The activity of covalently immobilized Grubbs-Hoveyda type catalyst is highly dependent on the nature of the support material

Article abstract of DOI:10.1016/j.jorganchem.2006.06.030

A Hoveyda-type catalyst for olefin metathesis was synthesized and covalently attached via an amide bond to four different solid supports. One of these supports was a home-made hybrid silica support, where an ultra-thin copolymer of poly(styrene) and poly(acrylamide) was grafted on. The three other supports were commercially available, namely HypoGel 400, PEGA and Trisoperl. It was demonstrated that the catalysts were active in ring closing metathesis (RCM) reactions as well as in cross metathesis (CM) and ring opening metathesis (ROM) reactions, but the activity of the catalyst was highly dependent on the nature of the support.

Full text of DOI:10.1016/j.jorganchem.2006.06.030

Journal of Organometallic Chemistry 691 (2006) 5172–5180
www.elsevier.com/locate/jorganchem
The activity of covalently immobilized Grubbs–Hoveyda type catalyst
is highly dependent on the nature of the support material
a
b
b,1
a,
*
Florian Michalek , Daniel M a¨ dge , J u¨ rgen R u¨ he , Willi Bannwarth
a
Institut f u¨ r Organische Chemie und Biochemie, Albert-Ludwigs-Universit a¨ t Freiburg, Albertstr. 21, 79104 Freiburg, Germany
Institut f u¨ r Mikrosystemtechnik, Albert-Ludwigs-Universit a¨ t Freiburg, Georges-Koehler-Allee 103, 79110 Freiburg, Germany
b
Received 25 April 2006; received in revised form 20 June 2006; accepted 20 June 2006
Available online 30 June 2006
Abstract
A Hoveyda-type catalyst for olefin metathesis was synthesized and covalently attached via an amide bond to four different solid sup-
ports. One of these supports was a home-made hybrid silica support, where an ultra-thin copolymer of poly(styrene) and poly(acrylam-
ide) was grafted on. The three other supports were commercially available, namely HypoGel 400, PEGA and Trisoperl. It was
demonstrated that the catalysts were active in ring closing metathesis (RCM) reactions as well as in cross metathesis (CM) and ring open-
ing metathesis (ROM) reactions, but the activity of the catalyst was highly dependent on the nature of the support.
ꢀ
2006 Elsevier B.V. All rights reserved.
Keywords: Alkenes; Immobilization; Olefin metathesis; Ruthenium; Supported catalysts
1
. Introduction
The most common method to overcome this problem is
immobilization of the transition metal catalyst on a solid
phase, which also allows for an easy separation from the
products. With the Grubbs – as well as with the Hoveyda
– type catalysts, immobilization proved to be, to a certain
degree, efficient in reducing the Ru-leaching. Meanwhile,
various alternative applications were developed using solid
phases, soluble polymers, ionic liquids or perfluoro-tagged
complexes [17–24].
One of the most impressive reactions developed in the
last years is olefin metathesis with all its synthetic mani-
foldness like ring closing metathesis (RCM), ring opening
metathesis (ROM), cross metathesis (CM) or enyne
metathesis [1–5]. The now widely available Ru-complexes
developed by Grubbs (Fig. 1) allow the construction of
highly diverse molecules or materials [6–9]. These com-
plexes show high activity along with relatively high stability
and they tolerate a broad spectrum of functional groups.
Hoveyda discovered a modified version of the Grubbs-type
catalyst, bearing a styrenyl ether (Fig. 1) [10,11]. The ether
chelate improved the stability towards air and moisture
even more, so that purification on silica gel and recycling
of these complexes became feasible. However, the observed
leaching of Ru into the products is a disadvantage and
makes additional purification necessary [12–16].
2. Results and discussion
Here, we report the synthesis and application of new,
immobilized Hoveyda-type catalysts on amino-functional-
ized solid supports of different nature. One of these materi-
als was a hybrid silica gel which consisted of porous silica
gel as matrix, on which an ultra-thin layer (ꢀ10 nm) of an
acrylamide-styrene copolymer was grafted (Fig. 2). The
organic layer mediates the contact with organic solvents
but shows no swelling. The loading of the support by
amino groups can be adjusted by the ratio of acrylamide
to styrene.
*
Corresponding author. Tel.: +49 761 203 6073; fax: +49 761 203 8705.
E-mail addresses: willi.bannwarth@organik.chemie.uni-freiburg.de
(W. Bannwarth), ruehe@imtek.uni-freiburg.de (J. R u¨ he).
1
Fax: +49 761 203 7162.
0
022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.06.030

F. Michalek et al. / Journal of Organometallic Chemistry 691 (2006) 5172–5180
5173
Ligand 7 was attached to the different solid supports
using DCC, HOBt and Huenig’s base for 24 h and no
amino functions were detected afterwards. Nevertheless,
this was followed by a masking step with acetic anhydride
to ensure that possibly unreacted free amino groups were
capped (Scheme 2). The immobilized catalysts were pre-
pared in the presence of 1a or 1b and CuCl as activator
N
N
R
Cl
R
PCy
Ru
3
Cl
Cl
N
N
Ru
O
PCy
Ru
3
3
R
Cl
R
Cl
Cl
Cl
Ru
PCy
O
PCy
Ph
Cl
Ph
3
Grubbs catalyst
Hoveyda catalyst
1
. Generation
2. Generation
1. Generation
2. Generation
(Scheme 2). For the removal of insoluble Cu-phosphine
1
a
1b
2a
2b
residues, we applied two different procedures. The silica-
based materials (8 and 11) were filtered after the reaction
and washed with DCM until the filtrates were colorless.
