Scope and limitations of ruthenium-catalyzed metathesis of simple polymer-bound alkenes

Article abstract of DOI:10.1139/v01-045

Synthetic procedures for the preparation of two types of functional resin are described, both based on 2% cross-linked polystyrene with a high density (>60%) of side-chains and terminated by a primary alcohol. In the first case the C₁₁ side-cha

Full text of DOI:10.1139/v01-045

1049
Scope and limitations of ruthenium-catalyzed
metathesis of simple polymer-bound alkenes
Peter G. Breed, James A. Ramsden, and John M. Brown
Abstract: Synthetic procedures for the preparation of two types of functional resin are described, both based on 2%
cross-linked polystyrene with a high density (>60%) of side-chains and terminated by a primary alcohol. In the first
case the C11 side-chain is linked to the polymer through a sulfide, and in the second an ether linkage is employed to
incorporate a (CH2CH2O)4 unit. In both cases the resins have 13C NMR spectra that are informative in the chain termi-
nus region without special operating conditions. Model intermolecular metathesis reactions were carried out on
allylcarbamic acid tert-butyl ester and various alkenes with Grubbs’ catalyst. On the basis of these experiments, gel-
phase metathesis was successfully demonstrated between a polymer-bound allyl ether and simple symmetrical
disubstituted alkenes, monitoring the extent of reaction by 13C NMR. These reactions did not go to completion even
with recycling and some evidence for competing interchain metathesis is presented, based on the increased broadening
and reduced mobility of the ensuing polymer.
Key words: alkene metathesis, ruthenium, gel-phase, 13C NMR.
Résumé : On décrit des méthodes de synthèse de deux types de résines fonctionnelles qui comportent toutes les deux
du polystyrène réticulé à 2%, une densité élevée (>60%) de chaînes latérales et qui se terminent par un alcool pri-
maire. Dans le premier cas, la chaîne latérale en C11 est liée au polymère par un sulfure et, dans le deuxième cas, on
utilise une liaison éther pour incorporer une unité (CH2CH2O)4. Dans les deux cas, les spectres RMN du 13C des rési-
nes fournissent de l’information sur la région terminale de la chaîne sans nécessiter de conditions spéciales. Utilisant le
catalyseur de Grubb, on a effectué des réactions modèles de métathèse intermoléculaire avec l’ester tert-butylique de
l’acide allylcarbamique et divers alcènes. Sur la base des résultats de ces expériences et faisant appel à la RMN du 13C
pour suivre le déroulement de la réaction, on a pu mettre en évidence la métathèse en phase gel entre un oxyde
d’allyle lié au polymère et des alcènes simples disubstitués de façon symétrique. Ces réactions ne sont pas complètes,
même si on fait du recyclage; de plus, en se basant sur une augmentation de l’élargissement des signaux et sur la mo-
bilité réduite du polymère qui en résulte, on présente des données qui mettent en évidence l’existence de réactions
compétitives de métathèse interchaînes.
Mots clés : métathèse d’alcène, ruthénium, phase gel, RMN du 13C.
[Traduit par la Rédaction] Breed et al. 1057
Introduction
rated from the medium by a simple filtration, and the reac-
tion rate controlled by catalyst concentration. In addition, all
the efforts that have been channeled into catalyst specificity
applied to chemo-, regio-, and stereo-control may be brought
to bear in solid-phase reactions. In some cases, the applica-
tion of catalysis to solid-phase reactions has been routinely
successful (e.g., in Suzuki coupling) (2) but in others it has
proved more difficult to reproduce the stereoselectivity of
solution-phase results across the board (e.g., in Sharpless
dihydroxylation) (3).
As in any other area of synthesis, progress in solid-phase
synthesis depends on methods for the analysis of product
purity. Although considerable strides have been made in di-
rect on-bead assay by IR (4), NMR (5), and other techniques
(6), it remains a challenge for the discipline. This is espe-
cially the case when reactions are conducted on resin phases
where the loading of reacting sites is low, as in the case of
the popular Wang resin (typically 0.5 mmol g–1) (7), Argogel
(typically 0.43 mmol g–1) (8), and Tentagel (typically
0.2 mmol g–1) (9). This provided a basis for the synthesis of
polystyrene resins with a high level of functionality, based
on a readily accessible precursor. The use of 2% cross-
linked 63% chloromethylated polystyrene (Fluka) provided
With the rapid development of solid-phase organic synthe-
sis in response to the demands of combinatorial chemistry
and high-throughput screening (1), suitable reaction types
have been appraised. Desirable qualities include the ability
to separate the polymer-bound product from reagents, sol-
vents, and other reaction components, appropriate reactivity
for the required functional transformation, and above all
quantitative conversion so that the product is a coherent spe-
cies. On this basis homogeneous catalysis seems ideal where
applicable, since the solution phase catalyst may be sepa-
Received September 12, 2000. Published on the NRC
Research Press Web site at http://canjchem.nrc.ca on July 11, 2001.
Dedicated to Professor Brian James, a pioneer of ruthenium
organometallic chemistry.
P.G. Breed, J.A. Ramsden, and J.M. Brown.1 Dyson
Perrins Laboratory, University of Oxford, South Parks Rd.
Oxford OX1 3QY, U.K.
1Corresponding author (telephone: 44 1865 275 642; fax:
44 1865 275674; e-mail: bjm@ermine.ox.ac.uk).
Can. J. Chem. 79: 1049–1057 (2001)
DOI: 10.1139/cjc-79-5/6-1049
© 2001 NRC Canada

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Can. J. Chem. Vol. 79, 2001
Scheme 1. (a) NaH, allyl bromide, THF, reflux 18 h, 76%; (b) KSC(O)CH3, DMF, 18 h, RT, 74%; (c) NaOH, MeOH, H2O, reflux
25 min, 49%; (d) PS, NaOMe, THF–DMF (1:3), 50°C, 60 h, 98%; (e) NaH, PS, THF, 60°C, 14 h, quant.; (f) SOCl2 then (C3H5)2NH,
C7H8, 69%; (g) NaOMe, THF, 1 h, then PS, THF, 55°C, 18 h, quant.
Scheme 2. Polymer synthesis in the polyoxyethylene series: (a) Na, allyl bromide, 18 h at RT, then 100°C, 50%; (b) PS, NaH, THF,
60°C, 18 h, 90% conversion.
Scheme 3. Examples of successful polymer-phase metatheses: (a) of polymer 4 with but-2-ene (50% in CH2Cl2, 3 mol% catalyst,
sealed tube, ambient, 84 h), quantitative; (b) of polymer 6 (CH2Cl2, 10 mol% catalyst, 48 h), quantitative; (c) of polymer 8 with Z-but-
2-en-1,4-diol (40% in diglyme, 3 mol% catalyst), 83–87% with reexposure to the catalyst.
