Catalysts on functionalized polymer chips (PC) as recyclable entities

Article abstract of DOI:10.1055/s-2005-918479

We describe surface-modified sintered polyethylene sheets as a suitable carrier system for various catalysts. The material shows high rigidity and no swelling properties and allows for easy removal and reuse of the supported catalysts. The application was demonstrated for Pd-, Rh-, and Ru-catalysts in Suzuki couplings, hydroformylation, and olefin metathesis, respectively. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2005-918479

3
362
PAPER
Catalysts on Functionalized Polymer Chips (PC) as Recyclable Entities
ities oç,a,1 Florian Michalek, Luigi Rumi, Willi Bannwarth,* Rainer Haag*
b
b
b
a,c
C
F
atalysts on
F
i
unction
k
a
lizedPolym
r
er Chip
e
s
(PC) as
R
t
ecyclable Ent
K
a
Department of Chemistry, University of Dortmund, Otto-Hahn-Str. 6, 44221 Dortmund, Germany
Department for Chemistry and Biochemistry, Albert-Ludwigs University Freiburg, Albertstraße 21, 79104 Freiburg, Germany
Fax +49(761)2038705; E-mail: Willi.Bannwarth@organik.chemie.uni-freiburg.de
Department of Chemistry, Free University of Berlin, Takustrasse 3, 14195 Berlin, Germany
Fax +49(30)83853357; E-mail: Haag@chemie.fu-berlin.de
b
c
Received 22 June 2005
Dedicated to Professor Steven V. Ley on the occasion of his 60 birthday
th
(
SPOS) or in solid phase peptide synthesis (SPPS), and
Abstract: We describe surface-modified sintered polyethylene
sheets as a suitable carrier system for various catalysts. The material
shows high rigidity and no swelling properties and allows for easy
11
they can be used for catalyst immobilization. In general,
these methods were developed to prepare resins which are
removal and reuse of the supported catalysts. The application was more practical to handle.
demonstrated for Pd-, Rh-, and Ru-catalysts in Suzuki couplings,
Here we report on a new, easy to handle, and very stable
hydroformylation, and olefin metathesis, respectively.
support (functionalized Polymeric Chip [PC]) for the im-
mobilization of catalytic systems (e.g., Pd, Rh, and Ru).
The advantage of PCs is their exclusive functionalization
on the highly porous surface so that swelling of the poly-
mer is not an issue anymore.
Key words: solid support, heterogeneous catalysis, palladium,
rhodium, ruthenium, Suzuki reaction, hydroformylation, olefin
metathesis
Furthermore, these PCs can be applied in continuous
flow-type processes due to their porous structure.
Development of new versatile, environmentally benign
and robust carrier systems for immobilization of different
transition-metal catalysts is of great importance due to These PCs, which are made of polyethylene and function-
their applications in organic synthesis. Nowadays synthet- alized with Boc-protected primary amines, are now com-
1
2
ic chemistry is no longer conceivable without the use of mercially available. Different ligands can be attached to
catalysts. Easy removal and recycling of expensive and them to immobilize transition metals for catalytic reac-
poisonous transition-metal catalysts is thus becoming tions or SPOS and SPPS can be performed directly or after
more and more significant.
functionalization with different linker systems. Here, we
report the immobilization of Pd-, Rh-, and Ru-complexes
on this new carrier system and demonstrate its various ap-
plications in catalysis.
2
3
Different soluble polymers and solid supports are used
as carriers to recover catalysts. Furthermore, various sol-
4
vent systems such as perfluorinated solvents, ionic liq-
5
6
uids, o7r supercritical CO are employed for this
2
purpose.
Immobilized Pd on PC in Suzuki Reactions
Over the last few years, functionalized polystyrene beads
have been increasingly used for immobilization of differ-
Pd-complexes are well-known for their ability to catalyze
various types of reactions, e.g., Suzuki and Stille cou-
8
ent catalysts. However, only a few examples are known
for polymeric carrier systems, which are easy to handle.
One system is the monolithic polymer disc of Stevenson,
which has good swelling characteristics in different sol-
9
vents. Another characteristic of this soft carrier is its re-
sistance to osmotic shock. These discs were prepared by
polymerizing styrene with different cross-linkers [divi-
nylbenzene, poly(ethylene glycol) (PEG)400 bisacrylate
or PEG 1000 bisacrylate] in a suitable solvent and used in
the Suzuki reaction.
The second type of support was reported by Bradley et
1
0
al. The main idea of this new methodology is to sinter
the resin into a polymer matrix. These ‘resin plugs’ were
used like normal resins in solid phase organic synthesis
SYNTHESIS 2005, No. 19, pp 3362–3372
x
x.
x
x
.
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0
0
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Advanced online publication: 14.11.2005
DOI: 10.1055/s-2005-918479; Art ID: C05305SS
Georg Thieme Verlag Stuttgart · New York
Figure 1 Catalyst-modified PC (left) during reaction and (right)
simple separation of the immobilized catalyst from the reaction mix-
ture.
©

PAPER
Catalysts on Functionalized Polymer Chips (PC) as Recyclable Entities
3363
plings, Heck reactions, carbonylations, asymmetric allyl-
ations, aminations, sp–sp cross-couplings, just to name a
few. Here, we present the application of immobilized Pd
on PC in Suzuki coupling reactions.
(
CH2O)n, HCl
2
P+
Cl–
P
95%
H
HOH C CH OH
2
2
1
Suzuki coupling is one of the most important carbon–car-
1
3
Scheme 2 Synthesis of the phosphonium salt.
bon bond-formation reactions. Generally, this reaction is
utilized to prepare biaryl systems. Commonly, a Pd(0)
species is used as catalyst; an aryl halide (A) and an aryl
boronic acid or ester (B) as components to be coupled in
the presence of a base (Scheme 1).
The reaction of phosphonium salt 1 with amine-function-
alized PC in the presence of Et N gave the anchor ligand
3
for immobilization of palladium (Scheme 3).
Reaction of Pd(dba) with 3 resulted after ligand exchange
reaction in a PC-immobilized Pd(dba) species 4a. The Pd
2
[
Pd], base
X
+
B(OR)2
R
R'
R
R'
content was determined by ICP–MS measurements.
A
B
C
Scheme 1 Suzuki reaction.
Different ligand systems and solid phases are known for
2
the immobilization of Pd, and different soluble and non-
3
soluble polymers have been employed as supports. Here,
we use a novel type of functionalized polyethylene (PE)
polymer chips (Figure 1) as a highly porous non-soluble
support for palladium. The immobilization of Pd on solid
3
,14
supports has been known for several years. However,
recycling is still problematic, because the used polymer
15
matrices are not stable under mechanical conditions. For
example, agitating with a stirrer bar typically destroys a
1
6
weakly cross-linked polymeric support. Reactions are
only possible under shaking conditions or by stirring very
Scheme 3 Construction of anchor and complexation of Pd(dba)2
slowly, which has a negative effect on reaction kinetics. with functionalized PC (3).
The use of PCs is very advantageous because of the nearly
unrestrained mechanical stability. They are also easy to
handle as they can be separated from the product by just
removing them from the reaction mixture with tweezers
These catalytically active PCs were then used in different
Suzuki coupling reactions.
In order to evaluate the catalysts recycling, the Suzuki re-
action of phenylboronic acid (5a) and p-bromoacetophe-
none (6a) was repeated five times (Table 1).
(
Figure 1). No filtration step is required! After a simple
washing procedure, they can be reused in the next reaction
or run.
From a variety of different Pd-ligand systems we selected
Table 1 Recyclable Suzuki Reaction of Phenylboronic Acid (5a)
the versatile bis(diphenylphosphanyl)methyl ligand sys- and p-Bromoacetophenone (6a)
tem, which is attached to amine-functionalized surfaces in
Pd(dba)
on PC
Cs2CO3
quantitative yields as has been demonstrated by several
O
O
B(OH)2
+
Br
groups. This bidentate anchor group is versatile in the
complexation of various transition metals, e.g., Pd, Rh, Ir,
and Ni as demonstrated by Reetz et al. by immobilization
DMF
5
a
6a
7a
1
7
on dendrimer shells.