The remaining Cu ions were then removed specifically by
rendering them soluble as neocuproine complex, and their
absence was confirmed by XPS-measurements [25]. In con-
trast, the catalysts on HypoGel 400 and on PEGA (9 and
Fig. 1. Olefin metathesis catalysts.
O
Si
O
Si
O
O
N
NH
2
O
co
O
O
O
O
O
10) were purified using a method described by Blechert
Si
N
m
co
n
et al., which exploited the different densities of the poly-
mer-attached catalysts and the Cu-residues [26]. Finally,
the Ru-loading of all immobilized catalysts was determined
by atom absorption or inductively coupled plasma mass
spectroscopy (ICP-MS) [27].
OR
y
x
Si OH
O
N
NH
2
O
Although the support materials have different proper-
ties, the immobilized Ru-complexes should react according
to the same principle. In the first turnover, the catalytically
active Ru-species should be released from the support and
catalyze the metathesis in a homogeneous fashion [28,29].
After depletion of the substrate, the Ru is recaptured by
the solid phase bound ligands. In such a mechanism, the
support should only play a minor role. In order to shed
more light on this issue, we investigated the immobilized
complexes in recycling experiments, using the ring closure
of 12a as a benchmark reaction (Scheme 3). Of each cata-
lyst 1 mol% was placed under air in a reaction tube and the
substrate was added from a stock solution. After 2 h, a
sample was drawn to determine the conversion by HPLC,
then the supernatant solution was separated and the solid
support was washed with DCM. In this way, five consecu-
tive runs were performed with each catalyst (Figs. 3 and 4).
As expected, the complexes 8b–11b bearing the N-het-
erocyclic carbene ligand performed better than 8a–11a car-
rying the phosphine ligand. When applying 8a–11a, in the
first recycling run itself, a drop in activity of almost all
complexes took place (Fig. 3) and a dependency of the sup-
port material was indicated.
Fig. 2. Novel hybrid support: silica gel with a thin layer of a copolymer of
styrene and acrylamide.
Besides this new, home-made material, commercially
available solid phases were also applied. These materials
were HypoGel 400, which is polystyrene bearing low
molecular weight oligo(ethylene glycol) units, PEGA, a
poly(acrylamide) interspaced with poly(ethylene glycol)
units, and Trisoperl, an aminopropyl-modified silica gel.
All these solid supports were tested side by side for their
suitability to act as carriers for the catalyst.
The synthesis of the ligand is depicted in Scheme 1. 5-
Bromosalicylaldehyde 3 was first reacted with 2-iodopro-
pane to yield the isopropoxy ether 4. In the following Heck
reaction, the carboxyl group was introduced as ethyl ester.
Then, the aldehyde 5 was transformed by Wittig reaction
into the styrene derivative 6 and subsequent saponification
led to ligand 7. All steps proceeded with fair to high yields.
The incorporated double bond should not hamper the ole-
fin metathesis because terminal olefins are favored to inter-
nal ones. Additionally, the isopropoxy ether might act as a
directing group for the catalytically active Ru-species.
O
O
O
O
OH
O
O
O
a)
b)
c)
d)
Br
Br
O
O
O
O
O
OH
3
4
5
6
7
Scheme 1. Synthesis of the ligand 7. a) iPrI, K
9%; c) Ph PCH
2
CO
3
, Cs
2
3 2 3 3
CO , DMF, 24 h, r.t., 96%; b) Ethyl acrylate, Pd(OAc) , P(o-Tolyl) , Et N, DMF, 5 h, 100 ꢁC,
8
3
3
Br, nBuLi, THF, 24 h, 0 ꢁC ! r.t., 72%; d) KOH, water/dioxane, 24 h, r.t., 92%.

5174
F. Michalek et al. / Journal of Organometallic Chemistry 691 (2006) 5172–5180
Cl
O
Cl
L
O
Ru
a)
b)
NH
2
H
N
H
N
O
O
8
- 11
NHC:
MesN
NMes
Support
Ligand
Solid Phase-bound Loading (µmol/g)
Catalyst
a
Hybrid Silica Gel PCy
NHC
PCy
NHC
PCy
NHC
PCy
NHC
3
8a
32
56
67
a
8b
b
HypoGel 400
PEGA
3
9a
b
9b
217
b
3
10a
10b
11a
11b
53
b
41
b
Trisoperl
3
16
b
5
a
Determined by ICP-MS [22].
Determined by AAS [22].
b
Scheme 2. Synthesis of the supported olefin metathesis catalysts. a) (1) 7, DCC, HOBt, Huenig’s base, DMF, 24 h, r.t.; (2) Ac
2
O, Et
3
2 2
N, DMAP, CH Cl ,
5
2 2
h, r.t., and b) 1a or 1b, CuCl, CH Cl , 4 h, rflx.