© 2001 NRC Canada

Breed et al.
1051
Fig. 1. MAS 13C NMR spectrum of polymer 4 suspended in
benzene-d6.
characterization of polymers, magic angle spinning (MAS)
was occasionally also used, and Fig. 1 records the spectrum
of 4 swollen in C6D6. For initial studies of metathesis, a re-
lated synthesis was conducted. 11-Acetylthioundecanoic
acid (5a) (17) was converted into the corresponding
diallylamide 5b via the corresponding acid chloride, and
then attached to polymer in the manner described for 3a,
again the reaction to form polymer 6 was quantitative as
judged by weight gain and 13C NMR results.
The related synthesis of O-linked polymers is shown in
Scheme 2. The allyl ether 7b of tetraethylene glycol 7a was
prepared, and its Na salt was reacted with PS for 18 h at
60°C in THF. These conditions, the result of some optimiza-
tion efforts, produced polymer 8 in 90% yield, with charac-
teristic 13C NMR fingerprint.
Metathesis experiments
Conditions suitable for cross-metathesis of a terminal
alkene 9 with Z-but-2-ene were established first. In these and
subsequent reactions the “standard” Grubb’s catalyst
(bis(tricyclohexylphosphine)benzylidineruthenium(IV)
dichloride) was utilized. It was found that employing a 100-
fold excess of Z-but-2-ene in CH2Cl2 at ambient temperature
with 2 mol% catalyst gave complete reaction to form a Z:E
mixture (1:3) of the disubstituted alkene 10. Applying these
exact conditions to the metathesis of polymer 4 did not re-
sult in observable metathesis or significant change in weight.
At first the thiolate residue was suspected, and hence, mono-
mer 11 was synthesized. This was shown to be reactive un-
der the conditions of metathesis, giving 12 as an E/Z mixture
in 85% yield. Furthermore, the intramolecular metathesis of
polymer 6 to give the corresponding pyrroline 13 occurred
smoothly, although 10% Ru catalyst and a reaction time of
48 h were required. It was noted that although the product
polymer gave a good 13C NMR spectrum corresponding to
complete loss of starting material and the formation of
cyclopentene, it appeared dark green-black under a micro-
scope, despite intensive washings with a variety of solvents.
polymers that were suitable for our purpose based on the cri-
teria of mechanical stability and solvent-swelling properties,
where the loading is in the 2 to 3 mmol g–1 region (for an al-
ternative dendrimer-based approach to high–loading polysty-
rene, see ref. 10). Methods for the incorporation of side-
chains, and the ease of obtention of good quality 13C NMR
spectra that reveal signals from the terminal region of the
side-chain have already been reported (11).
In the present paper the application of alkene metathesis
to solid-phase chemistry is described, using high-loading
resins. In prior work, Bletcher and co-workers (12) demon-
strated that Tentagel or polystyrene bound dialkenes could
be subjected to efficient Ru-complex catalyzed
intramolecular metathesis leading from 70 to >90% of the
ring-closed product based on isolation by cleavage from the
resin. In addition intermolecular metathesis between poly-
mer-bound terminal alkenes and disubstituted alkenes was
similarly shown to occur in 46 to >95% yield. A contempo-
rary study employed solid-phase metathesis for the simulta-
neous cyclization and release of the product from the
polymer (13). The high reactivity of norbornene in ring-
opening metathesis has been exploited with styrene as the
solution coreactant (14); the reverse strategy with
vinylpolystyrene and norbornene leads to ring opening
methathesis polymerization (ROMP) in the solid state and
results in a support with a far higher density of functional
sites than the original (15). The significance of solid-phase
reactions has been recognized in recent reviews on alkene
metathesis by Grubbs and others (16).
Results and discussion
Polymer synthesis
For the preparation of sulfide-linked polymers, the syn-
thetic route of Scheme 1 was adopted. Commercially avail-
able 11-bromoundecanol (1) was converted into its allyl
ether 2, which was in turn converted into the S-thioester 3a
by SN2 displacement. Hydrolysis then produced the thiol 3b.
Two strategies were adapted for the polymer linkage step;
either the thiolate anion was generated in situ from 3a, or di-
rectly from the thiol. In both cases the reaction with 63%
chloromethylated polystyrene (2% crosslinked) gave poly-
mer 4 quantitatively within experimental error. Although
most use was made of standard 13C NMR spectra in the
This appeared to indicate some catalyst decomposition and
irreversible reaction with the polymer.
On the basis of this set of experiments there appeared to
be two further explanations for the failure of polymer cross-
metathesis; firstly that the concentration of reagent and (or)
catalyst in the polymer interstices was intrinsically low, and
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Can. J. Chem. Vol. 79, 2001
Fig. 2. (a) Polymer 8 swollen in CDCl3, 125 MHz; (b) after one
cycle of metathesis with Z-but-2-en-1,4-diol to give predomi-
nantly 17; (c) after two cycles of metathesis. Note the broaden-
ing of both resin and solvent (78 ppm) resonances.
of the polymer became broader after each cycle (Fig. 2).
This indicates that a change in the morphology of the poly-
mer takes place during metathesis. The simplest interpreta-
tion is that crosslinking takes place within the bead by
interchain metathetical reactions. Indeed an additional 1 to
2% of linkages would be expected to make a profound dif-
ference to the mobility of polymer-bound chains and thus af-
fect the 13C NMR line-widths. At this level there should be
detectable additional signals in the NMR spectrum and there
was an unassigned shoulder at 127.5 ppm in the spectra of
samples of polymer 17. This was close to, but not coincident
with, the alkene carbon resonance of model compound 16d
at 129 ppm, taken in the presence of polymer 8 to best simu-
late the signal environment of the trace impurity in 17.
In summary these experiments demonstrate the feasibility
of metathesis reactions on the pendant side-chains of high-
loading polystyrene resins, and the feasibility of monitoring
the product directly by 13C NMR. Under the conditions de-
scribed, the utility is limited because of the low on-polymer
reactivity and the lack of quantitative reaction (a pre-
requisite for successful solid-state combinatorial chemistry)
with any but the most simple alkene reactants.
secondly that the polymer environment led to a lowered re-
activity. The first of these possibilities was tested in part by
changing the reaction conditions, conducting metathesis of
polymer 4 in CH2Cl2:Z-but-2-ene (1:1) in a sealed tube with
3 mol% catalyst. After 3.5 days at ambient temperature,
workup gave a polymer whose 13C NMR spectrum indicated
complete reaction to form an E:Z isomeric mixture of the
butenyl ether 14 (Scheme 3). This success could not, how-
ever, be duplicated with other alkenes and cross-metathesis
of polymer 4 with either E-hex-2-ene (15) or the bis-
TBDMS ether of Z-but-2-en-1,4-diol 16a failed.