Cycle
Temp. (°C) Conversion after
h (%)a
Conversion after
6 h (%)a
2
In general, bis(diphenylphosphanyl)methyl functionality
is introduced by methylphosphanylation of amines (Man-
nich-type reaction) using diphenylphosphine and para-
formaldehyde. This method was demonstrated by Alper et
1
120
100
120
120
120
95.6
55.1
93.6
76.4
63.5
98.0
96.7
97.3
97.8
96.0
2b
3
1
8
al. on amino-functionalized dendrimers. In this work we
introduced the bis(diphenylphosphanyl)methyl function-
ality via reaction of the primary amine with a preformed
4
phosphonium salt (Scheme 2) in the presence of Et N.
3
5
The easily accessible phosphonium salt has several ad-
vantages compared to free diphenylphosphine due to its
easier handling, oxidation stability, and non-pyrophorici-
a
1
Conversion determined by H NMR or GC–MS.
Reaction temperature: 100 °C for 2 h and 120 °C for 4 h.
b
1
9,20
ty.
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3
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F. Koç et al.
PAPER
The reaction of phenylboronic acid (5a) and p-bromoace- mol% immobilized Pd in the scale-up reaction, which is a
tophenone (6a) was performed in DMF in the presence of very low amount for heterogeneous reaction conditions.
Pd-loaded PC and Cs CO as a base on a 0.5 mmol scale. After additional experiments the TON and TOF could be
2
3
In order to study the temperature effect in cycle two, the calculated for the catalytic active 4a (TON = 360; TOF =
–
1
temperature was decreased to 100 °C and a significant ef- 36 h ).
fect on reaction kinetics was observed. In cycles three to
In order to show the general activity of prepared Pd-PC
4a) species, various boronic acids and also an electroni-
cally disfavored aryl halide were utilized in Suzuki reac-
tions. In entry 2 of Table 2, the reaction of phenylboronic
acid (5a) with p-bromoanisole (6b) is shown. This reac-
tion gave the desired biaryl system 7b in over 75% con-
version. For variation on the boronic acid side, p-nitrile-
five, the reaction temperature was increased again to 120
C and no big difference in conversion was observed after
six hours reaction time compared with the first cycle. In
all cases high conversions (> 95%) were obtained after six
hours. The conversion only decreased slightly after two
hours in cycles four and five.
(
°
(
5b), p-acetophenone- (5c), and p-methoxyphenylboronic
acid (5d) were chosen. Only the reaction with the p-nitrile
substituent (5b) worked with moderate conversions
(
65%). The experiment of 5c (entry 3) and 5d (entry 4) re-
sulted in good conversions (83% and 70%) and no starting
material could be detected. All reactions were performed
overnight (15 h) to get maximum conversions in an ac-
ceptable time range.
Immobilization of Rh on PC for Hydroformylation
Reactions
Figure 2 Recycling of the PC (4a) using 5a and 6a as substrates in PC 3 with the bisdiphenylphosphanyl ligand, which was
Suzuki reaction.
used for the immobilization of Pd, also proved useful to
support rhodium complexes. Here we immobilized a
Due to the relatively small quantity of starting material, a rhodium (I) species, which is a very common homoge-
5
-mmol scale-up of this reaction was performed. The neous catalyst for hydroformylation reactions
amount of catalytically active Pd-PC was kept nearly on (Scheme 4).
the same level (scale-up: 0.157 mol% as opposed to 1.55
mol% for the reaction in small scale). This reaction dem-
onstrated the easy handling of immobilized Pd on PC. Af-
ter completion of the Suzuki reaction 4a was fished out
with tweezers (Figure 1) and 7a was isolated in nearly
quantitative yields (99.5%) after an extraction to remove
inorganic salts produced without using any tedious col-
umn chromatography.
To determine the immobilized Pd amount, an ICP–MS
measurement was performed which resulted in 1191.6
ppm Pd. This means 11.20 mmol Pd per kg PC and 0.157
Scheme 4 Immobilization of [Rh(cod)]BF on functionalized PC 3
to form 4b.
4
Table 2 Suzuki Reaction with Various Substituted Aryl Halides and Aryl Boronic Acids
4a,
Cs2CO3,
DMF
R1
B(OH)2 + Br
R2
R1
R2
1
20 °C,
24 h
5a–d
6a–b
7b–e
Entry
R1
H
Boronic acid
R2
Aryl halide
Yield (%)
Product
7b
1
2
3
4
5a
5b
5c
5d
OMe
6b
6a
6a
6a
75
65
83
70
CN
COMe
COMe
COMe
7c
COMe
OMe
7d
7e
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PAPER
Catalysts on Functionalized Polymer Chips (PC) as Recyclable Entities
3365
The immobilization of homogeneous rhodium catalysts is
1
8,21
currently being investigated by several groups.
Be-
sides polymer beads, which are commonly used as solid
supports, silica was also utilized to immobilize rhodium.
In both cases, significant leaching has been observed. Hy-
2
2
droformylation reactions are atom-economic, but they
are still cost- and purification-intensive.
Hydroformylation is the reaction between an olefin and
syngas (CO, H ) in the presence of a homogeneous transi-
2
tion-metal catalyst, which results in a linear (n-) or
branched (iso-) aldehyde.
This reaction and their applications in synthetic organic
chemistry is part of extensive research in several
groups.
1
8,23,24,25
Figure 3 1H NMR spectrum of crude 4-(phthalimidyl)-3-methyl-
butyraldehyde (9).
Here, we used Rh-PC (4b) as an easily recyclable catalyst
in hydroformylation reactions. The starting material for
this representative reaction was methallylphthalimide (8).
This compound has the advantage that it forms only the n-
product and no side-products such as iso-product or
Olefin Metathesis
Since the development of Ru catalysts by Grubbs et al.,
olefin metathesis has become a valuable tool in the syn-
thetic repertoire of organic chemistry (Figure 4). Di-
verse applications like ring-closing metathesis (RCM),
ring-opening metathesis (ROM), cross metathesis (CM),
and enyne metathesis have offered new synthetic path-
2
6a
isomerization products. This compound is also interest-
ing, because primary amines are accessible after deprotec-
tion of the phthalimide functionality, which makes it even
more attractive for different investigations as demonstrat-
ed by Eilbracht et al. over the last two years.2
27
6
The hydroformylation was performed in a stainless auto- ways in the development of synthetic routes to important
clave whereby methallylphthalimide (8) was dissolved in organic compounds.28 The common catalysts 10a,b are
toluene (Scheme 5). PC-Rh 4b was inserted into the reac- easy to handle and show a wide tolerance for functional
tion mixture, and the mixture was pressurized with a 100 groups. Their only drawback is that they cannot be recov-
bar 1:1 mixture of syngas (CO/H ) before heating up to ered and that the leaching of Ru into the product is diffi-
2
1
00 °C for 48 hours. After reaction the PC-Rh 4b catalyst cult to control.
was fished out with tweezers and after solvent removal the
target aldehyde 9 was isolated without any further purifi-
cation in quantitative yield and very high purity (see the
N
N
R
R
PCy3
Ru
N
N
Cl
Cl
1
R
R
Cl
PCy3
Ru
Ru
H NMR spectrum in Figure 3).
Cl
Cl
Cl
Cl
Ru
Cl
Ph
Ph
O
O
PCy3
PCy3
O
O
Complex 4b
1
00 bar syngas (1:1)
N
N
O
1
0a
10b
11a
11b
48 h, 100 °C
quant.
