Synthesis of macrocyclic polyethers via Ru complex-catalyzed metathesis cyclization and their use as the ring component of rotaxanes

Article abstract of DOI:10.1016/j.jorganchem.2006.09.032

Ring closing metathesis of the vinyl group-terminated oligoethers catalyzed by RuCl₂({double bond, long}CHPh)(PCy₃)₂ yielded macrocyclic polyethers containing vinylene group. The ¹H and ¹³C NMR spectr

Full text of DOI:10.1016/j.jorganchem.2006.09.032

Journal of Organometallic Chemistry 691 (2006) 5260–5266
www.elsevier.com/locate/jorganchem
Synthesis of macrocyclic polyethers via Ru complex-catalyzed
metathesis cyclization and their use as the ring component of rotaxanes
*
Takeshi Umemiya, Daisuke Takeuchi, Kohtaro Osakada
Chemical Research Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
Received 28 June 2006; received in revised form 16 September 2006; accepted 16 September 2006
Available online 23 September 2006
Abstract
Ring closing metathesis of the vinyl group-terminated oligoethers catalyzed by RuCl2(@CHPh)(PCy3)2 yielded macrocyclic polyethers
containing vinylene group. The 1H and 13C NMR spectra indicated the presence of C@C double bond (trans/cis = ca. 80:20). The
obtained 23-membered cyclic ether reacted with benzyl(anthrylmethl)ammonium hexafluorophosphate to produce the pseudo-rotaxane
as colorless crystals. X-ray crystallography revealed N–Hꢀ ꢀ ꢀO hydrogen bonds and stacking of the aromatic planes between the host and
1
guest molecules, which stabilized the rotaxane structure in the solid state. The H NMR spectra of the solutions containing the macro-
cyclic polyether and several secondary ammonium salts indicated the formation of pseudo-[2]-rotaxanes.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Ru-carbene complex; Ring-closing metathesis; Macrocycle; Rotaxane; Polyether; Metathesis; Ruthenium complex; Si-compound
1. Introduction
well as direct synthesis of the interlocked molecules such
as catenanes and rotaxanes [6–8]. Metathesis of the Cu(I)
complexes with the phenanthroline ligands containing the
two terminating vinyl groups was found to produce the
catenane via selective coupling of the pairs of vinyl groups
efficiently [7]. Very recently, Grubbs succeeded new synthe-
sis of the rotaxane formed by the crown ether and the sec-
ondary ammonium cation with bulky terminal groups via
repeated ring-opening and ring closing metathesis reaction
of the polyether catalyzed by Ru complex [8].
In this paper, we report preparation of macrocyclic
polyethers containing a C@C bond via the ring-closing
metathesis [9] and its complexation with the secondary
ammonium cations leading to the pseudo-rotaxanes as well
as results of structure determination of the new pseudo-
rotaxanes by X-ray crystallography.
Rotaxanes [1] have attracted recent attention because of
the unique structure that is composed of interlocked cyclic
and linear molecules components and because of possible
application to the molecular materials such as molecular
machines [2], switching devices [3], and so on. There have
been a number of reports of the rotaxanes and pseudoro-
taxanes containing crown ethers as the cyclic component
and secondary ammonium salts as the axis component.
Dibenzo[24]crown-8 (DB24C8) has the cavity size that is
suited to form stable pseudo-rotaxanes with the secondary
ammonium cations. The crown ethers composed of the
–C–C–O– units, having other ring sizes such as dibenzo
[18]crown-6 (DB18C6), dibenzo[30]crown-10 (DB30C10),
dinaphtho[38]crown-10 (DN38C10) and dinaphtho[30]
crown-10 (DN30C10), form the pseudo-rotaxanes with
smaller association constants [4].
2. Results and discussion
Recent progress of the ring-closing metathesis reaction
[5] enabled formation of molecules with large size ring as
Acyclic oligoethers 1a and 1b undergo ring-closing
metathesis reaction in the presence of catalytic amount of
RuCl2(@CHPh)(PCy3)2 at room temperature to produce
*
Corresponding author. Tel.: +81 45 924 5223; fax: +81 45 924 5224.