Appraisal of the results at this stage suggested that the re-
activity of polymer 4 in metathesis was substantially lower
than expected from the model experiments. One possibility
was that the polarity of the polymer medium was lower than
that of the solution because of the high density of hydrocar-
bon chains. This could lead to both unfavourable partition
and lower reactivity of the catalyst in the polymer phase. For
these reasons further metathesis experiments were carried
out with the polymeric allyl ether 8. Since the initial experi-
ments failed completely for alkenes other than Z-but-2-ene,
the polyether polymer 8 was reacted first with Z-but-2-en-
1,4-diol 16b. Under a variety of conditions slow metathesis
was observed, but the 13C NMR of the product 17 always
showed some unreacted starting material. A single run with
the corresponding ether 16c went to completion, however.
For the diol, best results were obtained when the solvent was
diglyme (83%, 3 mol% catalyst, 168 h) Less successful ex-
periments were conducted in CH2Cl2 (63%, 18 h) and THF
(30%, 18 h). The presence of 10% of MeOH appeared to
slow the turnover rate in CH2Cl2 even though it makes the
partly immiscible diol fully soluble. In DMSO, DMF, or
MeCN turnover was not observed, although there is some
swelling of the polymer in these solvents. No discernable re-
action took place in water (18).
Experimental
General
Reactions involving air-sensitive reagents were performed
under a dry argon atmosphere, using standard vacuum line
techniques in Schlenk glassware. Solvents were
deoxygenated where necessary by repeated freeze-thaw-
freeze cycles, in which the solvent was frozen using liquid
nitrogen, and allowed to warm until fully molten in vacuo or
by pump-fill degassing, in which case the solvent was cooled
to near freezing, usually using a dry ice – acetone bath,
evacuated, and refilled with argon while swirling using a
Whirlimixer™ to facilitate complete gas exchange. Transfers
were carried out using stainless steel cannula wire or by sy-
ringe. For reactions using resin bound substates, “Swirler”
refers to a Büchi Rotavapor M and “Bubbler” refers to a de-
signed piece of glassware where the resin was supported on
a glass sinter in solvent and agitated by argon passage.
Solvents were purchased from Rathburns, Fisons,
Ultrafine, Aldrich, or Prolabo and dried immediately before
use by distillation from standard drying agents (19).
Merrifield resin was purchased from Fluka, and was
2% crosslinked with divinylbenzene (~4.3 mmol Cl
per g resin) 200–400 mesh. Flash chromatography was per-
formed using Fluorochem Silca gel 60, 40–63 µm, 550 m2 g–1,
or with commercial Biotage apparatus; KP-SilTM 90 g car-
tridges (32–63 µm, 60 Å, 500–550 m2 g–1 silica). Melting
points were recorded by the author on a Reichert–Koffler
block apparatus and are uncorrected. Infrared spectra were
recorded on PerkinElmer 1750 or PerkinElmer Paragon 1000
1
FT spectrometers. H and 13C NMR spectra were recorded
on Varian Gemini 200 (200 MHz), Bruker AM 200
(200 MHz), Bruker WH 300 (300 MHz), Bruker DPX 400
(400 MHz), Bruker AMX 500 (500 MHz), or Bruker AM
500 (500 MHz) spectrometers. MAS spectra were recorded
on a Bruker MSL 200 (50.3 MHz) spectrometer. Polymer
samples to be analyzed were prepared by placing an appro-
priate amount of polymer (usually ~120–130 mg) in a 5 mm
Since only 83% yield was observed under the most fa-
vourable conditions, the polymer 17, thus formed, was re-
subjected to the same reaction conditions. This, however, led
to a rather small enhancement of the overall yield (83–87%).
At the same time it was noted that the 13C NMR resonances
© 2001 NRC Canada

Breed et al.
1053
NMR tube and small amounts of solvent until the polymer
was fully swollen and 2–4 mm of excess solvent remained.
The tube was then vibrated either using a sonicator,
whirlimixer, or by gently tapping the tube on a wooden sur-
face until no air bubbles were visible and the suspension ap-
peared homogeneous. The samples were then allowed to
settle for a minimum of 10 min before being place in the
spectrometer. For MAS samples by swelling the polymer in
the solvent and transferring to a sinter. The excess solvent
was removed by brief suction (~30 s) the sample was then
transferred to the rotor. Unless otherwise stated operations
were performed at room temperature.
2853 (s, C-H2, str), 1694 (s, C=O, str), 1647 (w, C=C, str),
1464 (s, C-H, def), 1429 (m, C-H, def), 1353 (s, CH3, def),
1262 (m), 1107 (s, C-O, str), 998 (m, -CH=CH2, def) 954,
923 (s, -CH=CH2, def), 801 (w), 722 (w, CH2, rocking), 672
(w), 627. 1H NMR (500 MHz, CDCl3) δ: 5.92 (ddt, J = 17.2,
10.8, 5.5 Hz, 1H, H2′), 5.27 (dq, J = 17.2, 1.4 Hz, 1H, H3′a),
5.16 (dq, J = 10.8, 1.4 Hz, 1H, H3′b), 3.96 (dt, J = 5.6,
1.4 Hz, 2H, H1′), 3.42 (t, J = 6.7 Hz, 2H, H1), 2.86 (t, J =
7.4 Hz, 2H, H11), 2.32 (s, 3H, H13), 1.67–1.52 (m, 4H, H2,
H10), 1.34–1.26 (m, 14H, H3–9). 13C NMR (125 MHz,
CDCl3) δ: 196.0 (C12), 135.1 (C2′), 116.6 (C3′), 71.7 (C1′),
70.5 (C1), 30.58 (C11), 29.7, 29.5, 29.4, 29.1, 29.1, 28.9
(C2,4–10,13), 26.1(C3).
Synthesis of polymers and their precursors
Preparation of poly[1-(11-allyloxy-undecylsulfanylmethyl)-
4-vinyl benzene-co-vinyl-benzene-co-divinyl-benzene] (4)
Preparation of 3-(11-bromo-undecyloxy)propene (2)
Sodium hydride (2.24 g, 60% in paraffin, 56 mmol) was
washed with pentane (3 × 10 mL) and then suspended in
THF (80 mL) and allyl bromide (10.4 mL, 120 mmol).