1st Generation 2nd Generation 1st Generation
Hoveyda catalysts
2nd Generation
O
O
Grubbs catalysts
8
9
Figure 4 Olefin metathesis catalysts.
Scheme 5 Hydroformylation of methallylphthalimide (8).
Hoveyda et al. prepared the catalysts 11a,b (Figure 4).29
These complexes were stable to air and moisture and
could even be successfully recycled by chromatography
on silica gel. The remarkable stability is caused by the
ether chelate which provides an additional coordination
site. During the catalytic cycle, the ligand is liberated, and
after having consumed the substrate, the styrene ligand re-
Further observation during this reaction was that the mix-
ture of solvent and product was colorless after the reac-
tion. This is good evidence that no leaching occurred
during this reaction. Generally, the reaction mixture with
homogenous catalyst, product, and solvent has an intense
color after hydroformylation. The same Rh-PC catalyst 4b
was used three times in the same hydroformylation reac-
tion without any loss of reactivity (> 98% conversion ac-
2
+
30
captures the Ru so that the catalyst is reformed.
1
cording to H NMR).
Several groups soon realized that Hoveyda’s complex
would be easily amenable to immobilizations on solid
supports. In the meantime, Hoveyda et al. reported a den-
drimeric analogue as well as the immobilization on sol-
gel.3 Blechert et al. used polymeric supports like Wang
1,32
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3
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F. Koç et al.
PAPER
resin, Merrifield resin, or PEGA.33 Examples of soluble tored by the TNBS test. Possibly unreacted amino func-
35
3
4
polymer-bound catalysts were also reported.
tions were masked by an acylation step with Ac O.
2
Finally, catalysts 18a,b and 19a,b were prepared by a Ru
exchange employing 1.3 equivalents of catalysts 10a and
The general immobilization strategy involves the synthe-
sis of a modified styrene, which allows a covalent attach-
ment of the ligand to the support. Reaction with one of the
Grubbs catalysts (10a or 10b) then yields the immobilized
catalyst.
1
0b, respectively. The reaction with 10a led to a higher
Ru content than with 10b as determined by ICP–MS, on
the polypropylene sheet as well as on the polyethylene
plate.
We present here a new version of an immobilized
Hoveyda-type catalytic system in which the catalyst is at-
tached to the surface of amino-modified sintered polyeth-
ylene plates or polypropylene membranes via an amide
bond. This required ligand modification with a carboxyl
function. As the starting point, we chose the cheap and
readily available 4-bromosalicylic aldehyde 12. Both the
necessary vinyl group as well as the isopropoxy ether
function could be introduced in a straightforward manner,
and a Heck reaction allowed for the modification with a
carboxyl group to yield 16 as outlined in Scheme 6.
At first, we examined the recycling ability of 18a, 18b,
1
9a, and 19b in a ring-closing metathesis employing 20 as
a substrate in five consecutive runs (Scheme 8). Usually,
.5–5 mol% of catalyst were applied to olefin metathesis
2
reactions. In preliminary experiments we had already ob-
served that 1 mol% was sufficient for this reaction. Hence,
we decided to use this amount for the further experiments.
Furthermore, all reactions were performed in reagent-
grade solvent and without an inert atmosphere.
OH
O
O
O
O
O
a
b
Br
Br
12
13
O
O
14
O
O
O
O
c
d
Scheme 7 Synthesis of the catalysts 18a,b and 19a,b: (a) 16, DCC,
O
O
HOBt, Hünigs base, DMF, 24 h, r.t. and then Ac O, Et N, DMAP,
O
O
O
OH
2 3
CH Cl , 5 h, r.t., (b) 10a or 10b, CuCl, CH Cl , 4 h, reflux.
2
2
2
2
14
15
16
Scheme 6 Synthesis of 16: (a) i-PrI, K CO , Cs CO , DMF, 24 h,
2
3
2
3
Ts
N
r.t., 96%; (b) ethyl acrylate, Pd(OAc) , P(o-Tol) , Et N, DMF, 5 h,
Ts
N
2
3
3
a
1
00 °C, 89%; (c) Ph PCH Br, n-BuLi, THF, 24 h, 0 °C → r.t., 72%;
3
3
(
d) KOH, H O–dioxane, 24 h, r.t., 92%.
2
2
0
21
All steps proceeded with fair to high yields. We envisaged
that the incorporated double bond would not interfere with
the metathesis reaction.
Scheme 8 a) 1 mol% catalyst, CH Cl , reflux, 1.5 h.
2
2
For the second-generation catalysts, high conversions
were observed in the first three runs (Figures 5 and 6). In
runs four and five, a drop in activity took place. This level
of performance was not reached by the first-generation
catalyst.
1
2
Both solid-phase materials, the polyethylene as well as
the polypropylene supports, were available in a length and
width of 12 cm by 8 cm. This size proved to be problem-
atic for the immobilization of 16 and its conversion into
the catalyst. Fortunately, due to curling of the polypro-
pylene membrane in DMF and CH Cl , it was possible to
Next, we tested the supported catalysts 18a, 18b, 19a, and
2
2
1
9b on different a,w-olefins as substrates. Here we also
perform the immobilization of the whole sheet in a round
bottom flask. The sintered polyethylene, however, proved
to be a very rigid material. Therefore, it was cut into sev-
eral small pieces, which were modified simultaneously.
The coupling of ligand 16 to the amino-modified supports
was performed using DCC and HOBt for 24 hours
used 1 mol% of catalyst. The reactions were performed in
a parallel manner to guarantee identical reaction condi-
tions. As shown in Table 3, high conversions were ob-
tained with almost all olefins. Although the ring-closure
of the tosyl amides 20 (entry 1) and 22 (entry 2) ran
smoothly, the olefin 24 (entry 3) hardly reacted. Surpris-
(
Scheme 7). The completion of the coupling was moni-
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PAPER
Catalysts on Functionalized Polymer Chips (PC) as Recyclable Entities
3367
Figure 6 Recycling of the catalysts on polypropylene using 20 as
substrate.
Figure 5 Recycling of the catalysts on polyethylene using 20 as
substrate.
ingly, catalysts 18a and 19a were more active than 18b or formed by cross metathesis. With olefin 30 (entry 6), we
9b. Reaction of 24 with higher catalyst loadings led to an also observed low to moderate conversions which could
1
increase of the conversion with 18a and 19a, whereas the be improved by employing 2.5 mol% of catalyst.
activity of 18b and 19b remained still low. Besides the de-
In summary, we have prepared new solid-supported olefin
sired 25, we observed a low amount of side-products
metathesis catalysts by attaching them to the surface of
1
which might correspond, according to H NMR and to
amino-modified polyethylene and polypropylene sheets
mass spectra, to the dimer and trimer of 24, possibly
Table 3 Ring-Closing Methathesis of Several a,w-Olefins
Entry
Starting materiala
RCM product
Catalyst
Conversionb
1
1
1
1
8a
8b
9a
9b
71%
> 98%
> 98%
96%
1
20
22
24
26
28
30
21
23
25
27
29
31
1
1
1
1
8a
8b
9a
9b
90%
> 98%
95%
2
3
4
5
6
97%
c
d
1
1
1
1
8a
8b
9a
9b
19% (36%, 36% )
9% (20%, 20% )
29% (40%, 59% )
6% (15%, 17% )
c
d
c
d
c
d
1
1
1
1
8a
8b
9a
9b
83%
95%
89%
96%
1
1
1
1
8a
8b
9a
9b
82%
96%
> 98%
95%
1
1
1
1
8a
8b
9a
9b
5% (89%)c
27% (87%)c
45% (94%)c
43% (90%)c
1
1
1
1
8a
8b
9a
9b
31%
84%
71%
63%
7
32
33
a
Reaction conditions: CH Cl , reflux, 1.5 h, 1 mol% catalyst.
2
2
b
c
d
Determined by NMR.
Catalyst (2.5 mol%).
Catalyst (5 mol%).