E-mail address: kosakada@res.titech.ac.jp (K. Osakada).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.09.032

T. Umemiya et al. / Journal of Organometallic Chemistry 691 (2006) 5260–5266
5261
the 23-membered macrocyclic polyether 2a and 26-mem-
bered polyether 2b in the respective yields 91% and 58%,
as shown in Eq. (1). The reactions were carried out in
polyethers contains the C@C double bond as a mixture of
trans and cis isomers (2a: 89:11; 2b: 87:13). Analogous
cyclization of the disilane-containing polyether terminated
by two vinyl groups, 1c, led to the corresponding 32-mem-
bered macrocycle 2c, as shown in Eq. (2). The cyclization
occurs more slowly than the reaction in Eq. (1). The
compound 1c was converted into 50% after 2.5 h and gave
the product 2c in the isolated yield of 31% (trans:cis =
84:16).
Addition of a solution of anthrylmethy(benzyl)ammo-
nium hexafluorophosphate in CDCl3/CD3CN (60:40, vol/
vol) to a solution of excess 2a causes separation of the
pseudo-rotaxane, 3, composed of the cyclic polyether and
the ammonium cation as shown in Eq. (3). Colorless crys-
tals of 3 were grown selectively from the reaction
O
n
O
O
O
O
O
O
1a: n = 1
1b: n = 2
ð1Þ
O
PCy
3 Ph
Ru
n
O
O
O
O
Cl
Cl
PCy3
O
O
CH2 CH2
ð3Þ
2a: n = 1
2b: n = 2
low concentration of the substrates (10 mM) in order to
suppress the intermolecular metathesis of the vinyl groups
to form their oligomers or polymers. These cyclic polye-
thers were isolated as white solids by recrystallization of
the products from MeOH and characterized by NMR spec-
troscopy. The H NMR spectra show two signals due to
vinylic hydrogens with different peak areas, indicating that
the macrocyclic
mixture that should contain an equilibrated mixture of 2a,
ammonium, and 3. Fig. 1a depicts the structure of 3 deter-
mined by X-ray crystallography. The nitrogen atom of the
cation is surrounded by the four oxygen atoms of the polye-
ther. Fig. 1b displays interaction between the cyclic molecule
1
Me Me
Me
Me
a
Si Si
O
O
O
O
O
O
O
O
b
1c
ð2Þ
Me Me
Si Si
Me
Me
O
O5
PCy
3 Ph
Cl
Cl
O
O
O4
2.56
H2
Ru
N
2.03
H1
2.43
PCy3
O
O
2.09
O1
O3
CH2 CH2
O2
O
O
O
O
Fig. 1. (a) ORTEP drawing of rotaxane 3 determined by X-ray crystal-
lography. (b) Distance between O and HN groups.
2c

5262
T. Umemiya et al. / Journal of Organometallic Chemistry 691 (2006) 5260–5266
1
and dialkyl ammonium group. The distances between the
four oxygen atoms and the nitrogen of the host and guest
are in the range, 2.97–3.21 A. Calculation of the hydrogen
anes is confirmed by the H NMR spectra which show the
1
signal at lower field positions. The H NMR spectrum of
˚
dibenzylammonium hexafluorophosphate shows the
CH2N hydrogen signal at d 4.18, while the spectrum of a
mixture of the ammonium salt with 2b shows not only the
signal at that position but also that at d 4.57. The latter sig-
nal is assigned to the CH hydrogens of the pseudorotaxanes
formed in the solution. (4-t-Butylbenzyl)hexylammonium
hexafluorophosphate whose cationic part is unsymmetrical
shows two signals due to CH2 hydrogens at d 4.12 and 2.98.
Both signals are shifted to lower magnetic positions. Table 1
summarizes the results of the complexation and includes the
NMR peak positions before and after complexation as well
as the equilibrium constants of the axes with the crown
ether 2b [13]. The ammonium salts having one bulky aro-
matic group and one benzyl group shows relatively high
association constants. The two aromatic groups may
enhance the pseudo-rotaxane formation, presumably via
the p–p stacking interaction. The association constant of
dibenzylammonium hexafluorophosphate is lower than
those of anthrylmethy(benzyl)ammonium hexafluorophos-
phate and (4-t-butylbenzyl)phenylammonium hexafluoro-
phosphate, although it has two phenyl group. The
presence of bulky groups such as anthryl group and 4-t-
butylphenyl group may serve to block the dissociation of
the macrocycle.
positions of attached to the nitrogen atom by assuming the
ideal geometry (d = 0.97 A) also indicated close contact of
˚
the hydrogen atoms with oxygen atoms of the polyether
˚
(N–H–O = 2.0–2.6 A). The four oxygen atoms form the
plane which contains the NH2 group of the guest molecule.