11-Bromoundecanol (10 g, 40 mmol) in THF (50 mL) was
added dropwise. The solution was heated under reflux for
18 h. The solvent was removed in vacuo, the residue was
dissolved in water (100 mL) and extracted with dichloro-
methane (1 × 125 mL, 1 × 100 mL). The combined organic
extracts were washed with water (100 mL), dried over mag-
nesium sulfate, and the solvent was removed in vacuo. The
product was further purified by column chromatography
(SiO2, pentane–toluene, 2:1) and Kugelrohr distilled (150°C,
4 mbar) to give a colourless oil (8.86 g, 76%). IR (thin film)
(cm–1): 3080 (m, C=C-H2, str), 2928 (s, C-H2, str), 2856 (s,
C-H2, str), 1728 (m), 1647 (w, C=C, str), 1464 (s, C-H, def),
1346 (s, CH3, def), 1254 (m), 1106 (s, C-O, str), 996 (m,
-CH=CH2, def), 922 (s, -CH=CH2, def), 722 (w, CH2, rock-
From thioacetic acid S-(11-allyloxy-undecyl)ester: To
a
suspension of sodium methoxide (730 mg, 13.5 mmol) in
THF (5 mL) was added dropwise, via cannula, a solution of
thioacetic acid S-(11-allyloxy-undecyl)ester (3.22 g,
11.25 mmol) in THF (5 mL). After 1 h, THF (10 mL) was
added, followed by dimethylformamide (30 mL). This solu-
tion was added via cannula to a flask containing Merrifield
resin (1.74 g, 4.3 mmol g–1) and this suspension was swirled
at 50°C for 60 h The suspension was then transferred to a
sinter and washed with dichloromethane (3 × 50 mL),
dimethylformamide (3 × 50 mL), dichloromethane (3 ×
50 mL), water (50 mL), methanol (50 mL), dichloromethane
(3 × 50 mL), dimethylformamide (3 × 50 mL), dichloro-
methane (3 × 50 mL), and pentane (3 × 50 mL). Drying in
vacuo gave the product as a colourless opaque tacky poly-
mer (3.28 g, 98%). IR (KBr disk) (cm–1): 3082 (vw, C=C-H2,
str) 3058 (vw, C=C-H2, str), 3024 (w, Ar-H, str), 2924 (s,
C-H2, str), 2852 (m, C-H2, str), 1723 (w) 1702 (w), 1647 (w,
C=C, str), 1604 (w, ar), 1510 (m, ar), 1494 (w), 1452 (m,
C-H, def), 1421 (w, C-H, def), 1347 (m), 1271 (w), 1239
(w), 1137 (vw), 1104 (s, C-O, str), 1018 (vw), 997 (w,
-CH=CH2, def), 920 (s, -CH=CH2, def), 827 (m, para Ar,
C-H bnd), 760 (m, Ph), 700 (s, Ph). 13C MAS NMR
(50.3 MHz, C6D6) δ: 135.9 (C2′), 115.8 (C3′), 71.8 (C1′), 70.5
(C1), 30.3, 30.0, 29.7, 29.3, 26.7 (C2–11).
1
ing), 645 (m, C-Br). H NMR (500 MHz, CDCl3) δ: 5.92
(ddt, J = 17.2, 10.6, 5.2 Hz, 1H, H2′), 5.27 (dq, J = 17.2,
1.6 Hz, 1H, H3′a), 5.17 (dq, J = 10.4, 1.3 Hz, 1H, H3′b), 3.96
(dt, J = 6.8, 1.3 Hz, 2H, H1′), 3.42 (t, J = 7.0 Hz, 2H, H1 or
H11), 3.41 (t, J = 7.1 Hz, 2H, H11 or H1), 1.85 (tt, J = 7.5,
7.0 Hz, 2H, H10), 1.58 (tt, J = 7.0, 7.0 Hz, 2H, H2), 1.43–
1.26 (m, 14H, H3–9). 13C NMR (125 MHz, CDCl3) δ: 135.1
(C2′), 116.6 (C3′), 71.7 (C1′), 70.5 (C1), 34.0 (C11), 32.8 (C10),
29.7, 29.5, 29.4, 29.4, 28.7, 28.1 (C2,4–9), 26.1 (C3).
Through isolation of the intermediate 11-allyloxy-undecane-
1-thiol (3b): Thioacetic acid S-(11-allyloxy-undecyl) ester
(4.29 g, 15 mmol) in methanol (50 mL) was placed in
round-bottom flask, and a solution of sodium hydroxide
(2.40 g, 60 mmol) in water (3.8 mL) – methanol (10 mL)
was added via cannula. The solution was heated at reflux for
25 min, then poured into phosphate buffer (pH 5.5, 100 mL).
The solution was extracted with dichloromethane (2 ×
100 mL, 1 × 25 mL). The combined extracts were washed
with water (1 × 100 mL), and solvent was removed in vacuo.
The product was further purified by column chromatography
(SiO2, pentane–toluene, 1:1) to give 11-allyloxy-undecane-
1-thiol as a colourless oil (1.784 g, 49%). CI-MS (NH4) m/z
Preparation of thioacetic acid S-(11-allyloxy-undecyl) ester
(3a)
To a solution of potassium thioacetate (5.71 g, 50 mmol)
in dimethylformamide (50 mL) was added 3-(11-bromo-
undecyloxy)propene (27.28 g, 25 mmol). The solution was
stirred for 18 h, then added to water (350 mL). This solution
was then extracted with ether (3 × 100 mL, 2 × 50 mL). The
combined ether extracts were washed with potassium car-
bonate solution (100 mL, 10%) and saturated potassium car-
bonate (2 × 100 mL), dried over sodium carbonate, and the
solvent was removed in vacuo. The product was further puri-
fied by column chromatography (SiO2, pentane–dichloro-
methane, 1:1) to give the product as a colourless oil (5.29 g,
74%). CI-MS (NH4) m/z (%): 287 ([M + H]+, 38), 245 ([M +
H – CH3CO]+, 39), 227 ([M + H – CH2CHCH2OH]+, 27),
187 ([M – CH3CO – OCH2CH=CH2]+, 100). HRMS calcd.:
287.2045; found: 287.2047. IR (thin film) (cm–1): 3369 (w,
COC-H3, str), 3079 (m, C=C-H2, str), 2924 (s, C-H2, str),
1
(%): 262 ([M + NH4]+, 22). H NMR (500 MHz, CDCl3) δ:
5.91 (ddt, J = 17.3, 10.6, 5.5 Hz, 1H, H2′), 5.26 (dq, J =
17.3, 1.6 Hz, 1H, H3′a), 5.16 (dq, J = 10.3, 1.5 Hz, 1H, H3′b),
3.95 (dt, J = 5.5, 1.5 Hz, 2H, H1′), 3.41 (t, J = 6.6 Hz, 2H,
H1), 2.51 (q, J = 7.3 Hz, 2H, H11), 1.75 (br s, 1H, SH), 1.63–
1.54 (m, 4H, H2, H10), 1.40–1.22 (m, 14H, H3–9). 13C NMR
© 2001 NRC Canada

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Can. J. Chem. Vol. 79, 2001
(125 MHz, CDCl3) δ: 135.0 (C2′), 116.6 (C3′), 71.7 (C1′), 70.5
(C1), 34.0 (C10), 29.7, 29.5, 29.4, 29.0, 28.3 (C2,4–9), 26.1
(C3), 24.6 (C11). Sodium hydride (288 mg, 60% in paraffin,
7.2 mmol) was washed with pentane (3 × 10 mL) and sus-
pended in THF (10 mL). Merrifield resin (1.047 g, 4.5 mmol)
was added washing into flask with THF (20 mL), followed
by 11-allyloxy-undecane-1-thiol (1.650 g, 6.75 mmol), rins-
ing the syringe with THF (15 mL). Upon addition of the
thiol, effervescence was observed. The suspension was
swirled at 60°C overnight. Water (10 mL) was added, and
the suspension was swirled for 10 min. The suspension was
transferred to a sinter and washed with dichloromethane
(25 mL), water (25 mL), dichloromethane (3 × 25 mL), and
ethanol (25 mL), and then dried in vacuo to give the product
as a colourless tacky polymer (1.993 g, quant.).