Ts
N
Conversion
00%
Ts
N
1
8
6
4
2
0%
0%
0%
0%
1
2a
13a
Scheme 3. Benchmark RCM-reaction.
Conversion
1
00%
0
%
8
0%
0%
0%
0%
0
1
2
3
4
5
6
Run
6
4
2
Fig. 4. RCM of 12a catalyzed by (h) 8b, (m) 9b, (s) 10b and (r) 11b.
Reaction conditions: 1 mol% Ru-complex, CH
determined by HPLC.
2 2
Cl , 2 h, rflx; Conversion
Regarding the complexes 8b–11b, the recycling experi-
ment showed again that the material had a major impact
on the activity of the immobilized Ru-complexes (Fig. 4).
The best results were obtained with 8b and 9b, where in
the first three runs almost complete conversion was
observed. Complexes 10b (attached to PEGA) and 11b
0
%
0
1
2
3
4
5
6
Run
(attached to Trisoperl) both showed a steady decrease in
Fig. 3. RCM of 12a catalyzed by (h) 8a, (m) 9a, (s) 10a and (r) 11a.
conversion, which was more pronounced for 10b than for
11b.
Reaction conditions: 1 mol% Ru-complex, CH
determined by HPLC.
2 2
Cl , 2 h, rflx; conversion

F. Michalek et al. / Journal of Organometallic Chemistry 691 (2006) 5172–5180
5175
Table 1
Ring closing metathesis of several olefins
a
b
Entry
Substrate
Product
Conversion run 1, run 2 (%)
8
a
8b
>98, >98
1
Ts
N
88, 46
N
Ts
12b
13b
2
Ts
N
Ts
14, 4
88, 76
N
1
2c
13c
3
4
Ts
25, 9
93, 84
94, 91
N
Ts
N
1
3d
1
2d
EtOOC
COOEt
EtOOC
COOEt
47, 27
12e
1
3e
5
6
84, 32
89, 51
85, 31
>98, 97
>98, 97
84, 50
OBn
OBn
1
3f
12f
OBn
OBn
1
3g
12g
7
O
O
Ph
Ph
13h
1
2h
a
Reaction conditions: 1 mol% 8a or 8b, CH
Determined by H NMR.
2
Cl
2
, 2 h, rflx.
b
1
We suppose that the high activities obtained with 8b and
b are due to the good accessibility of the Ru centers at the
surface of the materials. This is obviously not the case with
Besides the RCM reaction, cross metathesis (CM) and
9
ring-opening metathesis (ROM) also represent important
applications of olefin metathesis. We tested both immobi-
lized catalysts and compared them with both Grubbs cata-
lysts in these reactions. The reaction conditions applied
here were 2.5 mol% of catalyst and a reaction time of
24 h because CM reactions occur normally at a slower rate
than RCM reactions. The catalysts of the first generation,
1a and 8a, hardly reacted. The second generation catalysts
1b and 8b showed different results. Both were highly active
in the CM to 15b, but the outcome of the CM to 15a and c
was unequal. With 1b, the formation of 15a worked better
while the CM yielding 15c showed higher conversion with
8b (see Scheme 4).
1
0b and 11b.
We further extended the applicability of the immobilized
complexes on our new hybrid material 8a,b to other ring
closure reactions (Table 1). With every substrate, two runs
were performed to demonstrate the recyclability. As in the
previous experiments, 1 mol% of catalyst was used and the
reactions were run simultaneously to guarantee identical
conditions. Except for 13h (entry 7), complex 8b was
always superior to 8a. As already seen in the recycling
experiments of the RCM of 12a and also with the other
substrates, a drop in activity was observed for the second
run using 8a. This was not the case with 8b, where even
the formation of the trisubstituted cyclic olefins 13c and d
ran smoothly (entry 2, 3).
Finally, we investigated the ring opening metathesis of
dicyclopentadiene 16 with 14a and 14b as partners
(Scheme 5). The ROM of 16 with 14a ran smoothly as

5176
F. Michalek et al. / Journal of Organometallic Chemistry 691 (2006) 5172–5180
O
O
a)
a)
a)
SiMe
3
+
+
+
SiMe
3
Ph
O
Ph
O
1
4a
14b
15a
OMe
MeO
MeO
Ph
MeO
Ph
1
4c
14c
15b
O
O
O
O
O
O
O
O
1
4d
14b
15c
a
Conversion (%)
Entry CM-Product
1a 8a 1b 8b
1
2
3
a
15a
15b
15c
0
0
83 63
46 11 >98 >98
65 83
0
1
1
Determined by H NMR.
Scheme 4. CM-reactions using 1a, 1b, 8a, 8b. a) 2.5 mol% Ru-complex, CH
2 2
Cl , 24 h, rflx.
SiMe
3
a)
b)
+
+
+
SiMe
3
SiMe3
16
14a
17a
17b
O
Ph
Ph
Ph
+
O
O
O
O
O
1
6
14b
18a
Cl
18b
Scheme 5. ROM/CM-reactions catalyzed by 8a and 8b. a) 0.5 mol% 8a or 8b, CH
7% + ROMP-polymers from 16.
