Macroporous chiral ruthenium porphyrin polymers: A new solid-phase material used as a device for catalytic asymmetric carbene transfer

Article abstract of DOI:10.1016/j.tetasy.2005.10.021

A chiral ruthenium porphyrin complex, functionalized with four vinyl groups, has been polymerized with styrene, divinylbenzene (or ethylene glycol dimethacrylate) to obtain supported ruthenium complexes. The asymmetric addition of ethyl diazoacetate (or d

Full text of DOI:10.1016/j.tetasy.2005.10.021

Tetrahedron:
Asymmetry
Tetrahedron: Asymmetry 16 (2005) 3829–3836
Macroporous chiral ruthenium porphyrin polymers:
a new solid-phase material used as a device for
catalytic asymmetric carbene transfer
*
´
Yann Ferrand, Paul Le Maux and Gerard Simonneaux
Laboratoire de Chimie Organome´tallique et Biologique, UMR CNRS 6509, Institut de Chimie, Universite´ de Rennes 1,
35042 Rennes cedex, France
Received 14 September 2005; accepted 14 October 2005
Available online 11 November 2005
Abstract—A chiral ruthenium porphyrin complex, functionalized with four vinyl groups, has been polymerized with styrene,
divinylbenzene (or ethylene glycol dimethacrylate) to obtain supported ruthenium complexes. The asymmetric addition of ethyl
diazoacetate (or diazoacetonitrile) to styrene derivatives was carried out by using these polymers as catalysts. The reaction
proceeded under mild conditions and gave trans-cyclopropanes with good enantiomeric excess (up to 90%).
Ó 2005 Elsevier Ltd. All rights reserved.
1. Introduction
reactions catalyzed by these polymers. It is expected
that these polymers containing large pores are well
suited for use in asymmetric reactions catalyzed by
rigid and large chiral metalloporphyrin species. As an
application, an asymmetric cyanocarbene transfer to
alkenes using diazoacetonitrile as a reactive reagent is
also described.
The design of new heterogeneous catalysts to induce
enantiocontrol in carbene transfer reactions is presently
under extensive investigation due to the inherent
advantages of heterogeneous catalysis in the industrial
preparation of fine chemicals.1–3 In an ideal case, the
supported catalysts can be recovered from reaction
mixtures by simple filtration, can be recycled and can
help selectivity. Chiral porphyrins are well-known
ligands with numerous variations of substituents and
their ruthenium complexes have been used in a large
number of homogeneous asymmetric reactions, in par-
ticular cyclopropanations.4,5 Thus, the development of
efficient methods to immobilize chiral metalloporphy-
rins will open a general way to the preparation of
heterogeneous catalysts for enantioselective reactions.
However, there are few strategies available to obtain
chiral heterogeneous metalloporphyrin catalysts.6–8
We have previously reported the use of optically active
electropolymers bearing chiral metallospirobifluorenyl-
porphyrins for asymmetric heterogeneous catalysis.8
Herein, we report the preparation of macroporous
optically active polymers bearing chiral metalloporphy-
rins and asymmetric heterogeneous carbene transfer
2. Results
2.1. Porphyrin and metalloporphyrin syntheses
The starting point of the work described herein was the
introduction of a vinyl group onto an optically active
ruthenium porphyrin with the aim of preparing
polymers using the chiral metalloporphyrin as a co-
monomer. We choose a C2-symmetric group, which
contains two norbornane groups fused to the central
benzene ring, previously reported by Halterman and
Jan.9 It was therefore necessary to first prepare the chi-
ral p-bromoaldehyde 210 and then introduce the vinyl
group using the Stille coupling reaction. Thus, addition
of tributylvinyltin in toluene solution to the optically
active aldehyde in the presence of Pd(Ph3P)2Cl211,12 gave
the expected chiral vinylaldehyde 3 in 90% yield. The
desired chiral metalloporphyrins were obtained using
the Lindsey procedure under mild conditions13 and
then metal insertion. The ruthenium complexes were
*
Corresponding author. E-mail: gerard.simonneaux@univ-rennes1.fr
0957-4166/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2005.10.021

3830
Y. Ferrand et al. / Tetrahedron: Asymmetry 16 (2005) 3829–3836
Fe/Br2
CCl4
H
H
H
PdCl2(PPh3)2
SnBu3
Br
O
O
O
1
3
2
1. pyrrole
BF3.OEt2
CO
Ru
Ru3CO12
180˚C
N
N
N
N
NH
N
2. Chloranil
HN
N
5
4
Scheme 1.
prepared by treatment of the porphyrins with Ru3CO12
in degassed o-dichlorobenzene at 180 °C for 2 h to give
the expected complex 5. The synthetic pathway is repre-
sented in Scheme 1. This route is particularly interesting
because it can open many different possibilities to
obtain various optically active polymers bearing chiral
metalloporphyrins.