69%). CI-MS (NH4) m/z (%): 340 ([M + H]+, 100), 298
([M – C3H5]+, 14). HRMS calcd.: 340.2310; found:
340.2309. 1H NMR (500 MHz, CDCl3) δ: 5.84–5.70 (m, 2H,
H2′), 5.25–5.05 (m, 2H, H3′), 3.98 (br d, J = 5.8 Hz, 2H,
H1′a), 3.86 (br d, J = 4.5 Hz, 2H, H1′b), 2.85 (t, J = 2.4 Hz,
2H, H11), 2.32 (s, 3H, H13), 2.30 (t, J = 7.6 Hz, 2H, H2),
1.63 (q, J = 7.3 Hz, 2H, H3 or H10), 1.55 (q, 7.4 Hz, 2H, H10
or H3), 1.37–1.22 (m, 16H, H4–9). 13C NMR (125 MHz,
CDCl3) δ: 196.0 (C12), 173.2 (C1), 133.4 (C2′a), 133.0 (C2′b),
117.0 (C3′a), 116.5 (C3′b), 49.1 (C1′a), 47.8 (C1′b), 32.9 (C2),
30.6 (C11), 29.4, 29.4, 29.4, 29.1, 29.0, 28.8 (C4–10, 13), 25.3
(C3).
Preparation of poly-[N,N-diallyl-11-(4-vinyl-benzyl
sulfanylundecanoic acid amide)-co-vinyl-benzene-co-
divinyl-benzene] (6)
Preparation of (11-allyloxy-undecylsulfanylmethyl)benzene
(11)
To sodium methoxide (194 mg, 3.6 mmol) was added a
solution of thioacetic acid S-(10-diallylcarbamoyl decyl) es-
ter (1.018 g, 3 mmol) in THF (2 mL). The solution was
stirred for 1 h, then a small aliquot removed and analyzed by
1H NMR, which showed complete deacetylation. The sol-
vent was then removed in vacuo, the solid was redissolved in
THF (10 mL), and the solution was added via cannula to a
flask containing Merrifield resin (465 mg, 4.3 mmol g–1)
swollen in THF (5 mL). The suspension was swirled at 55°C
for 18 h, then transferred to a sinter and washed with di-
Sodium hydride (180 mg, 60% in paraffin, 4.5 mmol) was
washed with pentane (3 × 5 mL) and suspended in THF
(6 mL). S-Benzylisothiouronium chloride (405 mg, 2 mmol)
was added and the mixture was heated at reflux for 150 min.
THF (10 mL) was added and the mixture was heated at re-
flux for 4 h. 3-(11-Bromo-undecyloxy)propene (583 mg,
2 mmol) was added and the mixture was heated at reflux for
18 h. After cooling, toluene (20 mL) and water (10 mL)
were added and the THF was removed in vacuo. Toluene
(40 mL) was added and the mixture was washed with water
(3 × 30 mL). The combined water washings were extracted
with toluene (20 mL), and the combined toluene extracts
were dried over sodium sulfate. The product was isolated by
column chromatography (SiO2, dichloromethane–pentane,
1:1) giving the product as a pale yellow oil (466 mg, 69%).
CI-MS (NH4) m/z (%): 335 ([M + H]+, 100). HRMS calcd.:
chloromethane (2
×
40 mL), water (40 mL),
dimethylformamide (4 × 40 mL), and dichloromethane (5 ×
40 mL), then dried in vacuo yielding the product as a colour-
less polymer (1.019 g, quant.). IR (KBr disk) (cm–1): 3081
(w, C=C-H2, str), 3024 (w, C=C-H or Ar-H, str), 2921 (s,
C-H, str), 2852 (m, C-H, str), 1701 (m, C=O, str), 1654 (s,
C=C, str), 1636 (s, C=C, str), 1458 (m, C-H, def), 1420 (m,
C-H, str), 1213 (br, m), 1113 (w), 1016, 989 (m, -CH=CH2,
def), 912 (m, -CH=CH2, def), 824 (m), 761 (m, Ph), 698 (m,
Ph). 13C NMR (125 MHz, CDCl3) δ: 173.2 (C1), 133.5,
133.0 (C2′), 117.1, 116.5 (C3′), 49.2, 47.8 (C1′), 33.0 (C2),
31.7, 29.4 (C4–11), 25.3 (C3).
1
335.2409; found: 335.2410. H NMR (500 MHz, CDCl3) δ:
7.31 (s, 2H, H15 or H14), 7.30 (s, 2H, H14 or H15), 7.27–7.20
(m, 1H, H16), 5.92 (ddt, J = 17.2, 10.4, 5.6 Hz, 1H, H2′),
5.27 (dq, J = 17.2, 1.7 Hz, 1H, H3′a), 5.17 (ddt, J = 10.4, 1.9,
1.3 Hz, 1H, H3′b), 3.96 (dt, J = 5.64, 1.4 Hz, 2H, H1′), 3.70,
(s, 2H, H12), 3.42 (t, J = 6.7 Hz, 2H, H1), 2.40, (t, J =
7.4 Hz, 2H, H11), 1.62–1.51 (m, 4H, H2, H10), 1.38–1.20 (m,
14H, H3–9). 13C NMR (125 MHz, CDCl3) δ: 138.6 (C13),
135.1 (C2′), 128.8 (C15), 128.4 (C14), 126.8 (C16), 116.7 (C3′),
71.8 (C1′), 70.5 (C1), 36.2 (C12), 31.3 (C11), 29.7, 29.5, 29.5,
29.2, 28.8 (C2,4–10), 26.1 (C3).