2
2
2 2
, 2 h, rflx; 8a > 98%, 8b > 98%; b) 2.5 mol% 8b, CH Cl , 6 h, rflx,
4
reported earlier, using only 0.5 mol% of each immobi-
lized catalyst [30]. However, it was not possible to
determine the ratio of the regioisomers despite detailed
The leaching of 8a,b was determined by performing the
RCM of 12a on a larger scale. After the separation of the
product by simple filtration, the Ru content was determined
by atomic absorption spectroscopy (AAS). In the case of 8a,
285 ppm of Ru were found in the product; with 8b, the value
was 684 ppm of Ru [43]. These results were not as low as the
best systems reported so far [31–35] but were in the range
observed for other supported Ru-complexes [36–42].
2
D-NMR experiments. The ROM using 14b instead gave
disappointing results. With catalysts 1a and 8a, only ring
opening metathesis polymerization (ROMP) of 16 was
observed. Only with 1b and 8b the ROM-products were
formed, although the ROMP of 16 also took place to
a certain extent. The conversion of the ROM could be
determined by proton NMR, but it was not possible to
separate 18a,b from the polymers. Probably, the olefin
3. Conclusion
1
4b is not reactive enough to prevent the competing
New Grubbs–Hoveyda-type catalysts were synthesized,
which were attached via an amide bond to four different
amino-functionalized solid supports. The activities of the
immobilized catalysts were highly dependent on the nature
of the support, which was demonstrated by recycling
experiments using the ring closing metathesis of N,N-diallyl
tosylamide. The best results were obtained applying a new
home-made hybrid silica material and HypoGel 400 as
supports. Furthermore, the catalysts on the hybrid silica
ROMP of 16.
The major drawback of olefin metathesis is the high
amount of Ru leaching into the product [12]. Several
time-consuming or cost-intensive methods were developed
to reduce the metal contamination after reaction [12–16].
Immobilization of the Ru-complexes is a strategy to avoid
the contamination from the very start as can be seen in the
literature [31–42].

F. Michalek et al. / Journal of Organometallic Chemistry 691 (2006) 5172–5180
5177
gel performed well in RCM, CM and ROM reactions of var-
4.2.2. Ligand (7) on HypoGel 400
ious substrates. The leaching of these catalysts into the prod-
uct was 285 ppm Ru and 684 ppm Ru for 8a and 8b,
respectively which is not as low as with the best systems
reported so far but similar to other values reported for immo-
bilized Ru complexes. Most importantly, our data indicate
that although at least partly homogeneous, the catalysis
was influenced by the nature of the applied support material.
IR (neat): 3509, 3329, 3083, 3059, 3027, 2935, 2603,
2504, 2338, 2260, 1946, 1874, 1806, 1748, 1668, 1623,
1601, 1539, 1495, 1448, 1420, 1348, 1304, 1243, 1088,
1046, 1030, 991, 956, 907, 843, 817, 802, 760, 702, 655,
ꢁ
1
642, 543 cm
.
4.2.3. Ligand (7) on PEGA
IR (neat): 3497, 3302, 3063, 2917, 2124, 1964, 1737,
1648, 1536, 1492, 1454, 1399, 1350, 1300, 1252, 1091,
4
. Experimental
ꢁ
1
1
043, 952, 852, 555 cm .
4
.1. General procedure
4
.2.4. Ligand (7) on Trisoperl
IR (neat): 3606, 3428, 2982, 2938, 1979, 1871, 1652,
All reagents were obtained from Aldrich, Fluka or Lan-
ꢁ1
caster and were of highest purity available. CH Cl was
1621, 1393, 1066, 917, 803, 673 cm .
2
2
dried over CaH . The synthesis of 7 was described earlier
2
[
44].
Melting points were measured with the electrothermal
4.3. General procedure: Solid phase-bound catalyst for
metathesis reactions (8–11)
digital melting device IA 9200 and are uncorrected. Col-
umn chromatography (CC) was performed using commer-
cially available MN Silica gel 60 (0.063–0.2 mm/70–230
mesh) ASTM for CC from Baker. NMR Spectra were
recorded on a 300 MHz (Varian), 400 and 500 MHz (Bru-
The solid phase was suspended in dry CH Cl under
argon. Grubbs catalyst 1a or 1b (1.3 equiv) and CuCl
1.3 equiv) were added and the reaction was heated to
2
2
(
reflux for 4 h. After cooling to r.t., the solid phase was
removed from the reaction mixture, washed with CH Cl ,
1
ker) spectrometer for H NMR, on a 100.6 and 125.7 MHz
2
2
1
3
(
Bruker) for C NMR; chemical shifts d in ppm rel. to
and dried in a desiccator.
The loading of Ru was determined by ICP-MS or
AAS.
1
Me Si (=0 ppm) for H-NMR and rel. to CHCl3
=77.0 ppm) for C-NMR respectively. J in Hz. MS:
4
1
3
(
TSQ-700 (EI, CI, ESI) mass spectrometer; IR spectra were
recorded on a SpectrumOne from Perkin Elmer. HPLC:
Agilent 1100 system with binary pump, sample changer,
column oven and diode array detector.
4
.3.1. (8a) (32 lmol/g Ru)
IR (neat): 3642, 3367, 3085, 3066, 3029, 2930, 2856,
991, 1878, 1743, 1623, 1494, 1453, 1413, 1373, 1123,
02, 699 cm
1
8
ꢁ
1
.