The distance between the anthryl group of the axis and the
˚
phenylene ring of the macrocycle is 3.4 A, indicating the
p–p stacking interaction of the host and guest. These aro-
matic planes are parallel from each other, similarly to the
previously reported rotaxanes of crown ethers with the sec-
ondary ammonium cation [4,10]. The stacking serves to sta-
bilize the pseudo-rotaxane formation.
The crystal structure indicates that the C@C bond of the
cyclic polyether has trans configuration in the crystal struc-
ture of rotaxane, although the starting cyclic compound is
a mixture of the trans and cis isomers. Dissolution of once
isolated the rotaxane 3 in CD3CN shows the presence of
the rotaxane in 22% and 2a and the ammonium salt in
78%. The NMR spectra show the presence of trans and
cis C@C double bond in the macrocyclic polyether in the
mixture. These results are explained by the results that
the pseudorotaxane contains both the cyclic polyether with
trans and cis C@C double bonds and that the pseudorotax-
ane with trans-C@C double bond forms single crystals
more easily than that with cis-C@C bond (see Fig. 2).
Reaction of the macrocyclic ethers 2a and 2b with vari-
ous ammonium salts form the rotaxanes although isolation
of the rotaxanes was not feasible. Formation of the rotax-
In summary, the metathesis reaction using Ru
complex-catalyzed ring closing metathesis of the vinyl
group-terminated polyethers produce the macrocyclic
polyethers with vinylene groups in 23 to 32-membered
ring-size. One of the cyclic polyethers forms rotaxanes
Hl
Hk
O
O
Hj
Hi
O
O
O
CD3CN
25 C, 24 h
O
Ha Hb
N
Hc
N
O
O
Hd
He
+
H2
O
O
Hh
H2
˚
O
O
O
O
PF6
Hg
PF6
Hf
Hh,Hk
Hi,Hj
Hl
Hg
He Hc
Hd
Hi*,Hj*
Hc*
Hd*
δ
3
9
8
7
6
5
4
trans
Hb
Ha
4.6
Hb*
Ha*
cis
δ
4.4
6.0
5.8
5.6
5.4
5.2
5.0
4.8
Fig. 2. 1H NMR spectrum (400 MHz) of a CD3CN solution of 3. Assignment of the peaks is shown in the chemical formula. The peak with asterisk is
assigned to the rotaxane, and the peak without asterisk is assigned to dissociated cyclic and linear molecules.

T. Umemiya et al. / Journal of Organometallic Chemistry 691 (2006) 5260–5266
5263
Table 1
Formation of pseudo-rotaxanes
1H NMRa
Kapp (Mꢁ1
)
b
Axes
Axe
Rotaxane
4.57 (t)
a 4.18 (t)
61
a
N
H2
PF6
a 3.12 (t)
b 2.98 (m)
4.26 (m)
2.34 (m)
83
a
b
N
H2
PF6
4.20 (t)
4.18 (t)
4.61 (t)
4.49 (t)
190
270
N
H2
PF6
a 5.20 (t)
b 4.44 (t)
5.45 (t)
5.26 (t)
a
b
N
H2
PF6
a 2.95 (m)
3.19 (m)
42
64
a
NH2
PF6
a 4.18 (t)
b 3.30 (m)
c 1.70
4.43 (br)
3.14 (br), 3.29 (br)
1.47 (br)
PF6
H2
a
b
d
N
d 1.40
1.10 (br)
N
c
H2
PF6
NMR data and apparent association constants.
a
Measured at 25 ꢁC in CDCl3/CD3CN (60:40).
b
Kapp (Mꢁ1) = [pseudorotaxanes][2a]ꢁ1[axe]ꢁ1
.
with the ammonium hexafluorophosphates having various
substituents at the nitrogen. H NMR study revealed the
looser host–guest binding than the ideal complexation of
crown ethers.
[11]. Ethylene glycol (2-(2-allyloxyethoxy)phenyl) ether
was synthesized similarly from 2-(2-hydroxyethoxy)phenol
and ethylene glycol allyl ether p-tosylate. 1H NMR,
13C{1H} NMR, and 29Si{1H} NMR spectra were taken
on a Varian Mercury-300 or JEOL GX-400 spectrometer.