Preparation of 2-(2-(1-(2-allyloxy-ethoxy)-ethoxy)-ethoxy)-
ethanol (7) (20)
A 500 mL round-bottom flask was charged with sodium
(5.93 g, 0.257 mol) and tetraethylene glycol (200 g). The so-
lution was stirred at 80°C for 18 h. The solution was allowed
to cool to room temperature, then 3-bromopropene (23 mL,
0.266 mol) was added dropwise over 15 min. The solution
was warmed to 70°C for 90 min and 100°C for 60 min. The
solution was allowed to cool to room temperature and added
to a mixture of saturated sodium chloride (400 mL) and wa-
ter (200 mL). The aqueous solution was extracted with di-
chloromethane (2 × 200 mL, 4 × 50 mL). The combined
extracts were extracted with water (2 × 200 mL, 11 ×
100 mL), however TLC showed that some product remained
in the dichloromethane layer. The solvent was reduced in
vacuo to 150 mL and the solution was further extracted with
water (2 × 150 mL). The solvent was then totally removed in
vacuo, and the oil was redissolved in ether (500 mL) and ex-
tracted with water (5 × 100 mL). Sodium chloride was
added to the combined water extracts until the solution was
saturated. The solution was extracted with dichloromethane
(3 × 150 mL, 6 × 100 mL), and the combined extracts were
Preparation of thioacetic acid S-(10-diallylcarbamoyl
decyl) ester (5b)
To
a solution of 11-acetylsulfamyl-undecanoic acid
(1.820 g, 7 mmol) in toluene (10 mL) was added thionyl
chloride (2 mL, 27 mmol), and the mixture was heated at re-
flux for 2 h. The solvent was removed in vacuo. The acid
chloride was dissolved in toluene (10 mL), and diallylamine
(5 mL, 40 mmol) was added. The mixture was stirred for 1 h
before the addition of saturated sodium hydrogen carbonate
(20 mL). Dichloromethane (100 mL) was then added; the
solution was washed with saturated sodium hydrogen car-
bonate (50 mL) and phosphate buffer (pH 5.5, 50 mL), then
dried over magnesium sulfate. The product was further puri-
fied by column chromatography (SiO2, pentane – ethyl ace-
tate, 5:1) to give the product as a pale yellow oil (1.569 g,
© 2001 NRC Canada

Breed et al.
1055
reduced in vacuo to 500 mL. The solution was dried over
sodium sulfate and solvent was removed in vacuo. The oil
was then fractional distilled using a 5 inch Vigreux column,
and the fraction at 102–112°C at 0.03–0.04 mm Hg (1 mm
Hg = 133.32 kPa) was collected. TLC showed this to be a
mixture consisting mainly of the desired product, but con-
tained small amounts of tetraethyleneglycol diallyl ether and
tetraethylene glycol. The oil was redissolved in saturated so-
dium chloride (300 mL), and extracted with ether (2 ×
200 mL, 5 × 100 mL). The combined extracts were dried
over magnesium sulfate, and solvent was removed in vacuo.
The oil was triturated with pentane (2 × 50 mL). Solvent
was removed in vacuo giving a colourless oil (30.76 g,
50%), which contained a slight trace of the diallyl ether of
tetraethyleneglycol, bp 102–112°C, 0.03–0.04 mm Hg ((lit.
(21) 99–101°C, 0.2 mm Hg). CI-MS (NH4) m/z (%): 235
tity of the two isomers was partially separated by prepara-
tive GLC (Peg 20M, 15%, 175°C). H NMR (500 MHz,
1
CDCl3) δ (Z)-isomer: 5.60 (dqd, J = 10.4, 6.7, 1.0 Hz, 1H,
H2), 5.42 (dtd, J = 10.4, 7.0, 1.0 Hz, 1H, H3), 4.48 (br s, 1H,
NH), 3.78 (br s, 2H, H4), 1.67 (dd, J = 6.7, 0.9 Hz, 3H, H1),
1.45 (s, 9H, H7); (E)-isomer: 5.60 (dq, J = 14.7, 7.0, 1H,
H2), 5.45 (dt, J = 14.7, 6.3 Hz, 1H, H3), 4.54 (br s, 1H, NH),
3.66 (br s, 2H, H3), 1.67 (d, J = 7.0 Hz, 3H, H1), 1.45 (s, 9H,
H7). 13C NMR (125 MHz, mixed isomers, CDCl3) δ: 155.8
(C5Z), 155.7 (C5E), 127.6 (C3E), 127.5 (C2E), 127.2 (C3Z),
126.7 (C2Z), 79.1 (C6), 42.5 (C4E), 37.3 (C4Z), 28.4 (C7),
17.6 (C1E), 12.9 (C1Z).
General procedure for screening of metathesis of allyl-
carbamic acid tert-butyl ester (9)
Allyl-carbamic acid tert-butyl ester (78.6 mg, 0.5 mmol)
and bis(tricyclohexylphosphine)benzylidineruthenium(IV)
dichloride (8.2 mg, 10 µmol) were placed in a Schlenk tube
and degassed. In a separate Schlenk tube dichloromethane
(10 mL) and the alkene (5 mmol) were degassed. The liquid
was transferred via cannula to the first Schlenk tube. The re-
actions were followed both by TLC and (or) by removing
aliquots (0.5 mL), removing the solvent in vacuo, and ana-
1
([M + H]+, 100). H NMR (500 MHz, CDCl3) δ: 5.87 (ddt,
J = 17.2, 10.3, 5.7 Hz, 1H, H2′), 5.22 (dq, J = 17.2, 1.6 Hz,
1H, H3′a), 5.13 (dm, J = 10.3 Hz, 1H, H3′b) 3.98 (dm, J =
5.6 Hz, 2H, H1′), 3.68–3.54 (m, 8H, H1–8), 2.81 (br s, 1H,
OH). 13C NMR (125 MHz, CDCl3) δ: 134.7 (C2′), 116.8
(C1′), 72.5 (C7), 72.0 (C1′), 70.5, 70.5, 70.5, 70.2 (C2–7), 69.3
(C1), 61.6 (C8).
1
lyzing by H NMR.