4.2. General procedure: (E)-3-(4-Isopropoxy-3-vinyl-
phenyl)-acrylic acid (7) coupled to solid support
4.3.2. (8b) (56 lmol/g Ru)
IR (neat): 3657, 3639, 3363, 3066, 3028, 2926, 1996,
874, 1619, 1493, 1453, 1420, 1376, 1072, 801, 699
For the coupling, HOBt (0.27 g, 2.00 mmol) and 7
1
(
0.46 g, 1.99 mmol) were dissolved in DMF (40 mL). To
this solution DCC (0.41 g, 1.99 mmol) and Huenig’s base
0.68 mL, 0.52 g, 4.03 mmol) were added. After 10 min,
the coupling mixture was added to the solid phase (2.10 g,
.13 mmol) suspended in fresh DMF and the flask was sha-
ꢁ1
cm
.
(
4
.3.3. (9a) (67 lmol/g Ru)
IR (neat): 3517, 3428, 3334, 3082, 3059, 3027, 3001, 2916,
338, 2305, 1944, 1870, 1803, 1743, 1669, 1627, 1602, 1590,
537, 1512, 1493, 1452, 1413, 1386, 1375, 1348, 1329, 1266,
0
2
1
1
7
ken at r.t. When the Kaiser-test for amino groups was neg-
ative, the solid phase was removed from the reaction and
washed consecutively with DMF, water, DMF and CH Cl .
248, 1206, 1103, 1030, 1003, 983, 951, 928, 850, 819, 799,
2
2
ꢁ1
60, 737, 705, 623, 562, 540, 519, 480 cm
.
Next, the solid phase was suspended in CH Cl . A solution
2
2
of Et N (0.62 mL, 0.45 g, 4.45 mmol) and DMAP (48 mg,
3
4.3.4. (9b) (217 lmol/g Ru)
3
90 lmol) in CH Cl (4 mL) was added, followed by a
2 2
IR (neat): 3942, 3513, 3332, 3082, 3059, 3027, 3002,
918, 2307, 2711, 2524, 2413, 1947, 1876, 1807, 1740,
667, 1626, 1602, 1540, 1512, 1493, 1453, 1422, 1399,
375, 1348, 1329, 1266, 1103, 1031, 982, 952, 909, 854,
solution of acetic anhydride (0.37 mL, 0.40 g, 3.92 mmol)
in CH Cl (2 mL), and the reaction mixture was shaken at
2
1
1
7
2
2
r.t. for 4 h. Finally, the solid phase was washed
with CH Cl , DMF, H O, DMF, CH Cl and Et O and
2
2
2
2
2
2
ꢁ
1
97, 733, 702, 646, 621, 579, 542 cm
.
dried.
4
.2.1. Ligand (7) on hybrid silica gel
IR (neat): 3652, 3331, 3085, 3065, 3028, 2979, 2927,
991, 1878, 1717, 1626, 1601, 1544, 1535, 1493, 1453,
4.3.5. (10a) (53 lmol/g Ru)
IR (neat): 3487, 3317, 3060, 2865, 2127, 1943, 1720,
1643, 1536, 1492, 1452, 1399, 1350, 1297, 1254, 1100,
1
1
ꢁ
1
ꢁ1
417, 1386, 1374, 1052, 801, 699 cm
.
1046, 1000, 949, 849, 731, 698, 559 cm
.

5178
F. Michalek et al. / Journal of Organometallic Chemistry 691 (2006) 5172–5180
+
4
.3.6. (10b) (41 lmol/g Ru)
[M ], 236 (7), 184 (85), 155 (40), 96 (87), 91 (37), 69
IR (neat): 3500, 3312, 3059, 2873, 2128, 1943, 1711,
643, 1539, 1489, 1455, 1400, 1350, 1297, 1255, 1119,
(35), 67 (30), 41 (24).
1
1
ꢁ
1
042, 997, 950, 851, 769, 731, 698, 580 cm
.
4.5.3. 3-Methyl-1-[(4-methylphenyl)sulfonyl]-2,5-dihydro-
1H- pyrrole (13c) [23]
1
4
1
4
1
4
.3.7. (11a) (16 lmol/g Ru)
IR (neat): 3606, 3431, 2982, 2935, 2857, 1979, 1872,
652, 1622, 1385, 1076, 916, 803, 673 cm
H NMR (400 MHz, CDCl ): d = 1.66 (m , 3H,
3
c
CH@C(CH )CH ), 2.43 (s, 3H, SO PhCH ), 3.95–3.98
3
2
2
3
ꢁ
1
.
(m, 2H), 4.05–4.09 (m, 2H), 5.25 (m , 1H, CH CH@
c
2
C(CH )CH ), 7.32 (m, 2H, arom.), 7.72 (m, 2H, arom.);
3
2
1
3
.3.8. (11b) (5 lmol/g Ru)
IR (neat): 3601, 3425, 2983, 2936, 1977, 1869, 1740,
653, 1623, 1384, 1080, 916, 804, 673 cm
C NMR (100.6 MHz, CDCl ): d = 14.1, 21.5, 55.1,
3
57.7, 119.1, 127.5, 129.7, 134.4, 135.1, 143.3; GC/MS–EI
ꢁ
1
+
.
