Calix[4]arene-Based Bis[2]catenanes: synthesis and chiral resolution

Article abstract of DOI:10.1002/chem.200601814

The exclusive formation of hydrogen-bonded dimers between tetraaryl and tetratosylurea calix[4]arenes has been used to prepare a series of ten "bisloop" tetraurea calix[4]arenes 3, in which adjacent phenylurea groups are covalently linked through α,ω-diox

Full text of DOI:10.1002/chem.200601814

FULL PAPER
DOI: 10.1002/chem.200601814
Calix[4]arene-Based Bis[2]catenanes: Synthesis and Chiral Resolution
Olena Molokanova,[a] Anca Bogdan,[a] Myroslav O. Vysotsky,[a] Michael Bolte,[b]
Tomoyuki Ikai,[c] Yoshio Okamoto,[c] and Volker Bçhmer*[a]
Abstract: The exclusive formation of
hydrogen-bonded dimers between tet-
raaryl and tetratosylurea calix[4]arenes
has been used to prepare a series of
ten “bisloop” tetraurea calix[4]arenes
3, in which adjacent phenylurea groups
are covalently linked through a,w-dioxy-
alkane chains. This dimerization with
tetratosylurea 2 as template preorga-
nizes the alkenyl residues of tetra(m-al-
kenyloxyphenyl) ureas 1 and enables
their selective connection in high yield
(up to 95%) by olefin metathesis fol-
lowed by hydrogenation. The “bisloop”
calixarenes 3 also exclusively form het-
erodimers with 1. Thus, in a separated
metathesis/hydrogenation sequence, a
series of 14 cyclic bis[2]catenanes 4, in
which two calix[4]arenes are connected
through their wide rims by two pairs of
interlocked rings (total size 29 to 41
atoms), were prepared in yields of up
to 97%. Optical resolution of these
chiral bis[2]catenanes was studied by
HPLC on chiral stationary phases. The
single-crystal X-ray structure of one ex-
ample (4(P,10)) confirmed the inter-
A
locking rings and revealed that the hy-
drogen-bonded dimeric capsule of the
calix[4]arene can be “completely”
opened.
Keywords: calixarenes · catenanes ·
chiral resolution
template synthesis
· metathesis ·
Introduction
sized on a statistical basis.[3] Preorganization on a molecular
level was first achieved through the use of covalent bonds in
a carefully designed multistep reaction.[4] Although the prin-
ciple of “covalent preorganization” has recently again been
used for the “large-scale” synthesis of [2]catenanes made up
of very large rings,[5] the breakthrough in catenane synthesis
came when the (reversible) coordination of suitable building
blocks to a metal cation was used for their appropriate pre-
organization in space.[6] The rapidly developing field of
“supramolecular chemistry” gave rise to numerous further
examples of the preorganization of reactive precursors
through reversible, noncovalent links. In addition to metal
coordination,[7] the use of coordination to anions,[8] apolar
forces,[9] (charge transfer complexes) or hydrogen bonds[10]
should also be mentioned, and often there is a combination
of several factors.
Catenanes are compounds in which (covalently linked) mac-
rocyclic molecules are (mechanically) connected as the rings
of a chain (latin: catena).[1,2] And similarly to the (tradi-
tional) preparation of a macroscopic chain, the synthesis of
catenanes requires macrocyclic rings to be closed while pen-
etrating other rings. Evidently an efficient synthesis needs
appropriate preorganization in both cases, although the first
catenanes, unlike their macroscopic analogues, were synthe-
[a]O. Molokanova, Dr. A. Bogdan, Dr. M. O. Vysotsky, Dr. V. Bçhmer
Fachbereich Chemie, Pharmazie und Geowissenschaften
Abteilung Lehramt Chemie, Johannes Gutenberg-Universität Mainz
Duesbergweg 10–14, 55099 Mainz (Germany)
Fax : (+49)6131-392-5419
Calix[4]arenes substituted on their wide rims by four urea
functions form hydrogen-bonded dimeric capsules in aprotic,
apolar solvents. This well known dimerization also brings
residues attached to the urea groups into unique positions
relative to each other. According to calculations (and consis-
tently with several X-ray structures[11]) the eight (two ”
four) p-methyl groups in a dimer of tetratolyl urea occupy
the corners of two regular squares with a common side
length of 13.4 Š (Figure 1. Both planes are close to the ref-