Preparation of poly[1-(2-(2-(1-(2-allyloxy-ethoxy)-ethoxy)-
ethoxy)-ethoxy methyl)-4-vinyl benzene-co-vinyl-benzene-
co-divinyl-benzene] (8)
Pent-2-enyl-carbamic acid tert-butyl ester (25): Using E-2-
hexene; H NMR (500 MHz, CDCl3) δ: 5.63 (dtt, J = 15.3,
1
6.2, 1.3 Hz, 1H, H3), 5.43 (dt, J = 15.3, 5.9 Hz, 1H, H4),
4.55 (br s, 1H, NH), 3.68 (br t, 2H, H5), 2.02 (qddd, J = 7.3,
6.2, 1.5, 1.2, 2H, H2), 1.44 (s, 9H, H8), 0.97 (td, J = 7.4, 1.2,
3H, H1). 13C NMR (125 MHz, CDCl3) δ: 155.7 (C6), 134.6
(C4), 125.3 (C3), 79.1 (C7), 42.5 (C5), 28.4 (C8), 25.2 (C2),
13.4 (C1).
Merrifield resin (1.164 g, 4.3 mmol g–1), sodium hydride
(800 mg, 60% in paraffin, 20 mmol), THF (20 mL), and
2-(2-(1-(2-allyloxy-ethoxy)-ethoxy)-ethoxy)-ethanol (7) (4.686 g,
20 mmol) were placed in 50 mL round-bottom flask, and
swirled at 60°C for 18 h. The suspension was transferred to
a sinter with THF, and washed with DMF (3 × 30 mL), wa-
ter (3 × 30 mL), methanol (3 × 30 mL), tetraethyleneglycol
dimethyl ether (3 × 30 mL), methanol (3 × 30 mL), and di-
chloromethane (3 × 30 mL) and dried in vacuo giving the
product as colourless opaque tacky polymer (2.056 g, 90%).
13C MAS NMR (50.3 MHz, (CD3)2SO) δ: 134.1 (C2′), 115.1
(C3′), 71.1 (C1′), 70.0 (C2–8), 69.1 (C1).
4-tert-Butoxycarbonylamino-but-2-enyl)-carbamic acid tert-
butyl ester:
Bis(tricyclohexylphosphine)benzylidineruthenium(IV)
dichloride (97 mg, 2 mol%) and allyl-carbamic acid tert-
butyl ester (1.00 g, 5.92 mmol) were placed in a Schlenk
tube. Chloroform (50 mL) was added via cannula and the so-
lution was stirred at 50°C for
bis(tricyclohexylphosphine)benzylidineruthenium(IV)
3
days. More
Experimental for metathesis reactions
Diallylcarbamic acid tert-butyl ester (21, 22), 2,5-
dihydropyrrole-1-carboxylic acid tert-butyl ester (23), and
allyl-carbamic acid tert-butyl ester (23) were prepared by lit-
erature procedures.
dichloride (97 mg, 2 mol%) was added and the solution was
stirred for a further 3 days at 50°C. The solvent was re-
moved in vacuo and the stereoisomeric products were sepa-
rated by chromatography on a Biotage apparatus (ethyl
1
acetate – pentane, 1:4). H NMR (500 MHz, CDCl3) E-iso-
Preparation of but-2-enylcarbamic acid-tert-butyl ester
(10) (24)
mer δ: 5.55 (br s, 2H, H1), 4.88 (br s, 2H, NH), 3.77 (br s,
4H, H2), 1.44 (s, 18H, H1). 13C NMR (125 MHz, CDCl3) δ:
1
Bis(tricyclohexylphosphine)benzylidineruthenium(IV)
dichloride (27.4 mg, 1 mol%) and allylcarbamic acid-tert-
butyl ester (9) (524 mg, 3.33 mmol) were placed in a
Schlenk tube fitted with a dry ice condenser. Dichloro-
methane (65 mL) was added via cannula. Z-2-Butene was
condensed into a Schlenk tube cooled in a dry ice – acetone
bath, and 3.5 mL was transferred into the tube using a dry
ice cooled syringe. The solution was stirred for 6 h, the con-
denser was then removed, a needle was inserted into the sep-
tum, and the solution was left overnight. The solvent was
then removed in vacuo and the product was isolated by col-
umn chromatography (SiO2, pentane – ethyl acetate, 2:1) to
give the product as brown oil (510 mg, 89%). A small quan-
155.7 (C3), 128.4 (C1), 79.4 (C4), 41.9 (C2), 28.4 (C5). H
NMR (500 MHz, CDCl3) Z-isomer δ: 5.61 (br s, 2H, H1),
4.63 (br s, 2H, NH), 3.72 (br s, 4H, H2), 1.44 (s, 18H, H5).
13C NMR (125 MHz, CDCl3) δ: 155.9 (C3), 128.9 (C1), 79.4
(C4), 37.1 (C2), 28.4 (C5).
Preparation of 11-(but-2-enyloxy-undecyl)-
sulfanylmethylbenzene (12)
Bis(tricyclohexylphosphine)benzylidineruthenium(IV)
dichloride (8.2 mg, 2 mol%) was placed in a Schlenk tube fit-
ted with a dry ice condenser. Z-2-butene was condensed into a
Schlenk tube cooled in a dry ice – acetone bath, and 0.5 mL
was transferred into the tube using a dry ice cooled syringe.
© 2001 NRC Canada

1056
Can. J. Chem. Vol. 79, 2001
11-(Allyloxy-undecylsulfanylmethyl)benzene (0.5 mmol,
167 mg) in dichloromethane (10 mL) was added via can-
nula, and the solution was stirred for 5.5 h. The solvent was
removed in vacuo and the product was further purified by
column chromatography (SiO2, dichloromethane–pentane, 1:1)
yielding the product as a yellow oil (134 mg, 85%). CI-MS
(NH4) m/z (%): 349 ([M + H]+, 100), 293 ([M – C4H7]+, 2).