(70 eV); m/z (%) = 237 (22) [M ], 236 (16), 222 (23)
+
+
[
[C
C H NO S ], 172 (5), 155 (92) [C H O S ], 91 (67)
1
1
12
þ
2
7
7
2
+
.4. General procedure: Recycling experiments with 12a
7
H ], 82 (100) [C H N ], 80 (10), 67 (7), 65 (17), 55 (10).
7
5
8
The supported catalysts 8–11 were placed in a reaction
4.5.4. 5-Methyl-1-[(4-methylphenyl)sulfonyl]-1,2,3,6-
tetrahydropyridine (13d) [23]
tube under air and 12a was added from a stock solution
1 mL, 50 lmol, 0.05 M in CH Cl ). The reaction mixture
1
(
H NMR (400 MHz, CDCl ): d = 1.64–1.66 (m, 3H,
2
2
3
was shaken for 2 h at 60 ꢁC (oil bath). Then, a sample of
the reaction mixture was taken to determine the conversion
by HPLC. After this, the supernatant solution was removed
and the solid phases were washed with CH Cl (3 · 1.5 mL).
Then, fresh substrate wasadded and the next run wasstarted.
In total, five consecutive runs were performed like this.
CH C(CH )@CHR), 2.08–2.13 (m, 2H, NCH CH ), 2.42
2
3
2
2
(s, 3H, SO PhCH ), 3.16 (t, J = 5.8 Hz, 2H, NCH CH ),
2
3
2
2
3.52 (ddq, J = 5.5, 2.3, 2.3 Hz, 2H, NCH CH@C(CH )-
2
3
CH ), 5.30 (ddq, J = 6.5, 3.2, 1.6 Hz, 1H, CH CH@
2
2
2
2
C(CH )CH ), 7.31 (m
0
0
, Japp = 8.2 Hz, 2H, arom.),
3
2
AA BB
1
3
7.67 (m
0
0
, Japp = 8.2 Hz, 2H, arom.);
C NMR
AA BB
(
100.6 MHz, CDCl ): d = 21.5, 22.9, 30.0, 42.9, 44.8,
3
4
.5. General procedure: RCM reactions
116.6, 127.7, 129.6, 132.8, 133.4, 143.4; GC/MS–EI
+
(
70 eV); m/z (%) = 252 (14), 251 (100) [M ], 237 (14), 236
+
+
The supported catalysts 8–11 were placed in a reaction
(92) [C H NO S ], 155 (61) [C H O S ], 147 (6), 96
12 14 2 7 7 2
(70) [C H N ], 94 (29), 91 (47) [C H ], 69 (55), 68 (15),
6 10
7
+
þ
7
tube under air and the a,x-olefin was added from a stock
solution (1 mL, 50 lmol, 0.05 M in CH Cl ). The reaction
67 (12), 65 (14), 53 (6), 41 (25).
2
2
mixture was shaken for 2 h at 60 ꢁC (oil bath). After cool-
ing to r.t., the supernatant solution was removed and the
solid phases were washed with CH Cl (3 · 1.5 mL). Then,
4.5.5. Cyclopent-3-ene-1,1-dicarboxylic acid diethyl ester
(13e) [47]
2
2
1
fresh substrate was added and the next run was started.
H NMR (400 MHz, CDCl ): d = 1.25 (t, J = 7.1, 6 H,
3
1
The conversions were determined by H-NMR.
ACH CH ), 3.01 (s, 4H, ACH ACH@CHACH A), 4.20
2
3
2
2
(
q, J = 7.1, 4H, ACH CH ), 5.61 (s, 2H, ACH ACH@
2
3
2
13
4
[
.5.1. 1-(Toluene-4-sulfonyl)-2,5-dihydro-1H-pyrrole (13a)
45]
CHACH A); C NMR (100.6 MHz, CDCl ): d = 14.0,
2
3
40.9, 58.9, 61.2, 127.8, 172.3; MS–EI (70 eV): m/z
(%) = 212 (63) [M ], 166 (60), 138 (100), 111 (38), 93
1
+
H NMR (400 MHz, CDCl ): d = 2.42 (s, 3H, Ar-CH ),
3
3
4
.12 (s, 4H, CH CH@CHCH ), 5.65 (s, 2H, CH CH@
(32), 79 (40), 66 (54).
2
2
2
CHCH ), 7.32 (m
0
0
, Japp = 8.1 Hz, 2H, arom.), 7.72
2
AA BB
1
3
(
m
0
0
,
Japp = 8.1 Hz, 2H, arom.);
C
NMR
4.5.6. (Cyclopent-2-enyloxymethyl)-benzene (13f) [48]
1
AA BB
(
100.6 MHz, CDCl ): d = 21.6, 54.9, 125.5, 127.5, 129.8,
H NMR (500 MHz, CDCl ): d = 1.82–1.89 (m, 1H,
3
3
+
0 0 0 0
H -4 /H -4 ), 2.12–2.19 (m, 1H, H -4 /H -4 ), 2.23–2.30
A B A B
1
1
34.4, 143.5; MS–EI (70 eV): m/z (%) = 223 (50) [M ],
0 0 0 0
(m, 1H, H -5 /H -5 ), 2.47–2.55 (m, 1H, H -5 /H -5 ),
A B A B
55 (52), 91 (92), 86 (13), 84 (20), 68 (100), 65 (24), 41 (24).