Chemical shifts were referenced with the solvent peaks.
1
3. Experimental
3.1. General, measurement, materials
3.2. Ethylene glycol allyl ether p-tosylate
All operations were carried out under dry nitrogen or
argon atmosphere unless stated otherwise. Column chro-
matography was performed using silica gel 60 N (spherical,
neutral, mesh 100–210) from Kanto Chemicals. Diethylene
glycol bis(2-hydroxyphenyl) ether was synthesized from 2-
benzyloxyphenol and diethylene glycol bis(p-tosylate)
according to the similar procedure reported previously
Ethylene glycol allyl ether p-tosylate was synthesized by
the modification of the reported procedure [12].
A solution of ethylene glycol monoallyl ether (18.3 g,
180 mmol) in THF (98 ml) was added to a 4.6 M aqueous
NaOH solution at 0 ꢁC. A THF solution (80 ml) of p-tolu-
enesulfonyl chloride (35.6 g, 188 mmol) was added drop-
wise over a period of 4 h at 0–5 ꢁC and stirred for 3 h at

5264
T. Umemiya et al. / Journal of Organometallic Chemistry 691 (2006) 5260–5266
the temperature. The reaction mixture was poured onto an
ice-water (30 ml) and extracted with CH2Cl2 (160 ml). The
organic phase was washed with water (120 ml · 2), and
dried over Na2SO4. The solvent was removed in vacuo to
afford the product as a clear oil by shaking vigorously with
hexane to remove unreacted p-toluenesulfonyl chloride
3.5. Diethylene glycol bis(2-(2-allyloxyethoxy)phenyl) ether(1a)
To a dry MeCN (50 ml) suspension of K2CO3 (2.88 g,
20.7 mmol) was added diethylene glycol bis(2-hydroxyphe-
nyl)ether (1.99 g, 6.87 mmol) and stirred vigorously at 85–
90 ꢁC for 30 min. After addition of a dry MeCN (32 ml)
solution of ethylene glycol allyl ether p-tosylate (3.54 g,
13.8 mmol) over a period of 30 min, the mixture was refluxed
for 18 h. The MeCN soluble part was separated and the res-
idue was extracted with ethyl acetate (30 ml) and then with
CH2Cl2 (30 ml). After the solvents were evaporated, the res-
idue wasdissolved in CH2Cl2 (50 ml), washedwith 1 M aque-
ous NaOH solution (50 ml) and then with water (50 ml) and
dried over MgSO4. The solvent was evaporated to give a yel-
low oil, which was purified by SiO2 column chromatography
hexane: acetone = 1:1 as eluent to give 1a (2.80 g, 89%). 1H
NMR (400 MHz; CDCl3): d 7.02–6.88 (8H, m, 2 · C6H4),
5.95 (2H, m, CH@CH2), 5.32 (2H, dd, CH@CH2), 5.20
(2H, dd, CH@CH2), 4.21 (8H, m, Hb and Hc), 4.12 (4H, d,
CH2@CH–CH2), 3.98 (4H, t, Hd), 3.83 (4H, t, Ha).
1
(38.2 g, 83%). H NMR (400 MHz; CDCl3): d 7.78 (2H,
d, J 8.4, C6H4), 7.32 (2H, d, J 8.4, C6H4), 5.86–5.73 (1H,
m, CH2@CH–), 5.23–5.11 (2H, m, CH2@CH–), 4.15 (2H,
t, J = 4.7, OCH2CH2OTs), 3.92 (2H, d, J 5.5, CH2@CH–
CH2), 3.60 (2H, t, J = 4.9 and 4.4, OCH2CH2OTs), 2.42
(3H, s, CH3). 13C{1H} NMR (100 MHz; CDCl3): dC
144.76 (C6H4), 134.04 (allyl), 132.98 (C6H4), 129.76
(C6H4), 127.93 (C6H4), 117.36 (allyl), 72.10 (OCH2),
69.19 (OCH2), 67.38 (OCH2), 21.57 (CH3).
Ethylene glycol (2-(2-allyloxyethoxy)phenyl) ether p-tos-
ylate was synthesized similarly by the tosylation of ethylene
glycol (2-(2-allyloxyethoxy)phenyl) ether.