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3
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F. Koç et al.
PAPER
via an amide bond. The modified ligand was synthesized PC-Lig (3)
IR (neat): 3645, 3602, 3270, 2923, 1563, 1456, 1366, 1358, 1334,
in a straightforward manner. These catalysts revealed high
activity even with a catalyst loading of 1 mol%. They
showed high stability when used in reagent-grade solvents
and in air. Furthermore, the supported catalyst could eas-
ily be removed after reaction and had the potential for re-
–
1
1
258, 1178, 1121, 1089, 1021 cm .
Solid-Phase Bound Catalyst for Suzuki Reactions
Bisdiphenylphosphine-modified PC 3 was suspended in anhyd
CH Cl (10 mL, degassed under Ar). To this suspension, a soln of
2
2
application when 18a, 18b, 19a, or 19b were applied Pd(dba) (35 mg, 60.87 mmol) in anhyd CH Cl (5 mL, degassed un-
2
2
2
although slight decreased yields were observed in consec- der Ar) was added dropwise. After shaking for 24 h at r.t., PC 4a
was obtained by filtration under Ar. After drying under high vacu-
um, a Pd-loading of 11.20 mmol/g was determined by ICP–MS mea-
surements.
utive runs. The ligand applied here has the further advan-
tage that it can be attached to any kind of amino-modified
solid support.
4
a
IR (neat): 3647, 3602, 3454, 3375, 3299, 3270, 2923, 1784, 1765,
683, 1573, 1456, 1367, 1348, 1336, 1254, 1176, 1123, 1077, 1034
cm .
Polymer chips and membranes were obtained from PolyAn
GmbH12 (polyethylene sinter material: Amino 3-D Matrix, order
no.: 10100031 polypropylene membrane: Amino 3-D Matrix, order
no.: 10100013).
1
–
1
Recycling Experiment Using 4a; General Procedure
All reagents were obtained from Aldrich, Fluka, or Lancaster and
were of highest purity available. THF was dried over Na/benzophe-
none and freshly distilled before use. CH Cl was dried over CaH .
Melting points were measured with the electrothermal digital melt-
ing device IA 9200 and are uncorrected. Column chromatography
To a soln of aryl halide (0.49 mmol) and aryl boronic acid (0.53
mmol) in DMF (12 mL, degassed under Ar) was added Cs CO
2
3
2
2
2
(0.398 g, 1.22 mmol). The mixture was heated to 120 °C, then 4a
(688 mg, 7.70 mmol, 1.55 mol%) was added. After 2 h, a sample of
1 mL of the reaction mixture was taken with a syringe. After evap-
was performed using commercially available MN Silica gel 60
oration of the solvent, the residue was dissolved in CDCl . The con-
3
1
1
(
0.063–0.2 mm/70–230 mesh) ASTM for CC from Baker. H NMR
version was determined by H NMR while the reaction was still
1
3
spectra were measured at 250, 300, 400, and 500 MHz and C NMR
spectra at 100.6 MHz and 125.7 MHz on Bruker AC 250, DRX400,
and DRX500 spectrometers, respectively. Chemical shifts (d) are
running. After 6 h, the conversion was determined again in the same
fashion. In total, five consecutive runs were performed like this. At
the end, 4a was removed from the product mixture using tweezers.
1
given in ppm relative to TMS (d = 0 ppm) for H NMR and relative
to CHCl (d = 77.0 ppm) for C NMR. J values are given in Hz. MS
1
3
3
Scale-Up of the Recycling Experiment
data were recorded on TSQ-700 (EI, CI, ESI) mass spectrometer. IR
spectra were recorded on a Perkin–Elmer SpectrumOne spectrome-
ter. Elemental analyses were performed on a Vario EL.
To a soln of p-bromoacetophenone (6a; 1.00 g, 5.02 mmol) and phe-
nyl boronic acid (5a; 5.30 mmol) in DMF (120 mL, degassed under
Ar) was added Cs CO (4.08 g, 12.52 mmol). The mixture was heat-
2
3
ed to 120 °C, then 4a (703 mg, 7.87 mmol, 0.157 mol%) was added.
After 24 h, 4a was taken out of the reaction mixture with tweezers.
Then, the solvent was removed under vacuum, and the residue was
dissolved in water (50 mL). After extraction with EtOAc (3 × 50
mL) and drying over Na SO , analytically pure 7a (980 mg, 5.00
Suzuki Coupling Experiment
Synthesis of Bis(hydroxymethyl)diphenylphosphonium
Chloride (1)20
To diphenylphosphine (5.00 g, 26.85 mmol) were slowly added un-
der Ar formaldehyde solution (35%, 5.0 mL, 66.25 mmol) and con-
cd HCl (2.5 mL), which was slightly exothermic. Upon cooling the
warm solution, bis(hydroxymethyl)diphenylphosphonium chloride
2
4
mmol, >98%) was isolated.
3
6
4-Phenylacetophenone (7a)
1
(
1) precipitated. The product was recrystallized from MeOH. Prod-
H NMR (400 MHz, CDCl ): d = 2.62 (s, 3 H, COMe), 7.38–7.49
(m, 3 H, arom), 7.60–7.63 (m, 2 H, arom), 7.66–7.69 (m, 2 H,
3
uct 1 (7.21 g, 25.50 mmol, 95%) was isolated as a colorless crystal-
line powder.
arom), 8.00–8.03 (m, 2 H, arom).
1
13
H NMR (400 MHz, DMSO-d ): d = 4.89 (s, 2 H, OH), 5.15 (s, 4 H,
2
C NMR (100.6 MHz, CDCl ): d = 26.3, 127.2, 127.3, 128.3,
6
3
CH OH), 7.67–7.95 (m, 10 H, arom).
128.9, 129.0, 135.8, 139.8, 145.7, 197.7.
1
3
+
C NMR (100.6 MHz, DMSO-d ): d = 54.8, 55.4, 117.0, 117.7,
MS (EI, 70 eV): m/z (%) = 196 (45) [M ], 181 (100), 153 (36), 152
(54), 151 (20), 76 (65).
6
1
31.1, 131.3, 134.8, 134.9, 136.2, 136.2.
3
1
P NMR (121 MHz, DMSO-d ): d = 17.7 (s, 1 P).
6
Suzuki Reaction; General Procedure
To a soln of aryl halide (0.38 mmol) and aryl boronic acid (0.41
mmol) in DMF (10 mL, degassed under Ar) was added Cs CO
3
Phosphinylation of PC17
Before coupling with 2, the Boc-protecting groups of the amino-
functionalized PC were cleaved off. Therefore, the material was
suspended in a 5–6-M HCl soln in i-PrOH for 30 min and succes-
sively washed with i-PrOH, MeOH and a solution of Hünig’s base
in DMF.
2
(
(
0.31 g, 0.95 mmol). The mixture was heated to 120 °C, then 4a
140 mg, 0.41 mol%) was added. After 24 h, the reaction was cooled
and the catalyst removed using tweezers. After the solvent was re-
moved under vacuum, the conversion was determined by H NMR.
1
For the coupling, the amino-functionalized PC 2 (616 mg) was sus-
pended in water (5 mL) and anhyd MeOH (10 mL), both degassed
under Ar. Then bis(hydroxymethyl)diphenylphosphonium chloride
-Methoxybiphenyl (7b)37
4
1
H NMR (400 MHz, CDCl ): d = 3.83 (s, 3 H, OMe), 6.95–6.97 (m,
3
2
1
H, arom), 7.25–7.40 (m, 2 H, arom), 7.50–7.54 (m, 5 H, arom).
(
1) (452 mg, 1.60 mmol) and Et N (209 mL, 151 mg, 1.50 mmol)
3
3
C NMR (100.6 MHz, CDCl ): d = 55.4, 114.2, 126.6, 126.7,
were added and the mixture was refluxed for 72 h. After cooling, the
PC 3 was isolated by filtration under Ar. It was then dried under
high vacuum.