4.51 (d, JAB = 11.7 Hz, 1H, HCHAAr), 4.55 (d,
4.5.2. 1-(Toluene-4-sulfonyl)-2,3,4,7-tetrahydro-1H-
azepine(13b) [46]
JAB = 11.7 Hz, 1H, HCHAAr), 4.67 (m , 1H, ˜CHOR),
c
0
0
5.88–5.91 (m, 1H, H-3 ), 6.01–6.04 (m, 1H, H-2 ), 7.24–
1
13
H NMR (300 MHz, CDCl ): d = 1.80 (m , 2H), 2.18
7.37 (m, 5H, arom.); C NMR (100.6 MHz, CDCl3):
3
c
(
m , 2H), 2.41 (s, 3H, CH AAr), 3.39 (t, J = 6.1 Hz,
d = 29.8, 31.1, 70.6, 84.5, 127.4, 127.8, 128.3, 130.8,
c
3
2
H, NACH ACH A), 3.83 (d, J = 4.5 Hz,
2
H,
135.7, 138.9; MS–CI (NH , 130 eV): m/z (%) = 192 (12)
2
2
3
+
+
NCH CH@CHA), 5.64 (dt, J = 5.1, 10.6 Hz, 1H, H-2/
[(M + NH ) ], 175 (4) [(M + H) ], 157 (10), 126 (21), 108
2
4
H-3), 5.77 (dt, J = Hz, 5.3, 10.9 Hz, 1H, H-2/H-3), 7.28
(17), 91 (36), 84 (100), 67 (7).
(
8
m
0
0
, Japp = 8.2 Hz, 2H, arom.), 7.68 (m
0
0
, Japp =
AA BB
AA BB
1
3
.1 Hz, 2H, arom.); C NMR (100.6 MHz, CDCl3):
d = 21.5, 26.9, 31.0, 46.4, 49.7, 126.7, 127.3, 129.6,
33.0, 136.5, 143.1; MS–EI (70 eV): m/z (%) = 251 (100)
4.5.7. (Cyclohex-2-enyloxymethyl)-benzene (13g) [49]
1
H NMR (500 MHz, CDCl ): d = 1.51–1.59 (m, 1H),
3
1
1.71–1.89 (m, 3H), 1.91–1.99 (m, 1H), 2.02–2.10 (m, 1H),

F. Michalek et al. / Journal of Organometallic Chemistry 691 (2006) 5172–5180
5179
3
.93–3.98 (br m, 1H, H-1), 4.55 (dAA
0
, J = 12.0 Hz, 1H,
J = 6.4 Hz, 2H, CH OAc), 5.17 (s, 2H, PhCH O), 5.88
2 2
CHHO), 4.61 (dAA , J = 12.0 Hz, 1 H, CHHO), 5.79–5.89
(
0
(dt, J = 15.6, 1.5 Hz, 1H, CH@CHCH2), 7.00 (dt,
1
3
m, 2H, H-2/H-3), 7.24–7.37 (m, 5H, arom.); C NMR
100.6 MHz, CDCl ): d = 19.3, 25.3, 28.4, 70.0, 72.2,
J = 15.6, 6.9 Hz, 1H, CH@CHCH ), 7.33–7.38 (m, 5H,
2
1
3
(
arom.); C NMR (100.6 MHz, CDCl ): d = 21.0, 24.4,
3
3
1
27.4, 127.6, 127.8, 128.3, 130.9, 139.1; MS–EI (70 eV):
28.1, 31.7, 64.0, 66.1, 121.5, 128.2, 128.2, 18.6, 136.1,
+
m/z (%) = 188 (5) [M ], 130 (9), 97 (48), 91 (100), 84 (8),
149.1, 166.4, 171.1; MS–EI (70 eV): m/z (%) = 276 (1)
þ
8
4
4
1 (13), 79 (13), 77 (7), 69 (22), 65 (11), 55 (10), 41 (15).
[M+], 216 (6) [C H O ], 169 (15), 156 (18), 127 (97),
1
4
17
2
+
þ
1
10 (32), 107 (30) [C H O ], 91 (100) [C H ], 81 (50), 68
7 7
+
7
7
.5.8. 2-Phenyl-3,6-dihydro-2H-pyran (13h) [50]
1
(13), 43 (10) [C H O ].
2 3
H NMR (300 MHz, CDCl ): d = 2.20–2.44 (m, 2H),
3
.33–4.39 (m, 2H), 4.56 (dd, J = 3.8, 10.0 Hz, 1H, O–
4.7. General procedure ROM-reactions
CHAAr), 5.77–5.85 (m, 1H), 5.88–5.96 (m, 1H), 7.25–
1
3
7
.41 (m, 5H, arom.); C NMR (100.6 MHz, CDCl3):
Dicyclopentadiene and the terminal olefin (each 1 equiv.)
were placed in a reaction tube under air (CH Cl , 1 mL,
d = 32.9, 66.6, 75.7, 124.5, 125.9, 126.4, 127.5, 128.4,
42.6; MS–EI (70 eV): m/z (%) = 160 (16) [M ], 105
2
2
+
1
0.07 M). The reaction was started by adding the catalyst.
The reaction mixture was shaken for 2 h at 60 ꢁC (oil bath).