2.2. Polymerization
First, the chiral ruthenium vinylporphyrin 5 was used
in different block copolymerizations with divinyl benz-
ene (DVB) using a protocol previously described for
the preparation of monolithic resins (Scheme 2).14–16
Three different chiral ruthenium polymers P1-(RuCO),
R
CO
CO
N
N
N
N
N
N
N
N
DVB or EGDMA, styrene
Ru
R
R
Ru
porogen, AIBN
R
R =
DVB =
6
5
O
O
R =
O
O
O
O
O
O
EGDMA =
Scheme 2.

Y. Ferrand et al. / Tetrahedron: Asymmetry 16 (2005) 3829–3836
3831
P2-(RuCO) and P3-(RuCO) were prepared from 5 by
changing the degree of cross-linking and the porogen
(toluene or chloroform/dodecan), using AIBN as a rad-
ical initiator. The different ratios are summarized in
Table 1. The orange-red polymers were ground and
the near quantitative incorporation of the ruthenium
porphyrin in the polymer was evidenced by the fact that
the chloroform washing solutions were colourless. These
polymers were characterized by IR spectroscopy (Fig. 1)
and scanning electron microscopy (Fig. 2). All the ruthe-
nium polymers showed the FT-IR band in KBr corre-
sponding to the CO ligand at 1945 cmꢀ1, which is
similar to the value observed for the monomer 5. The
ruthenium contents were determined by electronic
microanalysis. The more polar monomer ethyleneglycol
dimethacrylate (EGDMA) was also chosen because it
forms highly cross-linked polymers, which can be used
as supports for metal catalysts.17 It must be emphasized
that such a system, supporting non-chiral ruthenium
porphyrins, has been recently reported by Nestler and
Severin for the epoxidation of olefins.18 Thus copoly-
merization of the ruthenium monomer 5 with ethylene
glycol dimethacrylate in the presence of toluene as the
porogen, which is necessary for creating the pore struc-
ture, resulted in the orange, insoluble polymer P4-
(RuCO).
Table 1. Polymerization conditions used for preparation of Ru catal-
ysts
Polymer
Monomer DVB/
Porogen
AIBN
(%)
(w/w)
styrene
2.3. Catalytic cyclopropanation reactions
P1-(RuCO) 5 (10%)
P2-(RuCO) 5 (10%)
P3-(RuCO) 5 (10%)
P4-(RuCO) 5 (10%)
1.2
5.0
1.2
1.2a
Toluene
Toluene
CHCl3/dodecane
Toluene
3
3
3
3
The bench-mark reaction between styrene and ethyl dia-
zoacetate to give cyclopropane esters was first tested
(Table 2). In all cases, the polymer catalyst was filtered
off and an additional quantity of substrates was added
to the solution to confirm the heterogeneous character
of the catalyst. We chose these two reagents, extensively
used both in homogeneous and heterogeneous pro-
cesses, as suitable substrates to show differences in terms
of enantioselectivity, diastereoselectivity and reactivity.1
Using P1-(RuCO) as the heterogeneous catalyst, the
cyclopropane was formed with good yield (77%), high
diastereoselectivity (trans/cis: 92/8) and good enantiose-
lectivity for the trans-isomer (82%) (Table 2, entry 1).
We also investigated the cyclopropanation of para-
substituted styrenes. As shown in Table 2, para-substitu-
tion (p-Y-styrene, Y = MeO and Br) has a weak effect
upon the enantioselectivity of styrene cyclopropanation,
the best ee (90%) being obtained with the bromo deriv-
ative. A similar effect was noted in the asymmetric cyclo-
propanation with ethyl diazoacetate using a different
chiral ruthenium catalyst.19
In an oven dried thermolysis tube, metalloporphyrin 5 was dissolved in
the porogen (toluene 1.5 mmol). Then, styrene and divinylbenzene
were added to the solution. The polymerization reaction was initiated
by AIBN (60 lmol). The mixture was heated at 65 °C for 16 h without
stirring.
a EGDMA/styrene.