3.3. 1,2-Bis(3-methoxymethoxyphenyl) 1,1,2,2-
tetramethyldisilane
Compounds 1b was prepared analogously. Compounds
1c was prepared from ethylene glycol (2-(2-allyloxyeth-
oxy)phenyl) ether p-tosylate and 1,2-bis(3-hydroxyphenyl)
1,1,2,2-tetramethyldisilane by the similar procedure. 1b:
1H NMR (300 MHz; CDCl3): d 6.97–6.85 (8H, m,
4 · C6H4), 5.93 (2H, m, CH@CH2), 5.31 (2H, dd, CH@
CH2), 5.18 (2H, dd, CH@CH2), 4.17 (8H, t, 4 · OCH2),
4.09 (4H, d, CH2@CH–CH2), 3.87 (4H, t, 2 · OCH2), 3.80
To a dry THF solution of 3-methoxymethoxyphenyl
magnesium bromide, formed in situ by adding a dry
THF solution (6 mL) of 3-methoxymethoxyphenyl bro-
mide (2.00 g, 9.2 mmol) to magnesium (0.243 g, 10 mmol)
in dry THF (2 mL), was added dropwise a THF solution
(6 mL) of 1,2-dichloro-1,1,2,2-tetramthyldisilane (0.842 g,
4.5 mmol) over a period of 1 h at room temperature, and
the reaction mixture was stirred at room temperature for
18 h and at 50 ꢁC for 7 h. NH4Cl aq. (20 mL) was added
to the reaction mixture and the organic fraction was
extracted with ether (40 ml · 3), which was washed with
brine (40 ml · 3) and dried over Na2SO4. The volatiles were
removed in vacuo and the residue was purified by SiO2 col-
umn chromatography hexane:acetone = 5:1 as eluent to
give 1,2-bis(3-methoxymethoxyphenyl) 1,1,2,2-tetramethyl-
1
(4H, t, 2 · OCH2), 3.75 (4H, s, 2 · OCH2). 1c: H NMR
(300 MHz; CDCl3): d 7.06–6.80 (16H, m, 4 · C6H4), 5.89
(2H, m, CH@CH2), 5.27 (2H, dd, CH@CH2), 5.14 (2H,
dd, CH@CH2), 4.35 (8H, t, Hb and Hc), 4.17 (4H, t, Hd),
4.06 (4H, d, CH2@CH–CH2), 3.80 (4H, t, Ha), 0.34 (12H,
s, Me). 29Si{1H} NMR (79 MHz; CDCl3): d ꢁ21.3.
d
c
O
O
O
1
disilane as yellow oil (0.78 g, 2.0 mmol, 44%). H NMR
O
O
b
(300 MHz; CDCl3): d 7.29–6.98 (8H, m, C6H4), 5.13 (4H,
s, OCH2O), 3.46 (6H, s, OCH3), 0.34 (12H, s, SiCH3).
29Si{1H} NMR (79 MHz; CDCl3): d ꢁ21.3.
a
O
O
3.4. 1,2-Bis(3-hydroxyphenyl) 1,1,2,2-tetramethyldisilane
Me Me
Si Si
MeOH (33 mL) and HCl aq. (1 N, 5.25 mL) were added
to 1,2-bis(3-methoxymethoxyphenyl) 1,1,2,2-tetramethyldi-
silane (1.56 g, 3.99 mmol) and the mixture was stirred at
45 ꢁC for 2.5 h. Brine (20 mL) was added to the reaction
mixture and the organic fraction was extracted with ether
(20 mL · 3), which was dried over Na2SO4. The volatiles
were removed in vacuo and the residue was purified by
SiO2 column chromatography hexane:acetone = 5:1 as elu-
ent to give 1,2-bis(3-hydroxyphenyl) 1,1,2,2-tetramethyldi-
silane (1.02 g, 3.37 mmol, 85%). 1H NMR (300 MHz;
CDCl3): d 7.26–6.80 (8H, m, C6H4), 6.00 (2H, br, OH),
0.29 (12H, s, SiCH3).