After cooling to r.t., the supernatant solution was removed
and the solid phases were washed with CH Cl (3 · 1.5 mL).
(
100), 77 (18), 54 (75).
4
.6. General procedure CM-reactions
2
2
Then, fresh substrate was added and the next run was
1
Both terminal olefins (each 1 equiv.) were placed in a
started. The conversions were determined by H-NMR.
reaction tube under air (0.2 mL CH Cl , 0.25 M). The
2
2
reaction was started by adding the catalyst. The reaction
mixture was shaken for 2 h at 60 ꢁC (oil bath). After
cooling to r.t., the supernatant solution was removed
and the solid phases were washed with CH Cl
4.7.1. Mixture of (2E)-3-(3-Vinyl-1,2,3,3a,4,6a-
hexahydropentalene-1-yl)-prop-2-ene-1- trimethylsilane
(17a) and (2E)-3-(3-Vinyl-1,2,3,3a,6,6a-
hexahydropentalene-1-yl)-prop-2-ene-1- trimethylsilane
(17b)
2
2
(
3 · 1.5 mL). Then, fresh substrate was added and the
1
next run was started. The conversions were determined
H NMR (500 MHz, CDCl ): d = ꢁ0.01 (s, 6H), 0.015
3
1
by H NMR.
(s, 1H), 0.018 (s, 2H), 1.20–1.30 (m, 1H, CHH), 1.41–1.45
(
m, 2H, CH SiMe ), 1.54–1.61 (m, 1H, CHH), 2.23–2.29
2 3
4
(
.6.1. (2E)-4-Trimethylsilanyl-but-2-enoic-acid-benzylester
14a)
(m, 2H, CH ), 2.53–2.69 (m, 2H, 2 · CH), 2.76–2.89 (m,
2
1H, CH), 3.18–3.29 (m, 1H, CH), 4.92–5.04 (m, 2H,
1
H
NMR (300 MHz, CDCl3): d = 0.04 (s, 9H,
@CH ), 5.12–5.32 (m, 1H, @CH), 5.34–5.45 (m, 1H,
2
ASi(CH ) ), 1.72 (d, J = 8.9 Hz, 2H, ACH Si), 5.15 (s,
CH@CH Si), 5.47–5.55 (m, 1H, @CH), 5.64–5.72 (m, 1H,
3
3
2
2
1
3
2
H, PhCH ), 5.70 (d, J = 15.4 Hz, ROOCCH@), 7.08 (dt,
@CH), 5.74–5.92 (m, 1H, CH@CH2);
C
NMR
2
J = 15.4, 8.9 Hz, @CHCH ), 7.29–7.35 (m, 5H, arom.);
(125.7 MHz, CDCl ): d = ꢁ1.9, ꢁ1.7, 22.8, 35.0, 35.3,
2
3
1
3
C NMR (100.6 MHz, CDCl ): d = 0.0, 26.9, 67.6,
43.9, 47.0, 47.4, 55.3, 114.3, 125.8, 130.3, 131.1, 131.4,
3
1
20.5, 129.86, 129.92, 130.3, 138.3, 150.6, 168.5; MS–CI
140.4; GC/MS–CI (NH , 130 eV); m/z (%) = 248 (21), 247
(100), 246 (6) [M ], 245 (10), 173 (4), 172 (4), 90 (56), 73 (3).
3
+
(
NH , 130 eV); m/z (%) = 268 (7), 267 (21), 266 (100),
3
2
49 (25), 194 (15), 108 (9), 90 (6); Anal. Calc. for
C H O Si: C 67.70, H 8.12; found: C 67.83, H 8.00%.
1
4
20
2
Acknowledgements
0
4
(
.6.2. 1,1 -(E)-Ethene-1,2-diylbis(4-methoxybenzene)
14b)
We thank Fluka for AAS-measurements and Novabio-
chem, Rapp-Polymers and VitraBio GmbH for samples
of solid supports. Also, we would like to thank Dr. M.
Keller, Mrs. M. Schonhard and Mr. F. Reinbold for
recording NMR spectra, Mr. C. Warth and Dr. J. W o¨ rth
for recording MS spectra, Mr. E. Hickl for performing
elemental analyses and Mrs. S. Hirth-Walter for perform-
ing AAS.
1
Mp.: 214–216 ꢁC;
d = 3.81 (s, 6H, OCH ), 6.87 (m
arom.), 6.91 (s, 2H, CH@CH), 7.41 (m
H, arom.); C NMR (100.6 MHz, CD Cl ): d = 55.6,
14.4, 126.4, 127.7, 130.8, 159.5; GC/MS–EI (70 eV); m/z
%) = 241 (17), 240 (100) [M ], 226 (8), 225 (48)
H
NMR (300 MHz, CDCl3):
, Japp = 8.6 Hz, 2H,
0
0
3
AA BB
0
0
, Japp = 8.6 Hz,
AA BB
1
3
2
1
(
[
2 2
+
+
M ꢁCH ], 182 (13), 181 (8), 166 (12), 165 (33), 154 (8),
3
1
53 (20), 152 (14), 120 (13); Anal. Calc. for C H O : C
16 16 2
References
7
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.6.3. Benzyl-(2E)-7-(acetyloxy)hept-2-enoate (14c)
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