO
Ph
O
O
6
2
3
4
1
22
72
95
61
65 (R)
21 (R)
29 (R)
NHMe
7
(S)(S)
Ph
O
HO
HN
Ph
9
O
Ph
(S)(S)
O
<5
Me
HO
N
H
10
O
O
(R)
5
6
22
22
50
55
39 (S)
50 (S)
O
O
HS
HS
NHMe
12
(R)
N
H
Ph
13
Table 4. Ruthenium-catalyzed transfer hydrogenation of acetophenone: influence of the cross-linking agent
Entry
Cross-linking agent (wt %)
Time (h)
Conversion (%)
ee (%) (configuration of phenylethanol)
O
O
3
94
71 (R)
1
O
O
O
O
6 (70%)
8 (30%)
O
O
2
3
72
22
51
58
57 (R)
44 (R)
11 (70%)
3. Conclusions
senting a specific surface area of 100 m2/g. These experi-
ments show the significant potential of such macroporous
ligands for heterogeneous asymmetric catalysis. Various
substrates and metals as well as other chiral copolymers
formed by means of various cross-linking agents will be
investigated in order to screen the scope and limitations
of these catalytic systems.
We have synthesized various chiral copolymers containing
enantiopure epoxide or thiirane groups with controlled
specific surface area. We have shown that these physical
properties could be controlled during the copolymerization
reaction by modifying the proportion and the nature of the
cross-linking agent. Polyamino alcohol and polyamino
thiol derivatives were obtained by the straightforward ring
opening of the oxirane or thiirane with benzylamine or
methylamine. They were subsequently used in ruthenium
complexes for asymmetric catalytic hydrogen transfer
reduction of acetophenone. We have shown that the effi-
ciency of the catalysts depended on the specific surface
area, on the nature and on the proportion of the cross-link-
ing agent. The best results (94% activity and 71% enantio-
selectivity), were obtained when benzylamine was
grafted onto poly(GMA-co-EDMA) 30/70 % wt/wt pre-
4. Experimental
4.1. General
Divinyl benzene (80%), racemic GMA (97%), EDMA
(98%), (2R,3R)-phenyl glycidol (97%), methacryloyl chlo-
ride (90%), polyvinylalcohol (89%), thiourea, and dodeca-
nol (98%) were purchased from Aldrich; (1R,2R)-1,
2-diaminocyclohexane-[N,N0-bis(3,5-ditertbutylsalicydene)

D. He´rault et al. / Tetrahedron: Asymmetry 17 (2006) 1944–1951
1949
cobalt(II)] from Strem; cyclohexanol, polyvinylpyrolidone
1,300,000, and AIBN (azobis isobutyronitrile) from Acros.
For hydrolysis kinetic resolution of glycidyl methacrylate
and hydrogen transfer reduction of acetophenone, enantio-
meric excesses, and conversions were determined by GC on
a Supelco b dex 225 (30 m · 0.25 mm) or Macherey-Nagel
lipodex A (25 m · 0.25 mm) chiral column, using a Shima-
dzu GC-14A equipped with a flame ionization detector
added to a methanol solution (350 mL) of (S)-GMA
(10 g, 70 mmol). The reaction mixture was stirred for
3 days, after which the methanol was removed under vac-
uum. Dichloromethane (150 mL) was added to precipitate
the urea and thiourea, which were separated by filtration.
After removing the solvent in vacuo, (S)-thiiranylmethyl-
methacrylate was obtained with a quantitative yield. Ee
>99.5% (determined by GC), [a]D = ꢀ37.8 (c 0.01,
1
1
connected to a Shimadzu C-R6A integrator. H and 13C
CH2Cl2), H NMR (300 MHz): 1.98 (m, 1H), 2.32 (dd,
NMR spectra were recorded with a Bruker AM300 (1H:
300 MHz, 13C: 75.5 MHz) using TMS as the internal stan-
dard and CDCl3 as solvent. Polarimetric measurements
were performed on a Perkin–Elmer 241 instrument, at
ambient temperature, at 589 nm concentration in grams
per 100 mL solution. Elemental analyses were carried out
J = 5.10 Hz, 1.50, 1H), 2.57 (dd, J = 6.20 Hz, 1.50, 1H),
3.15–3.24 (m, 1H), 4.17–4.32 (m, J = 3.3, 12.30 Hz, 1H)
5.63–5.65 (m, 1H), 6.15–6.18 (m, 1H), 13C NMR
(75 MHz): 18.7, 24.2, 31.3, 68.9, 126.5, 136.4, 167.1.
4.3. Copolymerization
´
by the CNRS (Service Central d’Analyse–Departement
´
´
Analyse Elementaire), Solaize, France. B.E.T. measure-
ments were performed on an automatic home made ‘Insti-
tut de Recherches sur la Catalyse’ apparatus by means of
N2 adsorption at ꢀ196 ꢁC. Before every measurement,
the support was heated to 240 ꢁC for 3 h in vacuo. The
Roberts’ model was used to determine the pore size.