Me
Me
d
O
O
c
O
O
O
O
a
b
O
O

T. Umemiya et al. / Journal of Organometallic Chemistry 691 (2006) 5260–5266
5265
3.6. Cyclic compound 2a–2c
method, and an empirical absorption correction (W scan)
was applied. Calculations were carried out by using a pro-
gram package TEXSAN on a DEC Micro VAX-II com-
puter. Atomic scattering factors were obtained from the
literature. A full-matrix least-squares refinement was used
for non-hydrogen atoms with anisotoropic thermal param-
eters. Hydrogen atoms were located by assuming the ideal
geometry and these locations were included in the structure
calculation without further refinement of the parameters.
C46H50O7NPF6, 0.5 · 0.38 · 0.35 mm, Mr = 873.87, mono-
Cl2(PCy3)2Ru@CHPh (9.0 mg, 0.011 mmol) was added
to a solution of diethylene glycol bis[2-(2-allyloxyeth-
oxy)phenyl]ether (199 mg, 0.434 mmol) in dry dichloro-
methane (20 ml) and the solution stirred at 40 ꢁC for 3 h.
The solvent was removed in vacuo and the residue was sub-
jected to column chromatography (CH2Cl2:EtOAc = 1:1
(v/v) as eluent) to yield 2a as a white, crystalline solid
1
(150 mg, 81%). H NMR (300 MHz; CDCl3): d 6.93–6.88
(8H, m, 2 · C6H4), 5.89 (1.6H, m, CH@CH (trans)), 5.77
(0.4H, m, CH@CH (cis)), 4.27 (0.8H, d, J 4.8, CH@
CHCH2 (cis)), 4.17 (11.2H, m, CH@CHCH2 (trans), Hb,
and Hc), 4.00 (4H, t, Hd), 3.84 (4H, t, Ha). 13C{1H}
NMR (100 MHz; CDCl3): d 149.40, 148.93, 141.06,
129.34, 121.93, 121.42, 115.90, 114.00, 71.17, 70.36,
69.89, 69.05, 68.33.
clinic, P21/c (No. 14), a = 11.180(2), b = 26.429(6), c =
3
˚
˚
14.842(5) A, b = 106.64(5)ꢁ, V = 4297 A , Z = 4, Dc =
1.351 g cmꢁ1
, , F(000) = 1832, graphite
l = 1.42 mmꢁ1
˚
monochromated Mo Ka radiation (k = 0.71069 A). The
structure was solved by direct methods and refined by
full-matrix least-squares technique to R = 0.087, Rw =
0.080 using 3080 reflections with Fo > 3r(Fo).
Compounds 2b and 2c were prepared analogously. 2c:
1H NMR (400 MHz; CDCl3): d 7.01–6.80 (16H, m,
4 · C6H4), 5.77 (1.6H, m, CH@CH (trans)), 5.70 (0.4H,
m, CH@CH (cis)), 4.32 (4H, t, Hd), 4.20 (4H, t, Hc), 4.14
(4.8H, m, CH@CHCH2 (cis) and Hb), 4.05 (3.2H, d,
CH@CHCH2 (trans)), 3.77 (4H, t, Ha), 0.33 (12H, s,
Me), 29Si{1H} NMR (79 MHz; CDCl3): d ꢁ21.4.
4. Supplementary material
CCDC 612398 contains the supplementary crystallo-
graphic data for 3. These data can be obtained free of
charge via www.ccdc.ac.uk/conts/retrieving.html, or from
the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-
033; or e-mail: deposit@ccdc.cam.ac.uk.
d
c
O
Acknowledgements
O
O
O
This work was supported by Grants-in-Aid for Scientific
Research from the Ministry of Education, Science, Sports,
and Culture, Japan and by 21st Century COE Program
‘‘Creation of Molecular Diversity and Development of
Functionalities’’.
O
O
b
O
a
References
Me Me
Si Si
Me
Me
[1] (a) C.A. Schalley, T. Weilandt, J. Bruggemann, F. Vo¨gtle, Top. Cur.
¨
Chem. 248 (2004) 141;
d
b
O
O
(b) T.J. Hubin, D.H. Busch, Coord. Chem. Rev. 200–202 (2000) 5;
(c) F.M. Raymo, J.F. Stoddart, Chem. Rev. 99 (1999) 1643.
[2] (a) J.C. Collin, V. Heitz, J.-P. Sauvage, Top. Cur. Chem. 262 (2005)
29;
(b) V. Balzani, A. Credi, F.M. Raymo, J.F. Stoddart, Angew. Chem.,
Int. Ed. 39 (2000) 3348.