It can also be seen from Table 2 that the use of CHCl3/
dodecane as a porogenic mixture: P3-(RuCO) seems to
be detrimental to the enantiomeric excess, the diastereo-
selectivity and the yield (entry 3). This may be due to the
reduced accessibility of the sites, as also evidenced by the
results obtained with P2-(RuCO), a polymer prepared
with a high DVD/styrene ratio (entry 2). To shed some
light on this area, we also carried out a comparative
study with a different polymer P4-(RuCO), using a
different cross-linker, ethylene glycol dimethacrylate.
Figure 1. IR spectrum of the chiral ruthenium polymer P1-(RuCO) in
KBr.
Figure 2. Scanning electron microscopy of P1-(RuCO).

3832
Y. Ferrand et al. / Tetrahedron: Asymmetry 16 (2005) 3829–3836
Table 2. Asymmetric cyclopropanation of styrene by ethyl diazoacetate catalyzed by Ru polymersa
c
c
Substrates
Catalysts
Yieldb (%)
trans/cis (%)
eetrans (1S,2S)
eecis (1R,2S)
Turnover
1
2
3
4
P1-(RuCO)
P2-(RuCO)
P3-(RuCO)
P4-(RuCO)
77
66
60
62
92/8
82
76
71
77
8
8
11
8
1075
905
820
850
85/15
82/18
89/11
5
6
P1-(RuCO)
P4-(RuCO)
88
81
92/8
91/9
80
79
14
16
1205
1110
MeO
Br
7
8
P1-(RuCO)
P4-(RuCO)
75
74
93/7
93/7
90
83
10
17
1030
1010
a Reactions were performed in CH2Cl2 at room temperature for 24 h with a catalyst/diazo/substrate molar ratio of 0.5/600/500.
b Isolated yields based on substrates.
c Determined by chiral GC (see Section 5).
Yield
Diastereoselectivity
Enantioselectivity
100
90
80
70
60
%
50
40
30
20
10
0
1
2
3
4
5
6
7
8
Cycle #
Figure 3. Recovery–reuse outcome from the cyclopropanation of styrene with ethyl diazoacetate using P1-(RuCO) as catalyst.
As can be seen in Table 2 (entries 4, 6 and 8), the results
are only slightly lower than those obtained with P1-
(RuCO).
The cyclopropane was formed with 63% yield, 67/33
trans/cis ratio and 66% enantioselectivity for the trans-
isomer (entry 1). We also investigated the cyclopropana-
tion of para-substituted styrenes (Table 3). As shown in
Table 3, para-substitution (p-Y-styrene, Y = MeO, Br
and H) does not have a significant effect upon the enanti-
oselectivity of styrene cyclopropanation and the best ee
(72%) for the trans-isomer was obtained with the para-
Br derivative. The different chiral ruthenium polymers
were also used with diazoacetonitrile and the representa-
tive results are summarized in Table 3. With the inserted
ruthenium porphyrins, porous solids exhibited moderate
activity and correct enantioselectivity in heterogeneous
cyclopropanation of styrene with diazoacetonitrile. The
best ee (71%, entry 9) was obtained with P1-(RuCO)
and is similar to those obtained with the homogeneous
chiral ruthenium porphyrins (Table 3, entry 8).
The recovery and recyclability of P1-(RuCO) polymer
have been also examined. The polymer was tested for
enantioselectivity and reactivity in the cyclopropanation
of styrene with ethyl diazoacetate leading three recycling
steps with a weak progressive decrease of enantioselec-
tivity (from 82% to 78%) and a decrease of yield (from
90% to 71%) (Fig. 3). However, the yield markedly dec-
reased to 53% after the eighth run whereas the enantio-
selectivity was maintained at ꢁ68%.
To evaluate the reactivity of the diazoacetonitrile, its
ruthenium-catalyzed decomposition was first examined
in the presence of styrene in dichloromethane at room
temperature under homogeneous conditions (Table 3).