A solution of AIBN in a mixture of enantiopure
monomer and cross-linking agent (DVB or EDMA)
was added to a solution of porogen solvents (cyclohexanol
and/or dodecanol). This organic mixture was added to
an aqueous solution (150 mL) of stabilizer (polyvinyl
pyrolidone or polyvinyl alcohol). The mixture was stirred
at 600 rpm, and heated to 70 ꢁC for 2 h and then 80 ꢁC
for a further 6 h. Two hours after allowing the mixture
to cool to room temperature, the spherical particles
formed were washed with acetone using a soxhlet and
dried in a vacuum oven. This procedure was used for
the syntheses of all the polymers using the quantities
below.
4.2. Preparation of enantiopure monomers
4.2.1. Preparation of enantiopure GMA monomer. Acetic
acid (76 lL, 1.336 mmol) was added to a solution of
(1R,2R)-1,2-diaminocyclohexane-N,N0-bis(3,5-ditertbutyl-
salicylidene)cobalt(II) (0.457 g, 0.668 mmol) in toluene
(12 mL). After stirring for 1 h at room temperature, the sol-
vent was removed under vacuum. Racemic glycidyl meth-
acrylate (19 g, 133 mmol) was added to the resulting
black residue, at 0 ꢁC, followed by bidistilled water (1.2 g,
66 mmol, 0.55 equiv). The reaction mixture was stirred
for 24 h at room temperature. (S)-Glycidyl methacrylate
(6.65 g, 46.55 mmol, yield 35%) was separated from the
diol by flash chromatography on silica gel (Merck 60,
40–60 mm) using dichloromethane as eluent. Ee >99.5%
(determined by GC), [a]D = +30.3 (c 0.01, CH2Cl2).
4.3.1. Poly((S)-GMA-co-EDMA) (30/70 % wt/wt) 1.
AIBN: 100 mg, (S)-GMA: 3 g, EDMA: 7 g, cyclohexanol:
12.06 g, dodecanol: 1.18 g, polyvinylpyrrolidone: 0.73 g.
Elemental analysis: Calcd: C: 60.17, H: 7.06, O: 32.77.
Found: C: 60.41, H: 7.48, O: 32.10%. Functional:
2.11 mmol/g. B.E.T. surface = 100 m2/g.
4.3.2. Poly((S)-GMA-co-EDMA) (70/30 % wt/wt) 2.
AIBN: 100 mg, (S)-GMA: 7 g, EDMA: 3 g, cyclohexanol:
12.06 g, dodecanol: 1.18 g, polyvinylpyrrolidone 0.73 g.
Elemental analysis: Calcd: C: 59.50, H: 7.19, O: 33.25.
Found: C: 59.86, H: 7.28, O: 32.85%. Functional:
4.92 mmol/g. B.E.T. surface = 50 m2/g.
4.2.2. Synthesis of (R,R)-phenyl glycidylmethacrylate (Ph-
GMA). At 0 ꢁC, methacryloyl chloride (8 mL, 80 mmol)
and dropwise triethylamine (18.75 mL, 133 mmol) were
added to a solution of (2R,3R)-phenylglycidol (10 g,
65 mmol) in toluene (100 mL). The reaction mixture was
then heated at 100 ꢁC for 3 h. At room temperature, the
reaction mixture was washed with brine (3 · 50 mL), an
aqueous solution of NaHCO3 (3 · 50 mL), and finally
dried over MgSO4. After removing the solvent in vacuo,
the oil obtained was purified by chromatography on alumi-
num oxide gel (Merck 150 type T 63-200) using heptane/
ethylacetate: 9/1 as eluent. The (R,R)-phenyl glycidylmeth-
acrylate was obtained with a yield of 90%. Ee >99.5%,
[a]D = +49.6 (c 0.01, CH2Cl2), 1H NMR (200 MHz):
1.98–2.00 (m, 1H), 3.30–3.35 (m, 1H), 3.84 (d, J = 2 Hz,
1H), 4.19 (dd, J = 5.80, 12.30 Hz, 1H), 4.57 (dd, J = 3.3,
12.30 Hz) 5.63–5.65 (m, 1H), 6.19–6.21 (m, 1H), 7.29–
7.42 (m, 5H), 13C NMR (50 MHz): 18.4, 56.5, 59.4, 64.5,
125.8, 126.4, 128.5, 128.6, 135.9, 136.3, 167.0.
4.3.3. Poly((R,R)-Ph-GMA-co-EDMA) (40/60 % wt/wt) 3.
AIBN: 100 mg, (R,R)-Ph-GMA: 4 g, EDMA: 6 g, cyclo-
hexanol: 15.27 g, dodecanol: 1.56 g, polyvinylpyrrolidone:
0.63 g. Elemental analysis: Calcd: C: 65.02, H: 7.80, O:
28.18. Found: C: 62.94, H: 6.96, O: 28.88%. Functional:
1.83 mmol/g. B.E.T. surface = 35 m2/g.
4.3.4. Poly((S)-GMA-co-DVB) (30/70 % wt/wt) 4. AIBN:
188 mg, (S)-GMA: 2.60 g, DVB: 6 g, cyclohexanol:
12.48 mL, dodecanol: 1.06 mL, polyvinylalcohol: 3 g. Ele-
mental analysis: Calcd: C: 81.87, H: 7.75, O: 10.37. Found:
C: 82.39, H: 7.98, O: 9.62%. Functional: 2.11 mmol/g.