3
1
28.2, 128.7, 135.2.
+
MS (EI, 70 eV): m/z (%) = 184 (100) [M ], 169 (39), 141 (35), 115
(
21), 75 (10).
Synthesis 2005, No. 19, 3362–3372 © Thieme Stuttgart · New York

PAPER
¢-Acetylbiphenyl-4-carbonitrile (7c)38
Catalysts on Functionalized Polymer Chips (PC) as Recyclable Entities
3369
4
8.9 Hz, 1 H, H-3), 7.59 (dd, J = 2.6, 8.9 Hz, 1 H, H-4), 7.91 (d, J =
1
H NMR (400 MHz, CDCl ): d = 2.68 (s, 3 H, COMe), 7.70–7.78
2.6 Hz, 1 H, H-6), 10.39 (s, 1 H, CHO).
3
(m, 6 H, arom), 8.10 (d, J = 8.4 Hz, 2 H, arom).
13
C NMR (100.6 MHz, CDCl ): d = 22.0, 71.8, 113.3, 116.1, 127.2,
3
1
3
C NMR (100.6 MHz, CDCl ): d = 27.0, 118.8, 127.6, 128.1,
131.1, 138.2, 159.5, 188.7.
3
1
29.4, 132.9, 133.2, 137.2, 143.8, 144.5, 197.7.
+
MS (EI, 70 eV): m/z (%) = 244 (12), 242 (12) [M ], 202 (85), 201
+
MS (EI, 70 eV): m/z (%) = 221 (40) [M ], 206 (100), 177 (34), 151
(64), 200 (100), 199 (64), 184 (14), 182 (11), 145 (13), 143 (13), 63
(20), 43 (17).
(
32).
Anal. Calcd for C H BrO : C, 49.41; H, 4.56. Found: C, 49.23; H,
-(4¢-Acetylbiphenyl-4-yl)ethanone (7d)39
10
11
2
1
4
.63.
1
H NMR (400 MHz, CDCl ): d = 2.60 (s, 6 H, COMe), 7.90–8.10
(
3
m, 8 H, arom).
(
E)-3-(3-Formyl-4-isopropoxyphenyl)ethyl Acrylate (14)
1
3
C NMR (100.6 MHz, CDCl ): d = 24.0, 128.4, 129.5, 136.5,
To a suspension of Pd(OAc) (0.35 g, 2.36 mmol, 5 mol%) and P(o-
3
2
1
42.1, 197.1.
Tol) (2.96 g, 9.73 mmol) in anhyd DMF (150 mL) were added an-
3
+
hyd Et N (13.6 mL, 9.87 g, 97.5 mmol), aldehyde 13 (11.83 g, 48.66
mmol) and ethyl acrylate (6.40 mL, 5.89 g, 58.9 mmol). The reac-
tion mixture was heated for 5 h at 100 °C (oil bath). After cooling
3
MS (EI, 70 eV): m/z (%) = 238 (50) [M ], 223 (100), 152 (20).
-(4¢-Methoxybiphenyl-4-yl)ethanone (7e)40
H NMR (400 MHz, CDCl ): d = 2.63 (s, 3 H, COMe), 3.87 (s, 3 H,
OMe), 7.00 (d, J = 8.5 Hz, 2 H, arom), 7.58 (d, J = 8.5 Hz, 2 H,
arom), 7.65 (d, J = 8.3 Hz, 2 H, arom), 8.01 (d, J = 8.3 Hz, 2 H,
arom).
1
1
to r.t., the mixture was poured into H O (1.2 L) and extracted with
2
3
Et O (10 × 100 mL). The combined organic fractions were washed
2
with sat. NH Cl soln (300 mL) and dried over MgSO . After purifi-
4
4
cation by flash column chromatography (cyclohexane–EtOAc, 50:1
5:1) the product (11.3 g, 43.1 mmol, 89%) was obtained as a yel-
→
1
3
C NMR (100.6 MHz, CDCl ): d = 31.4, 55.4, 114.4, 121.7, 126.6,
28.3, 128.9, 136.4, 142.0, 161.2, 197.1.
3
low solid; mp 56–59 °C; R 0.32 (cyclohexane–EtOAc, 5:1).
f
1
1
H NMR (300 MHz, CDCl ): d = 1.33 (t, J = 7.1 Hz, 3 H,
3
+
MS (EI, 70 eV): m/z (%) = 226 (70) [M ], 211 (100), 183 (15), 168
OCH CH ), 1.43 [d, J = 6.0 Hz, 6 H, CH(CH ) ], 4.26 (q, J = 7.1
2
3
3 2
(
20), 152 (15), 139 (25).
Hz, 2 H, OCH CH ), 4.74 [septet, J = 6.1 Hz, 1 H, CH(CH ) ], 6.38
2
3
3 2
(
d, J = 16.0 Hz, 1 H, ArCH=CHCOOEt), 7.01 (d, J = 8.8 Hz, 1 H,
arom), 7.63 (d, J = 16.1 Hz, 1 H, ArCH=CHCOOEt), 7.68 (dd, J =
.3, 8.8 Hz, 1 H, arom), 8.00 (d, J = 2.5 Hz, 1 H, arom), 10.47 (s, 1
Hydroformylation Experiments
Solid-Phase Bound Catalyst for Hydroformylation Reactions
Bisdiphenylphosphine modified PC 3 was suspended in anhyd
2
H, CHO).
13
CH Cl (10 mL, degassed under Ar). Then, a soln of [Rh(cod) ]BF
2
2
2
4
C NMR (100.6 MHz, CDCl ): d = 14.4, 22.0, 60.5, 71.6, 114.2,
3
(30.04 mg, 70.01 mmol) in anhyd CH Cl (5 mL, degassed under Ar)
2
2
1
17.6, 125.7, 127.0, 128.2, 135.1, 143.0, 161.8, 167.0, 189.5.
was added dropwise. After shaking for 24 h at r.t., PC 4b was fil-
tered using a filtration setup under Ar. The PC 4b was dried under
high vacuum to give a PC with a Rh-loading of 4b of 10.42 mmol/g
+
MS (EI, 70 eV): m/z (%) = 262 (21) [M ], 220 (100), 192 (51), 191
(14), 175 (85), 148 (47), 146 (28).
(determined by ICP–MS measurements).
Anal. Calcd for C H O : C, 68.68; H, 6.92. Found: C, 68.60; H,
1
5
18
4
IR (neat): 3447, 3402, 3394, 3374, 3289, 3268, 2921, 1571, 1466,
7.11.
–
1
1
452, 1365, 1345, 1340, 1336, 1330, 1244, 1177, 1121, 1071 cm .
(
E)-3-(4-Isopropoxy-3-vinylphenyl)ethyl Acrylate (15)
Preparation of Phthalimidyl-3-methylbutyraldehyde (9)26a
A solution of methallylphthalimide (8; 250 mg, 1.24 mmol) in an-
hyd toluene (10 mL) and 4b (150 mg, 0.41 mol%) was placed in an
Methyltriphenylphosphonium bromide (18.6 g, 52.1 mmol) was
suspended in anhyd THF (250 mL) and cooled to 0 °C. Under ice-
cooling, BuLi (1.6 M in hexane; 32.3 mL, 51.7 mmol) was added
dropwise over 50 min and the mixture was stirred for further 30 min
at 0 °C. In the meantime, a soln of aldehyde 16 (11.3 g, 43.1 mmol)
in anhyd THF (50 mL) was prepared and also cooled to 0 °C. After
adding the ylide to the aldehyde soln via transfer needle, the reac-
tion mixture was stirred overnight at r.t. Then, the solvent was re-
autoclave. The autoclave was pressurized with 100 bar CO–H (1:1)
2
and heated to 100 °C for 2 d. After cooling, 4b was removed using
tweezers. The solvent was removed in a rotary evaporator to give
pure 9 (286 mg, 1.24 mmol, > 98%) as a colorless wax.