We used 720 (Scheme 3), a chiral ruthenium catalyst,
whose structure is directly related to that found in the
polymers. This ruthenium porphyrin catalyst is particu-
larly interesting since the enantiomeric excesses are quite
high (90%) when the catalytic reactions are undertaken
under homogeneous conditions with ethyl diazoacetate20
and diisopropyl diazomethylphosphonate21 as reagents.
3. Discussion
Optically active cyclopropane-containing compounds
are of great interest, particularly to synthetic organic
chemists and to bioorganic chemists.22 Thus optically
active ruthenium porphyrin complexes have been the

Y. Ferrand et al. / Tetrahedron: Asymmetry 16 (2005) 3829–3836
3833
Table 3. Asymmetric cyclopropanation of styrene by diazonitrile catalyzed by Ru polymersa
c
c
Substrates
Catalysts
Yieldb (%)
trans/cis (%)
eetrans (1S,2S)
eecis (1R,2S)
1
2
3
4
5
7d
63
53
46
35
61
67/33
76/24
64/36
62/38
76/24
66
70
52
41
69
27
20
20
12
23
P1-(RuCO)
P2-(RuCO)
P3-(RuCO)
P4-(RuCO)
6
7
7
P1-(RuCO)
44
55
68/32
70/30
69
68
7
16
MeO
Br
8
9
7
P1-(RuCO)
47
40
70/30
75/25
72
71
29
29
a Reactions were performed in CH2Cl2 at room temperature for 24 h with a catalyst/diazo/substrate molar ratio of 0.5/100/500.
b Isolated yields based on diazoacetonitrile.
c Determined by chiral GC (see Section 5).
d 7: chiral ruthenium porphyrin prepared following Ref. 21 (Scheme 3).
reaction was observed, due to a weak rigidity of the cat-
alytic sites, grafted on the support.
The recovery and recyclability of the polymers were
examined. Although, no leaching of the metalloporphy-
rins was observed, a significant decrease of reactivity is
noted whereas the enantioselectivity is maintained. It
is difficult to suggest an explanation at this stage but it
should be noted that the CO ligand is replaced by the
carbene ligand in the first catalytic cycle. The IR
spectrum shows the disappearance of the vibration
corresponding to the CO ligand at 1945 cmꢀ1. The
coordination of by-products may be responsible of the
deactivation and, if the situation is reversible, recovery
of theses polymers under CO atmosphere may improve
the catalytic recyclability.
CO
Ru
N
N
N
N
7
Scheme 3.
focus of intense studies by us4,21,23 and others5,24–26 as
catalysts for asymmetric cyclopropanation. In contrast,
immobilizing chiral metalloporphyrins as insoluble
materials is still rare.6–8 We previously reported the
use of optically active electropolymers bearing chiral
The different chiral ruthenium polymers were also used
for the asymmetric cyclopropanation with diazoaceto-
nitrile. Diazoacetonitrile can be a potent explosive28
and does not appear to have many applications in the
field of organic synthesis29–31 and, as far we are aware,
only a single example of enantioselective intermolecular
cyclopropanation is known.32 This situation may be due
to the small size of the cyano substituent, which disfa-
vours high diastereoselectivity for the trans-isomer. A
few publications also exist on the racemic synthesis of
cyanocyclopropane by means of reaction of diazoaceto-
nitrile with alkenes29–31 or cyanoalkenes with tosylhyd-
razones.33 Thus it was quite exciting to explore the
catalytic properties of these polymers towards diazo-
acetonitrile addition to olefinic bonds. The results
reported herein demonstrate that the asymmetric
cyclopropanation using diazoacetonitrile catalyzed by
chiral metalloporphyrins, both under homogeneous
and heterogeneous conditions, occurs in a good stereo-
selective manner, offering for the first time, a general
access to optically active trans-cyanocyclopropanes,
with possible biological applications after subsequent
reduction with LiAlH4.34 Furthermore, the crude
material can be readily enriched by recrystallization in
a mixture of dichloromethane/pentane to give trans-
cyanocyclopropanes in 50% isolated yield and 99% ee.