B.E.T. surface = 275 m2/g.
4.3.5. Poly((S)-TMA-co-EDMA) (30/70 % wt/wt) 5.
AIBN: 280 mg, (S)-TMA: 4 g, EDMA: 9 g, cyclohexanol:
19.2 mL, polyvinylpyrrolidone: 0.98 g. Elemental analysis:
Calcd: C: 58.30, H: 6.80, O: 28.50. Found: C: 57.60, H:
4.2.3. Synthesis of (S)-thiiranylmethylmethacrylate (TMA).
At room temperature, thiourea (10.65 g, 140 mmol) was

1950
D. He´rault et al. / Tetrahedron: Asymmetry 17 (2006) 1944–1951
Table 5. Grafting of amine onto chiral copolymers
Initial polymer (f0 in mmol/g)a
Nucleophile
T (ꢁC)
Conversion (%)b
Final polymer (f in mmol/g)c
1 (2.11)
1 (2.11)
2 (4.92)
3 (1.83)
3 (1.83)
4 (2.11)
5 (1.94)
5 (1.94)
Benzylamine (60 equiv)
Methylamine (10 equiv, 2.0 M in THF)
Benzylamine (60 equiv)
Benzylamine (60 equiv)
Methylamine 40% aq (3 equiv) with DMF
Benzylamine (60 equiv)
100
50
100
100
80
100
50
100
85
43
92
49
29
77
55
78
6 (1.46)
7 (0.85)
8 (2.90)
9 (0.65)
10 (0.51)
11 (1.28)
12 (0.90)
13 (1.11)
Methylamine (10 equiv, 2.0 M in THF)
Benzylamine (60 equiv)
a f0 = mmol of heterocyclopropane function/g of polymer.
b Conversion = (%Nfound/%Ncalcd) · 100 (Table 6).
c f = (f0/(1 + f0Mamine)) · (%Nfound/%Ncalcd).
Table 6. Elemental analysis of grafting copolymers
Final polymer
Elemental analysis (%)
Found
Calculated
C: 63.54, H: 7.31, O: 26.74, N: 2.41
Poly(benzylamine-((S)-GMA-co-EDMA)) 6
Poly(methylamine-((S)-GMA-co-EDMA)) 7
Poly(benzylamine-((S)-GMA-co-EDMA)) 8
Poly((S,S)-benzylamine-(Ph-GMA-co-EDMA)) 9
Poly((S,S)-methylamine-(Ph-GMA-co-EDMA)) 10
Poly(benzylamine-((S)-GMA-co-DVB)) 11
Poly((R)-methylamine-(TMA-co-EDMA)) 12
Poly((R)-benzylamine-(TMA-co-EDMA)) 13
C: 61.12, H: 7.42, O: 29.39, N: 2.07
C: 58.85, H: 7.62, O: 30.75, N: 2.78
C: 64.57, H: 7.63, O: 25.49, N: 2.30
C: 63.76, H: 7.29, O: 27.18, N: 1.76
C: 63.04, H: 8.16, O: 26.40, N: 2.36
C: 81.79, H: 8.05, O: 8.12, N: 2.03
C: 57.40, H: 7.50, O: 27.50, N: 2.20, S: 5.30
C: 61.11, H: 7.28, O: 24.99, N: 1.79, S: 4.81
C: 57.78, H: 7.36, O: 33.66, N: 1.20
C: 62.40, H: 7.75, O: 28.50, N: 1.35
C: 62.50, H: 7.35, O: 29.27, N: 0.86
C: 62.60, H: 7.06, O: 29.64, N: 0.70
C: 83.42, H: 7.44, O: 7.56, N: 1.57
C: 57.30, H: 7.34, O: 30.03, N: 1.22, S: 4.07
C: 57.63, H: 7.26, O: 30.72, N: 1.40, S: 3.49
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7.10, O: 28.60%. Functional: 1.72 mmol/g. B.E.T. sur-
face = 92 m2/g.
4.4. Typical polyamino alcohol or polyamino thiol synthesis
7. Pohl, C. A.; Stillian, J. R.; Jackson, P. E. J. Chromatogr., A
1997, 789, 29–41.
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mechanically stirred (100 rpm) in the amine solution with
or without solvent at the appropriate temperature for
48 h (Tables 5 and 6). The polymer was recovered by filtra-
tion and washed with water, and then for one day with ace-
tone with a soxhlet and dried in a vacuum oven (50 ꢁC).
4.5. Typical reduction procedure for acetophenone
11. Onjia, A.; Milonjic, S. K.; Jovanovic, N. N.; Jovanovic, S. M.
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13 lmol) was introduced in a 5 mL vial with supported
ligand (52 lmol) (6–13) and 2 mL of degassed isopropanol.
The suspension was stirred and heated at 80 ꢁC for 1 h,
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red. The reaction was allowed to cool to room temperature
and an isopropanolic solution (2 mL) of potassium tert-
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