1
H NMR (500 MHz, CDCl ): d = 1.01 (d, J = 6.8 Hz, 3 H, Me),
3
moved in vacuo and the residue was taken up in Et O (200 mL). The
precipitate was separated, and the filtrate was washed with sat. brine
2
2
7
.21–2.66 (m, 3 H, NCH CHR ), 3.58–3.65 (m, 2 H, CH CHO),
.68–7.88 (m, 4 H, arom), 9.72 (s, 1 H, CHO).
2
2
2
(150 mL). After drying over MgSO the product was purified by
4
1
3
C NMR (125.7 MHz, CDCl ): d = 17.8, 30.0, 43.3, 48.5, 123.3,
3
column chromatography (cyclohexane–EtOAc, 20:1). A pale yel-
low-colored solid (8.09 g, 31.1 mmol, 72%) was obtained; mp 46–
1
31.9, 134.0, 168.6, 201.2.
4
8 °C; R 0.59 (cyclohexane–EtOAc, 5:1).
f
Olefin Metathesis Experiments
-Bromo-2-isopropoxybenzaldehyde (13)
To a solution of 5-bromo-2-hydroxybenzaldehyde (12; 10.22 g,
0.84 mmol) in DMF (150 mL) were added K CO (13.88 g, 100.4
1
H NMR (300 MHz, CDCl ): d = 1.33 (t, J = 7.2 Hz, 3 H, CH CH ;
3
2
3
5
signal partially superimposed by the doublet of the isopropoxy
group), 1.37 [d, J = 6.2 Hz, 6 H, CH(CH ) ], 4.26 (q, J = 7.1 Hz, 2
H, CH CH ), 4.60 [sept, J = 6.1 Hz, 1 H, CH(CH ) ], 5.28 (dd, J =
1
CH=CHH), 6.33 (d, J = 16.0 Hz, 1 H, ArCH=CHCOOEt), 6.87 (d,
J = 8.6 Hz, 1 H, arom), 7.02 (dd, J = 11.2, 17.8 Hz, 1 H, CH=CH2),
3
2
5
2
3
2
3
3 2
mmol) and Cs CO (3.27 g, 10.0 mmol). To the resulting yellow
2
3
.3, 11.1 Hz, 1 H, CH=CHH), 5.76 (dd, J = 17.7 Hz, 1.3 Hz, 1 H,
suspension was added dropwise 2-iodopropane (15.0 mL, 25.5 g,
50 mmol). After stirring for 24 h at r.t., the reaction mixture was
1
poured into H O (500 mL) and extracted with Et O (4 × 100 mL).
2
2
7
.38 (dd, J = 2.2, 8.6 Hz, 1 H, arom), 7.64 (d, J = 16.0 Hz, 1 H,
ArCH=CHCOOEt; this doublet surrounds the following doublet),
.64 (d, J = 2.2 Hz, 1 H, arom).
The combined organic fractions were washed with H O (5 × 200
2
mL) and dried over MgSO . The product 13 (11.87 g, 48.83 mmol,
4
7
9
6%) was isolated as a yellow solid; mp 31–33 °C.
13C NMR (100.6 MHz, CDCl
): d = 14.4, 22.2, 60.4, 71.0, 113.7,
15.0, 116.0, 126.7, 126.9, 128.2, 128.9, 131.6, 144.5, 157.1, 167.4.
1
3
H NMR (300 MHz, CDCl ): d = 1.40 [d, J = 6.0 Hz, 6 H,
3
1
CH(CH ) ], 4.65 [septet, J = 6.0 Hz, 1 H, CH(CH ) ], 6.89 (d, J =
3
2
3 2
Synthesis 2005, No. 19, 3362–3372 © Thieme Stuttgart · New York

3
370
F. Koç et al.
PAPER
+
MS (EI, 70 eV): m/z (%) = 260 (57) [M ], 218 (100), 190 (25), 173
72), 146 (69), 145 (22), 127 (15), 115(31), 57 (24), 43 (34).
id phase was removed from the reaction mixture, washed with
CH Cl , and dried in a desiccator.
(
2
2
Anal. Calcd for C H O : C, 73.82; H, 7.74. Found: C, 73.83; H,
The loading of Ru was determined by ICP–MS.
8a
16
20
3
7
.88.
1
(
E)-3-(4-Isopropoxy-3-vinylphenyl)acrylic Acid (16)
The cinnamate derivative 15 (8.09 g, 31.1 mmol) was dissolved in
,4-dioxane (220 mL) and an aq 1 M KOH–solution (220 mL) was
Ru loading: 7.8 mmol/g.
IR (neat): 3979, 3915, 3647, 3606, 3373, 2940, 2662, 2529, 2417,
1
2
1
327, 2151, 2019, 1897, 1820, 1661, 1468, 1368, 1353, 1306, 1253,
176, 1103, 1080, 925, 852, 731, 719, 518, 480 cm .
added slowly at r.t. After stirring for 24 h at r.t., the mixture was
acidified with 2 M HCl (120 mL) until the precipitation of the prod-
uct was complete. The precipitate was filtered and washed with cold
H O (10 mL). After treatment with MeCN, the pure 16 (6.64 g, 28.6
mmol, 92%) was obtained as a colorless solid; mp 124–128 °C.
–1
1
8b
2
Ru loading: 4.5 mmol/g.
IR (neat): 3979, 3915, 3647, 3606, 3372, 2874, 2662, 2528, 2417,
1
H NMR (300 MHz, CDCl ): d = 1.38 [d, J = 6.0 Hz, 6 H,
3
2
1
327, 2150, 2019, 1897, 1820, 1660, 1623, 1465, 1368, 1353, 1305,
256, 1176, 1106, 982, 956, 854, 721, 580, 469 cm .
CH(CH ) ], 4.62 [septet, J = 6.1 Hz, 1 H, CH(CH ) ], 5.30 (dd, J =
–1
3
2
3 2
1
.2, 11.3 Hz, 1 H, CH=CHH), 5.78 (dd, J = 1.2, 17.7 Hz, 1 H,
CH=CHH), 6.34 (d, J = 16.0 Hz, 1 H, ArCH=CHCOOH), 6.88 (d,
J = 8.6 Hz, 1 H, arom), 7.02 (dd, J = 11.1, 17.9 Hz, 1 H CH=CH2),
1
9a
Ru loading: 210 mmol/g.
7
7
.42 (dd, J = 2.1, 8.6 Hz, 1 H, arom), 7.67 (d, J = 2.1 Hz, 1 H, arom),
.75 (d, J = 16.0 Hz, 1 H, ArCH=CHCOOH).
IR (neat): 3334, 3061, 2922, 2839, 2723, 2582, 1943, 1735, 1660,
1
9
539, 1489, 1455, 1377, 1359, 1304, 1250, 1168, 1103, 998, 974,
1
3
C NMR (100.6 MHz, CDCl ): d = 22.2, 71.0, 113.7, 114.9, 115.2,
3
26, 899, 851, 842, 812, 746, 727, 703, 649, 623, 565, 518, 479
1
26.5, 127.1, 128.3, 129.3, 131.5, 147.0, 157.5, 172.8.
–1
cm .
+
MS (EI, 70 eV): m/z (%) = 251 (13) [M ], 236 (10), 222 (20), 186
(13), 155 (77), 96 (63), 91 (100), 84 (29), 41 (31).
19b
Ru loading: 134 mmol/g.
Anal. Calcd for C H O : C, 72.39; H, 6.94. Found: C, 72.10; H
14
16
3
6
.92.