[3] J.-C. Chambron, J.-P. Sauvage, Chem. Eur. J. 4 (1998) 1362.
c
O
O
O
O
O
O
´
´
[4] P.R. Ashton, R. Ballardini, V. Balzani, M. Gomez-Lopez, S.E.
a
´
´
Lawrence, M.V. Martınez-Dıaz, M. Montalti, A. Piersanti, L. Prodi,
J.F. Stoddart, D.J. Williams, J. Am. Chem. Soc. 119 (1997) 10641.
[5] (a) D. Astruc, New. J. Chem. 29 (2005) 42;
(b) T.M. Trnka, R.H. Grubbs, Acc. Chem. Res. 34 (2001) 18;
(c) S.K. Armstrong, J. Chem. Soc. Perkin Trans. 1 (1998) 371;
(d) R.H. Grubbs, S. Chang, Tetrahedron 54 (1998) 4413.
[6] (a) D.G. Hamilton, N. Feeder, S.J. Teat, J.K.M. Sanders, New J.
Chem. (1998) 1019;
3.7. X-ray crystallography
Crystals of 3 suitable for X-ray diffraction study were
obtained by recrystallization from CH2Cl2-hexane and
mounted in glass capillary tubes under argon. Intensities
were collected for Lorentz and polarization effects on a
Rigaku AFC-5R automated four-cycle diffractometer by
(b) J.A. Wisner, P.D. Beer, M.G.B. Drew, M.R. Sambrook, J. Am.
Chem. Soc. 124 (2002) 12469;
´
(c) J.D. Badjic, S.J. Cantrill, R.H. Grubbs, E.N. Guidry, R. Orenes,
J.F. Stoddart, Angew. Chem., Int. Ed. 43 (2004) 3273;
(d) E.N. Guidry, S.J. Cantrill, J.F. Stoddart, R.H. Grubbs, Org.
Lett. 7 (2005) 2129.
˚
using Mo Ka radiation (k = 0.71069 A) and x-2h scan

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[7] (a) B. Mohr, M. Weck, J.-P. Sauvage, R.H. Grubbs, Angew. Chem.,
Int. Ed. Engl. 36 (1997) 1308;
(b) M. Weck, B. Mohr, J.-P. Sauvage, R.H. Grubbs, J. Org. Chem.
64 (1999) 5463.
[8] A.F.M. Kilbinger, S.J. Cantrill, A.W. Waltman, M.W. Day, R.H.
Grubbs, Angew. Chem., Int. Ed. 42 (2003) 3281.
A. Piersanti, N. Spencer, J.F. Stoddart, M. Venturi, A.J.P. White,
D.J. WilliamsJ. Am. Chem. Soc. 120 (1998) 11932.
[11] (a) R.W. Kierstead, A. Faraone, F. Mennona, J. Mullin, R.W. Guthrie,
H. Crowley, B. Simko, L.C. Blaber, J. Med. Chem. 26 (1983) 1561;
(b) E. Weber, H.-P. Josel, H. Puff, S. Franken, J. Org. Chem. 50 (1985)
3125;
[9] (a) Early reports on the ring-closing-metathesis-based synthesis of
crown ethers. B. Ko¨nig, C. Horn, Synlett (1996) 1013;
(b) M.J. Marsella, H.D. Maynard, R.H. Grubbs, Angew. Chem., Int.
Ed. Engl. 36 (1997) 1101.
(c) B.J. Ball, M.J. Cooper, B.G. Main, Eur. J. Med. Chem. Chim. Ther.
20 (1985) 137.
[12] P. Roveri, V. Cavrini, R. Gatti, M.R. Cesaroni, R. Gaggi, Eur. J.
Med. Chem. Chim. Ther. 18 (1983) 555.
[10] P.R. Ashton, R. Ballardini, V. Balzani, I. Baxter, A. Credi, M.C.T.
[13] P.R. Ashton, M.C.T. Fyfe, S.K. Hickingbottom, J.F. Stoddart, A.J.P.
White, D.J. Williams, J. Chem. Soc. Perkin Trans. 2 (1998) 2117.
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Fyfe, M.T. Gandolfi, M. Gomez-Lopez, M.-V. Martinez-Dıaz