HRMS calcd.: 349.2565; found: 349.2575. 1H NMR
(500 MHz, CDCl3) δ: 7.31 (s, 2H, H14 or H15), 7.30 (s, 2H,
H15 or H14), 7.27–7.20 (m, 1H, H16), 5.75–5.53 (m, 2H, H2′
and H3′), 4.02 (ddt, J = 6.6, 1.5, 1.0 Hz, 2H, H1′Z), 3.88 (dt,
6.2, 1.2 Hz, 2H, H1′E), 3.70 (s, 2H, H12), 3.41 (t, J = 6.9 Hz,
2H, H1Z), 3.39 (t, J = 6.9 Hz, 2H, H1E), 2.40 (t, J = 7.6 Hz,
2H, H11), 1.71 (ddt, J = 6.5, 1.6, 1.2 Hz, 3H, H4′E), 1.66 (ddt,
J = 6.8, 1.7, 0.9 Hz, 3H, H4′Z), 1.61–1.51 (m, 4H, H2 and
H10), 1.40–1.14 (m, 14H, H3–9). 13C NMR (125 MHz,
CDCl3) δ: 138.7 (C13), 129.2 (C2′E), 128.8 (C15), 128.4 (C14),
127.8 (C3′E), 127.5 (C2′Z), 127.1 (C3′Z), 126.8 (C16), 71.5
(C1E), 70.4 (C1Z), 70.3 (C1′E), 66.0 (C1′Z), 36.3 (C12), 31.4
(C11), 29.8, 29.5, 29.5, 29.2, 28.9 (C2,4–10), 26.2 (C3), 17.7
(C4′E), 13.2 (C4′Z).
room temperature for 84 h. The lower half of the tube was
then cooled in liquid nitrogen and the upper part was bro-
ken. The polymer was transferred to a sinter with dichloro-
methane and washed with dimethylformamide (3 × 25 mL),
dichloromethane (3 × 25 mL), and pentane (3 × 25 mL), and
dried in vacuo yielding the pale orange product polymer
(206 mg, 94%). IR (thin film) (cm–1): 3052 (w, C-H, str),
3023 (m, Ar-H or C=C-H, str), 2926 (s, C-H, str), 2850 (m,
C-H, str), 1720 (m), 1702 (m), 1603 (m, Ar-H, def), 1509
(m, Ar-H, def), 1492 (m, Ar-H, def), 1440 (m, C-H, def),
1420 (m, C-H, def), 1364 (w, C-H3, def), 1312 (w), 1260
(m), 1212 (w), 1180 (w, C-O, str), 1144 (w), 1108 (m, C-O,
str), 1066 (w), 1018 (w), 965 (m, (E)-H-C=C-H, def), 908
(w), 823 (m, para Ar, C-H bnd), 759 (m, Ph, bnd), 747 (m),
698 (m, Ph, bnd), 672 (w), 661 (m). 13C NMR (125 MHz,
CDCl3) δ: 128.9 (C2′), 127.6 (C3′), 71.2 (C1), 70.0 (C1′), 31.2,
29.3, 25.8 (C2–11), 17.6 (C4′E), 13.0 (C4′Z).
From Resin-OH and crotyl bromide: Potassium
hydride
(35% in mineral oil) was placed in a preweighed Schlenk
tube and washed with pentane (3 × 10 mL). The residual
pentane was removed in vacuo to give (120 mg, 3.0 mmol).
The Schlenk tube was cooled in dry ice – acetone bath, and
solution of 18-crown-6 (555 mg, 2.1 mmol) in THF (22 mL)
was added slowly via cannula. Resin-OH (12) was placed in
the swirler, and the potassium hydride solution was added
via cannula. As the suspension warmed to room temperature
effervescence was observed. The suspension was allowed to
warm to room temperature and swirled for 30 min. Crotyl
bromide (1.0 mL, 10 mmol) was added and the suspension
was swirled overnight, then transferred to a sinter with di-
chloromethane, and washed with dimethylformamide (3 ×
30 mL), dichloromethane (30 mL), and pentane (30 mL),
then dried in vacuo to give the product as a colourless tacky
polymer (521 mg, 18% (by 13C NMR)).
Preparation of poly[1-(2,5-dihydro-pyrrol-1-yl)-11-(4-vinyl
benzyl sulfanyl)-undec-1-one-co-vinyl-benzene-co-divinyl-
benzene] (6)
Bis(tricyclohexylphosphine)benzylidineruthenium(IV) di-
chloride (26 mg, 31 µmol) and resin 75 (150 mg, 312 µmol)
were placed in a round-bottom flask and dichloromethane
(6 mL) was added. The suspension was swirled under argon
for 48 h, before being transferred to a sinter with dichloro-
methane, and washed with dichloromethane (3 × 25 mL),
dimethylformamide (3 × 25 mL), and various combinations
of ethanol, methanol, dimethylformamide, pentane, toluene,
acetonitrile, and dimethylsulfoxide. However no washing
solvent, or combination successfully removed the dark-green
colour from the bead. The polymer was finally washed with
dichloromethane (3 × 25 mL), and dried in vacuo, giving the
product as a dark green polymer (142 mg, 92%). IR (KBr
disc) (cm–1): 3081 (w), 3055 (w), 3024 (m), 2926 (s), 2848
(m), 1944 (br, m), 1719 (s), 1702 (s), 1654 (s), 1648 (s),
1420 (m), 1263 (m), 1198 (m), 1107 (m), 1069 (w), 997 (m),
917 (m), 823 (s), 737 (s), 695 (m, Ph), 669 (s). 13C NMR
(125 MHz, CDCl3) δ: 171.8 (C1), 126.0 (C2′), 53.5 (C1′a),
52.9 (C1′b), 34.5, 33.2, 29.44, 26.3, 25.0 (C2–11).
General procedure for screening of metathesis of resin 8
and various alkenes
Resin 8 (150 mg, 0.32 mmol) and bis(tricyclohexyl-
phosphine)benzylidineruthenium(IV) dichloride (7.8 mg, 3
mol%) were loaded into a small Schlenk tube with a small
magnetic follower. The contents of the Schlenk tube were
degassed. The alkene and solvent were placed in a separate
Schlenk tube, degassed, and added via cannula. The suspen-
sion was stirred slowly for the stated amount of time, then
transferred to a sinter with a solvent (usually dichloro-
methane) and washed with some of the following solvents:
dichloromethane, dimethylformamide, methanol, pentane,
tetraglyme, THF, and dried in vacuo For the cross-
metathesis product with Z-but-2-en-1,4-diol. 13C NMR
(125 MHz, CDCl3) δ: 133.2 (C3′), 127.4 (C2′), 70.9 (C3′),
69.8, 67.2 (C1–8), 62.8 (C1′), 58.6 (C4′).
Preparation of poly-[11-but-2-enyloxy-undecyl sulfanyl
methyl-(4-vinyl benzene)-co-vinyl-benzene-co-divinyl-
benzene] (14)
From metathesis of resin 4 with Z-2-butene: Resin 4 (200 mg,
2.27 mmol g–1) was placed in a thick walled glass tube
(12 mm bore) and washed down with THF. The solvent was
removed by blowing argon over the suspension until no sol-
vent was visible outside the polymer. The polymer was then
dried in vacuo. The tube was then cooled in a dry ice – ace-
tone bath. Z-2-Butene was condensed into a Schlenk tube
cooled in a dry ice – acetone bath, and 0.6 mL was trans-
ferred into the tube using a dry ice cooled syringe.
Bis(tricyclohexylphosphine)benzylidineruthenium(IV)
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