IR (neat): 3314, 3061, 2920, 2839, 2723, 2582, 1948, 1730, 1658,
1
623, 1600, 1544, 1489, 1456, 1377, 1359, 1303, 1255, 1168, 1113,
(
E)-3-(4-Isopropoxy-3-vinylphenyl)acrylic Acid 16 Coupled to
998, 974, 956, 927, 900, 855, 841, 811, 750, 704, 647, 580, 460
cm .
–
1
Solid Support
Before the coupling with 16, the Boc-protecting group of the amino-
functionalized polymer was cleaved off. Therefore, the material
was suspended in a 5–6 M HCl solution in i-PrOH for 30 min, and
successively washed with i-PrOH, MeOH and a soln of Hünig’s
base in DMF.
Recycling Experiment Using 20; General Procedure
For each catalyst, five flasks filled with 1 mL of a 0.05-M stock soln
of 20 in CH Cl were prepared. The catalyst was added to the first
2
2
flask and shaken for 90 min at 60 °C oil bath. Then, 20 mL of the
reaction mixture were taken to determine the conversion by HPLC.
The piece of catalyst was removed from the reaction using tweezers,
washed with CH Cl (2 mL) and the next run was started. In total,
For the coupling, HOBt (0.27 g, 2.00 mmol) and 16 (0.46 g, 1.99
mmol) were dissolved in DMF (40 mL). To this solution DCC (0.41
g, 1.99 mmol) and Hünig’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 (9.80 g, 127–137 mmol) suspended in fresh DMF and the
flask was shaken at r.t. When the TNBS test for amino groups was
negative, the solid phase was removed from the reaction and
washed consecutively with DMF, H O, DMF, and CH Cl . Next,
2
2
five consecutive runs were performed like this.
Ring-Closing Metathesis; General Procedure
To a stock soln of the a,w-olefin (160 mL, 50 mmol, 0.3 M in
CH Cl ) were added CH Cl (850 mL) and the catalyst (1.0 mol%,
2
2
2
2
2
2
2
0
.5 mol). The reaction mixture was heated to reflux (60 °C oil bath)
the solid phase was suspended in CH Cl . A solution of Et N (0.62
2
2
3
and shaken for 90 min. Then, the catalyst was removed with twee-
zers and the reaction mixture was quenched with 0.001 M ethyl vi-
nyl ether (0.1 mL) in CH Cl . The solvent was removed in vacuo
mL, 0.45 g, 4.45 mmol) and DMAP (48 mg, 390 mmol) in CH Cl
2
2
(
4 mL) was added, followed by a solution of Ac O (0.37 mL, 0.40
2
2
2
g, 3.92 mmol) in CH Cl (2 mL), and the reaction mixture was shak-
2
2
1
and the conversion was determined by H NMR.
en at r.t. for 4 h. Finally, the solid phase was washed with CH Cl ,
2
2
DMF, H O, DMF, CH Cl , and Et O and dried in a desiccator.
2
2
2
2
-(Toluene-4-sulfonyl)-2,5-dihydro-1H-pyrrole41 (21)
1
1
H NMR (400 MHz, CDCl ): d = 2.42 (s, 3 H, ArCH ), 4.12 (s, 4 H,
3
3
PE-Lig
IR (neat): 3978, 3903, 3647, 3606, 3370, 2919, 2662, 2529, 2417,
CH CH=CHCH ), 5.65 (s, 2 H, CH CH=CHCH ), 7.32 (m ,
2
2
2
2
AA¢BB¢
Japp = 8.1 Hz, 2 H, arom), 7.72 (mAA¢BB¢, Japp = 8.1 Hz, 2 H, arom).
2
1
327, 2019, 1897, 1820, 1663, 1470, 1368, 1353, 1306, 1260, 1176,
117, 1083, 1019, 799, 731, 719, 540 cm .
–
1
13
C NMR (100.6 MHz, CDCl ): d = 21.6, 54.9, 125.5, 127.5, 129.8,
3
1
34.4, 143.5.
PP-Lig
+
MS (EI, 70 eV): m/z (%) = 223 (50) [M ], 155 (52), 91 (92), 86 (13),
IR (neat): 3300, 3071, 2923, 2839, 2723, 2582, 2123, 1658, 1622,
8
4 (20), 68 (100), 65 (24), 41 (24).
1
9
600, 1548, 1491, 1456, 1377, 1359, 1304, 1253, 1168, 1116, 998,
74, 956, 900, 857, 841, 811, 752, 704, 653, 607, 531, 459 cm .
–
1
-(Toluene-4-sulfonyl)-2,3,4,7-tetrahydro-1H-azepine42 (23)
1
1
H NMR (300 MHz, CDCl ): d = 1.80 (m , 2 H), 2.18 (m , 2 H), 2.41
3
c
c
Solid-Phase-Bound Catalyst for Metathesis Reactions (18a,b;
9a,b)
The solid phase 2 was suspended in anhyd CH Cl under Ar. Grubbs
(
s, 3 H, CH Ar), 3.39 (t, J = 6.1 Hz, 2 H, NCH CH ), 3.83 (d, J =
3
2
2
1
4
3
8
.5 Hz, 2 H, NCH CH=CH), 5.64 (dt, J = 5.1, 10.6 Hz, 1 H, H-2, H-
2
), 5.77 (dt, J = 5.3, 10.9 Hz, 1 H, H-2, H-3), 7.28 (mAA¢BB¢, Japp
.2 Hz, 2 H, arom), 7.68 (mAA¢BB¢, Japp = 8.1 Hz, 2 H, arom).
2
2
=
catalyst 10a or 10b (1.3 equiv) and CuCl (1.3 equiv) were added and
the reaction was heated to reflux for 4 h. After cooling to r.t., the sol-
Synthesis 2005, No. 19, 3362–3372 © Thieme Stuttgart · New York

PAPER
Catalysts on Functionalized Polymer Chips (PC) as Recyclable Entities
3371
1
3
C NMR (100.6 MHz, CDCl ): d = 21.5, 26.9, 31.0, 46.4, 49.7,
tra, Mr. C. Warth and Dr. J. Wörth for recording MS spectra, and
Mr. Hickl for performing elemental analyses.
3
1
26.7, 127.3, 129.6, 133.0, 136.5, 143.1.
+
MS (EI, 70 eV): m/z (%) = 251 (100) [M ], 236 (7), 184 (85), 155
(
40), 96 (87), 91 (37), 69 (35), 67 (30), 41 (24).
References
1
-(Toluene-4-sulfonyl)-1,2,3,4,5,8-hexahydroazocine42 (25)
(1) Present address: Abdiibrahim Pharmaceuticals, Hosdere
Mevkii Tunç Cad. No: 3, 34860 Hadimköy, Istanbul,
Turkey.
(2) For recent reviews see: (a) Haag, R.; Roller, S. Top. Curr.
Chem. 2004, 242, 1. (b) Bergbreiter, D. E.; Li, J. Top. Curr.
Chem. 2004, 242, 113.
(3) (a) McNamara, C. A.; Dixon, M. J.; Bradley, M. Chem. Rev.
2002, 102, 3275. (b) Calpham, B.; Reger, T. S.; Janda, K. T.
Tetrahedron 2001, 57, 4637. (c) de Miguel, Y. R.; Brule, E.;
Margue, R. G. J. Chem. Soc., Perkin Trans. 1 2001, 3085.
1
H NMR (300 MHz, CDCl ): d = 1.50–1.61 (m, 2 H, CH ), 1.63–
3
2
1
3
5
.72 (m, 2 H, CH ), 2.35–2.41 (m, 2 H, 5-CH ), 2.42 (s, 3 H, CH ),
2
2
3
.29 (t, J = 5.4 Hz, 2 H, 8-CH ), 3.81 (d, J = 5.8 Hz, 2 H, 2-CH ),
2
2
.40 (dt, J = 5.6, 11.2 Hz, 1 H, NCH CH=CH), 5.78 (dt, J = 8.5, 11.1
2
Hz, 1 H, NCH CH=CH), 7.29 (mAA¢BB¢, Japp = 7.9 Hz, 2 H, arom),
7
2
.67 (mAA¢BB¢, Japp = 7.9 Hz, 2 H, arom).