metallospirobifluorenylporphyrins
for
asymmetric
heterogeneous catalysis.8 However, despite their good
stability and recyclability, these polymeric catalysts
suffer from the drawback of moderate enantioselectivity
compared to the homogeneous counterpart. We describe
herein the development of novel chiral ruthenium por-
phyrin polymers for asymmetric heterogeneous carbene
transfer to olefins showing much higher enantioselectiv-
ity in the cyclopropanation reaction. The best ee was
obtained with the less cross-linked polymer and it
should emphasized that the results obtained with this
polymer P1-(RuCO) are similar to those obtained with
the homogeneous chiral ruthenium porphyrins.20 How-
ever, with all series, the rigidity of the chiral macrocycle
seems to be maintained. Thus, the polymer morphology,
which is controlled by the degree of cross-linking, the
nature of the porogen and the cross-linker determines
the performance of the polymer catalyst. This situation
was previously observed with the immobilization of pyr-
idine-bis(oxazoline) chiral ligand2 and bis(oxazoline)-
copper27 complexes but much larger influence of the
polymeric matrix on the stereochemical course of the

3834
Y. Ferrand et al. / Tetrahedron: Asymmetry 16 (2005) 3829–3836
These cyclopropanes can be used as direct precursors of
several melatonin agonists.35
5.2.2. (ꢀ)-10-Vinyl-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-di-
methanoanthracene-9-carboxaldehyde (ꢀ)-3. To solu-
tion of pure bromoaldehyde (+)-2 (1.58 mmol) in dry
toluene (15 mL) was added a solution of tributylvinyltin
(2 mmol) followed by Pd(Ph3P)2Cl2 (0.079 mmol) at
room temperature. The resulting mixture was heated
at 60 °C for 12 h. The reaction was monitored by TLC
and when the starting material had completely reacted,
the mixture was allowed to cool to room temperature.
The solvent was removed and the crude product was
purified by column chromatography (pentane/CH2Cl2
9/1). A white waxy solid was thus obtained in 90% yield.
½aꢂD ¼ ꢀ44 (c 0.50, CH2Cl2). H NMR d 10.46 (s, 1H);
6.92 (dd, 1H); 5.64 (m, 2H); 4.20 (m, 2H); 3.65 (m, 2H);
2.00 (m, 4H); 1.75 (m, 2H); 1.57 (m, 2H); 1.20 (m, 4H).
13C NMR d 192.2, 148.4, 144.5, 133.7, 130.4, 122.1,
120.4, 49.3, 41.7, 41.5, 26.9, 26.6. Mass EI
(m/z): calculated for C19H20O (M+Å): 264.1514, found:
264.1507.
4. Conclusion
In summary, the heterogeneous asymmetric cyclopropa-
nation of styrene catalyzed by new chiral ruthenium
porphyrin polymers occurs in a highly stereoselective
manner. Additionally, application to the synthesis of
cyanocyclopropane unknown in optically active form
was successful. Investigation of the catalytic properties
of these chiral ruthenium polymers for the epoxidation
of olefins is currently underway in our laboratory and
will be reported in due course.
20
1
5. Experimental
5.1. General experiments
5.2.3. 5,10,15,20-Tetrakis-[(1S,4R,5R,8S)-10-vinyl-1,2,
3,4,5,6,7,8-octahydro-1,4:5,8-dimethanoanthracene-9-yl]-
porphyrin 4. In a round bottom flask, a solution of
(ꢀ)-3 (0.75 mmol) in CHCl3 (60 mL) was mixed with
freshly distilled pyrrole (0.75 mmol). Argon was bubbled
through the solution for 5 min and BF3ÆEt2O
(0.22 mmol) was then added. The reaction mixture, pro-
tected from light, was stirred for 16 h at room temper-
ature, then p-chloranil (0.56 mmol) was added. The
solution was heated under reflux for 1 h and then
allowed to cool to room temperature. The solution was
concentrated and purified by column chromatography
(pentane/CH2Cl2 8/2) to give porphyrin 4 (26%). 1H
NMR d 8.80 (s, 8H); 7.26 (dd, 4H); 5.77 (m, 8H); 3.94
(m, 8H); 2.83 (m, 8H); 2.10–1.85 (m, 16H); 1.55–1.20
(m, 32H). UV–vis (CH2Cl2): kmax/nm (loge): 425 (5.75);
517 (4.41); 554 (4.22); 592 (4.14); 649 (4.19). Mass
(ESI, CH2Cl2/MeOH 9/1) (m/z): calculated for
C92H87N4[M+H]+: 1247.6930, found:1247.6921.