+
MS (EI, 70 eV): m/z (%) = 265 (17) [M ], 250 (8), 224 (38), 184
(
(
100), 155 (99), 138 (29), 110 (38), 91 (66), 82 (11), 79 (17), 68
10).
(
4) (a) Horvath, I. T.; Rabai, J. Science 1994, 266, 72.
(b) Horvath, I. T.; Rabai, J. U.S. Patent, 5463082, 1995.
Cyclopent-2-enyloxymethyl)benzene43 (27)
H NMR (500 MHz, CDCl ): d = 1.82–1.89 (m, 1 H, H -4¢, H -4¢),
(
1
(5) (a) Ionic Liquids in Synthesis; Wasserscheid, P.; Welton, T.,
Eds.; VCH–Wiley: Weinheim, 2002. (b) Wasserscheid, P.;
Keim, W. Angew. Chem. Int. Ed. 2000, 39, 3772; Angew.
Chem. 2000, 112, 3926. (c) Welton, T. Coord. Chem. Rev.
3
A
B
2
2
.12–2.19 (m, 1 H, H -4¢, H -4¢), 2.23–2.30 (m, 1 H, H -5¢, H -5¢),
A
B
A
B
.47–2.55 (m, 1 H, H -5¢, H -5¢), 4.51 (d, J = 11.7 Hz, 1 H,
A
B
AB
HCHAr), 4.55 (d, JAB = 11.7 Hz, 1 H, HCHAr), 4.67 (m , 1 H,
CHOR), 5.88–5.91 (m, 1 H, H-3¢), 6.01–6.04 (m, 1 H, H-2¢), 7.24–
7
c
2
004, 248, 2459.
(
(
6) Leitner, W. Top. Curr. Chem. 1999, 206, 107.
7) Tzschucke, C. C.; Markert, C.; Bannwarth, W.; Roller, S.;
Hebel, A.; Haag, R. Angew. Chem. Int. Ed. 2002, 41, 3964;
Angew. Chem. 2002, 114, 4136.
.37 (m, 5 H, arom).
1
3
C NMR (100.6 MHz, CDCl ): d = 29.8, 31.1, 70.6, 84.5, 127.4,
3
1
27.8, 128.3, 130.8, 135.7, 138.9.
+
MS (CI, NH , 130 eV): m/z (%) = 192 (12) [M + NH ] , 175 (4)
(8) Leadbeater, N. E.; Marco, M. Chem. Rev. 2002, 102, 3217.
(9) Hird, N.; Hughes, I.; Hunter, D.; Morrison, M. G. J. T.;
Sherrington, D. C.; Stevenson, L. Tetrahedron 1999, 55,
9575.
(10) Atrash, B.; Bradley, M.; Kobylecki, R.; Cowell, D.; Reader,
J. Angew. Chem. Int. Ed. 2001, 40, 938; Angew. Chem. 2001,
113, 964.
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44, 4779.
12) PolyAn GmbH, Rudolf-Baschant-Str. 2, 13086 Berlin,
Germany; www.polyan.de.
3
4
+
[M + H] , 157 (10), 126 (21), 108 (17), 91 (36), 84 (100), 67 (7).
(
Cyclohex-2-enyloxymethyl)benzene44 (29)
1
H NMR (500 MHz, CDCl ): d = 1.51–1.59 (m, 1 H), 1.71–1.89 (m,
3
3
H), 1.91–1.99 (m, 1 H), 2.02–2.10 (m, 1 H), 3.93–3.98 (br m, 1 H,
H-1), 4.55 (dAA¢, J = 12.0 Hz, 1 H, CHHO), 4.61 (dAA¢, J = 12.0 Hz,
H, CHHO), 5.79–5.89 (m, 2 H, H-2, H-3), 7.24–7.37 (m, 5 H,
arom).
1
(
1
3
C NMR (100.6 MHz, CDCl ): d = 19.3, 25.3, 28.4, 70.0, 72.2,
3
1
27.4, 127.6, 127.8, 128.3, 130.9, 139.1.
(
13) Suzuki, A.; Miyaura, N. Chem. Rev. 1995, 95, 2457.
+
MS (EI, 70 eV): m/z (%) = 188 (5) [M ], 130 (9), 97 (48), 91 (100),
8
(14) (a) Horn, J.; Michalek, F.; Tzschucke, C. C.; Bannwarth, W.
Top. Curr. Chem. 2004, 242, 43. (b) Uozumi, Y. Top. Curr.
Chem. 2004, 242, 77.
(15) A typical polystyrene resin (2% cross-linked with DVB) is
completely destroyed by normal magnetic stirring (300
rpm).
(16) Haag, R.; Hebel, A.; Stumbé, J.-F. In Handbook of
Combinatorial Chemistry; Nicolaou, K. C.; Hanko, R.;
Hartwig, W., Eds.; Wiley-VCH: Weinheim, 2002, 24–58.
4 (8), 81 (13), 79 (13), 77 (7), 69 (22), 65 (11), 55 (10), 41 (15).
2
-Phenyl-3,6-dihydro-2H-pyran45 (31)
1
H NMR (300 MHz, CDCl ): d = 2.20–2.44 (m, 2 H), 4.33–4.39 (m,
2
3
H), 4.56 (dd, J = 3.8, 10.0 Hz, 1 H, OCHAr), 5.77–5.85 (m, 1 H),
.88–5.96 (m, 1 H), 7.25–7.41 (m, 5 H, arom).
5
1
3
C NMR (100.6 MHz, CDCl ): d = 32.9, 66.6, 75.7, 124.5, 125.9,
3
1
26.4, 127.5, 128.4, 142.6.
(
17) Reetz, M. T.; Lohmer, G.; Schwickardi, R. Angew. Chem.,
+
MS (EI, 70 eV): m/z (%) = 160 (16) [M ], 105 (100), 77 (18), 54
Int. Ed. Engl. 1997, 36, 1526; Angew. Chem. 1997, 109,
(
75).
1559.
(
18) (a) Bourque, S. C.; Alper, H.; Manzer, L. E.; Arya, P. J. Am.
Chem. Soc. 2000, 122, 956. (b) Arya, P.; Rao, N. V.;
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S.-M.; Alper, H. J. Org. Chem. 2004, 69, 3558.
4
6
Cyclopent-3-ene-1,1-dicarboxylic Acid Diethyl Ester (33)
1
H NMR (400 MHz, CDCl ): d = 1.25 (t, J = 7.1 Hz, 6 H, 2 ×
CH CH ), 3.01 (s, 4 H, CH CH=CHCH ), 4.20 (q, J = 7.1 Hz, 4 H,
3
2
3
2
2
2
× CH CH ), 5.61 (s, 2 H, CH CH=CHCH ).
2
3
2
2
1
3
C NMR (100.6 MHz, CDCl ): d = 14.0, 40.9, 58.9, 61.2, 127.8,
3
1
72.3.
+
MS (EI, 70 eV): m/z (%) = 212 (63) [M ], 166 (60), 138 (100), 111
(
38), 93 (32), 79 (40), 66 (54).
(h) Reynhardt, J. P. K.; Yang, Y.; Sayari, A.; Alper, H.
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Germany, 1996.
Acknowledgment
(
Generous financial support from PolyAn GmbH, Berlin (D) is gra-
tefully acknowledged. Also we would like to thank Dr. M. Keller,
Ms. M. Schonhard, and Mr. F. Reinbold for recording NMR spec-
(20) Fawcett, J.; Hoye, P. A. T.; Kemmitt, R. D. W.; Law, D. J.;
Russell, D. R. J. Chem. Soc., Dalton Trans. 1993, 2563.
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Synthesis 2005, No. 19, 3362–3372 © Thieme Stuttgart · New York