All reactions were performed under argon and were mag-
netically stirred. Solvents were distilled from appropriate
drying agent prior to use: Et2O and THF from sodium
and benzophenone, toluene from sodium, CH2Cl2 from
CaH2, CHCl3 from P2O5 and all other solvents were
HPLC grade. Commercially available reagents were used
without further purification unless otherwise stated. All
reactions were monitored by TLC with Merck pre-
coated aluminium foil sheets (Silica gel 60 with fluores-
cent indicator UV254). Compounds were visualized with
UV light at 254 and 365 nm. Column chromatographies
were carried out using silica gel from Merck (0.063–
0.200 mm). 1H NMR and 13C NMR in CDCl3 were
recorded using Bruker (Advance 500dpx and 300dpx
spectrometers) at 500 and 75 MHz, respectively. High-
resolution mass spectra were recorded on a ZabSpec
TOF Micromass spectrometer in ESI positif mode at
the CRMPO. Liquid UV–visible spectra were recorded
on a UVIKON XL from Biotech. All catalytic reactions
were controlled on a Varian CP-3380 Gas Chromato-
graph equipped with a CP-Chirasil-Dex Column.
5.2.4. Carbonyl[5,10,15,20-tetrakis-[(1S,4R,5R,8S)-10-
vinyl-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanoanthra-
cene-9-yl]-porphyrinato] ruthenium (II) 5. A mixture of
the free base porphyrin 4 (48 lmol) and Ru3CO12
(144 lmol) in refluxing o-dichlorobenzene was let to
react for 2 h. The solvent was removed under high vac-
uum, and the crude product was purified by column
chromatography (pentane/CH2Cl2 8/2) to obtain the
pure metalloporphyrin 5 (43 lmol 90%). 1H NMR d
8.62 (AB system (5 Hz), 8H); 7.26 (dd, 4H); 5.73 (m,
8H); 3.91 (m, 8H); 2.95 (m, 4H); 2.64 (m, 4H); 2.15–
1.90 (m, 16H); 1.55–1.20 (m, 32H); UV–vis (CH2Cl2):
kmax/nm (loge): 416 (5.45), 531 (4.47). Mass (ESI,
CH2Cl2/MeOH 9/1) (m/z): calculated for C93H84ON4Ru
[M+H]+: 1397.5586, found: 1397.5663; IR (KBr):
5.2. Preparation of ruthenium porphyrin monomer
5.2.1. (+)-10-Bromo-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-di-
methanoanthracene-9-carboxaldehyde (+)-2.10 To iron
powder (4.2 mmol) was added Br2 (12.6 mmol) to form
the corresponding Lewis acid, after 30 min, pure alde-
hyde (+)1 (4.2 mmol) in CCl4 (20 mL) was added. After
24 h at room temperature, the mixture was extracted
with 10% aqueous NaOH and water. Then, the com-
bined aqueous portions were extracted with CH2Cl2
three times. The combined organic portions were dried
and evaporated to give a brown solid. The crude prod-
uct was purified by column chromatography (pentane/
CH2Cl2 9/1) to give the pure bromoaldehyde (+)-2
m
CO = 1943.9 cmꢀ1
.
20
1
(80%). ½aꢂD ¼ þ44 (c 0.48, CH2Cl2). H NMR d 10.44
(s, 1H); 4.26 (m, 2H); 3.61 (m, 2H); 2.06–1.89 (m, 4H);
1.80 (m, 2H); 1.57 (m, 2H); 1.25–1.10 (m, 4H). 13C
NMR d 190.6, 149.0, 146.2, 128.6, 126.8, 48.5, 43.6,
42.3, 26.3, 25.7. Mass EI (m/z): calculated for
C17H17OBr (M+Å): 316.0462, found: 316.0460.
5.3. Preparation of polymers
In an oven dried hemolysis tube, metalloporphyrin 5
(7.2 lmol) was dissolved in the porogen (toluene
1.5 mmol). Then, styrene (277 lmol) and divinylbenzene
(or EGDMA) (340 lmol) were added to the solution.

Y. Ferrand et al. / Tetrahedron: Asymmetry 16 (2005) 3829–3836
3835
The polymerization reaction was initiated by AIBN
(60 lmol). The mixture was heated at 65 °C for 16 h
without stirring. The resulting polymer was extracted
from the polymerization tube, crushed in a mortar,
washed with dichloromethane and filtered on Buchner
¨
funnel (85 mg).
121.7; 22.7; 13.0; 6.5. Mass (EI): (m/z): calculated for
C10H8N 79Br [M+Å]: 220.9840, found: 220.9839.
Absolute configurations were determined from the spe-
cific rotations by comparison with previously reported
cyanocyclopropanes.36,37
5.4. General procedure for cyclopropanation reactions
with ruthenium porphyrin complexes
5.5. Gas chromatography conditions
Cyclopropanation of styrene with diazoacetonitrile:
GC CP-Chirasil-Dex column, injector 200 °C (pulsed
split mode), detector (FID 220 °C, oven: 120 °C;
2.5 °C minꢀ1), pressure = 15 psi. cis-(1R,2S) sr = 14.56
min and cis-(1S,2R) sr = 14.80 min; trans-(1R,2R)
sr = 13.76 and trans-(1S,2S) sr = 14.21 min.
For homogeneous reactions, the catalyst (0.2%, w/w)
was placed in an oven-dried thermolysis tube. This tube
was evacuated, and backfilled with argon. CH2Cl2
(1 mL) was added via syringe, followed by alkene
(1 mmol). Then, diazoacetonitrile (0.2 mmol) was added
slowly to the mixture over a period of 3 h. After 24 h,
the enantiomeric excess was measured by GC and the
resulting mixture was evaporated and purified by flash
silica gel chromatography to give pure cis- and trans-
diastereoisomers. trans-Cyanocyclopropanes (ee > 70%)
can be recrystallized in pentane/CH2Cl2 to give enantio-
merically pure compounds. For cyclopropanation reac-
tions with ruthenium polymers, the same procedure
was used. Then, the filtered polymer was washed several
times by acetone and dichloromethane. The polymer
was dried under vacuum and used for another run with
the same experimental conditions.
Cyclopropanation of 4-OMe styrene with diazoaceto-
nitrile: GC CP-Chirasil-Dex column, injector 200 °C
(pulsed split mode), detector (FID 220 °C, oven:
120 °C; 2.5 °C minꢀ1), pressure = 15 psi. cis-(1R,2S)
sr = 23.49 min and cis-(1S,2R) sr = 23.82 min; trans-
(R,R) sr = 22.94 and trans-(S,S) sr = 23.10 min.
Cyclopropanation of 4-Br styrene with diazoaceto-
nitrile: GC CP-Chirasil-Dex column, injector 200 °C
(pulsed split mode), detector (FID 220 °C, oven:
120 °C; 2.5 °C minꢀ1), pression = 15 psi. cis-(1R,2S)
sr = 27.40 min and cis-(1S,2R) sr = 27.96 min; trans-
(R,R) sr = 26.50 and trans-(S,S) sr = 26.66 min.
5.4.1. 2-Phenylcyclopropanecarbonitrile: trans-isomer.
1H NMR (CDCl3, 500 MHz): d (ppm) 7.34 (m, 2H);
7.18 (m, 1H); 7.13 (m, 2H); 2.66 (m, 1H); 1.65 (m,
1H); 1.58 (m, 1H); 1.48 (m, 1H). 13C NMR (CDCl3,
Acknowledgement
75 MHz) d (ppm) 137.6; 128.8; 127.5; 126.3; 121.6;
20
24.9; 15.3; 6.7. Optical rotation: ½aꢂD ¼ þ240 (c 0.88,
This work was made possible by the generous financial
support of the Girex company.
CH2Cl2). cis-Isomer 1H NMR (CDCl3, 500 MHz): d
(ppm) 7.39 (m, 2H); 7.31 (m, 3H); 2.57 (m, 1H); 1.87
(m, 1H); 1.58 (m, 2H). 13C NMR (CDCl3, 75 MHz) d
(ppm) 135.2; 128.6; 128.0; 127.7; 119.5; 23.2; 12.9; 6.4.
Mass (EI): (m/z): calculated for C10H9N [M+Å]:
143.0735, found: 143.0747.
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