erence plane (of the methylene bridges) of the other calixar-
ene (distance 0.2 Š), while they are 9.9 Š apart from each
E-mail: vboehmer@mail.uni-mainz.de
[b]Dr. M. Bolte
Institut für Anorganische Chemie
Johann Wolfgang Goethe-Universität, Marie-Curie-Strasse 11
60439 Frankfurt/Main (Germany)
[c]Dr. T. Ikai, Prof. Y. Okamoto
Science Institute, Nagoya University, Furo-cho
Chikusa-ku, Nagoya 464-8603 (Japan)
Supporting information for this article is available on the WWW
under http://www.chemeurj.org/ or from the author: H NMR spectra
of the bisloop and bis[2]catenanes and X-ray crystallographic file
(CIF).
1
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Figure 2. Schematic representation of the synthesis of bisloop compounds
(Y,n) by metathesis of 1(Y,m) through the use of tetratosylurea 2 as
3
A
ACHTREUNG
template. Compounds are characterized by the number 1 or 3, followed
(in brackets) by the ether residue Y (M=methyl, P=pentyl, D=decyl),
and the number of carbon atoms in the alkenyl residue (m) or in the con-
necting chain (n = 2m-2).
Figure 1. Hydrogen-bonded dimer of tetraurea calix[4]arene seen from
different directions (relevant distances are indicated) and short represen-
tation of a dimer, illustrating potential covalent connection points.
other. Thus, the distance between adjacent p-methyl groups
belonging to different calixarenes is only slightly shorter
(1.1 Š) than the distance to the adjacent group in the same
calixarene. This unique arrangement in space[12] inspired the
idea that covalent connection between functional groups at-
tached to the urea groups of a calix[4]arene should give rise
to novel and interesting catenanes.
calix[4]arene with an activated bisurethane or a diisocyanate
under high-dilution conditions. A better strategy, however,
is again based on the metathesis of tetraalkenylureas 1 in
heterodimers 1·2 with tetratosylurea
2
as template
(Figure 2).[17]
This heterodimerization prevents undesired transcavity
connections and, in the case of the tetramethyl ethers
1(M,m), forces the molecules to assume the required cone
A
conformation.[18] Metathesis occurs smoothly in benzene or
toluene in the presence of the first generation of Grubbsꢁ
catalyst. To suppress reactions between heterodimers the
concentration was kept around 0.5 mm. After the reaction,
the heterodimer is easily split by use of hydrogen bond-
breaking solvents, usually THF. After hydrogenation of the
double bonds, to avoid stereochemical complications due to
cis/trans isomerism, the bisloop compounds 3 were isolated
in yields of up to 95% (see Table 1).
Syntheses
For the covalent linkage of urea residues we chose metathe-
sis reactions between alkenyl ether groups, with subsequent
hydrogenation of the olefinic double bonds to avoid stereo-
chemical complications. This reaction has often been used to
establish similar connections within larger molecules (e.g.,
dendrimers[13]) or molecular assemblies[14]. The required tet-
raurea calixarenes 1 are easily prepared by acylation of the
corresponding tetraaminocalix[4]arene with the activated
urethanes, which in turn are obtained from m-hydroxyaceta-
nilide by O-alkylation, hydrolysis of the amide group, and
acylation with p-nitrochloroformate.[15]
Bisloop compounds 3 do not form homodimers; obviously
this would result in unfavorable overlap of the chains con-
necting adjacent urea residues. The tendency to dimerize in
apolar solvents thus results in the exclusive formation of
heterodimers in a stoichiometric mixture of 3 with 1, since
this is the only way to get all urea groups incorporated in
the favorable hydrogen-bonded belt. This dimerization can
An early attempt, direct metathesis with the dimer
1
G
ACHTREUNG
1
A
be easily monitored by H NMR. Again, in such a dimer 1·3
two a-connections were present, a tetrabridged capsule (two
b-connections), and a doubly bridged [2]catenane (a- and b-
connections).
The difficult separation of these isomeric compounds
could be avoided by starting with tetraurea calix[4]arene 3,
in which adjacent urea residues are already covalently
linked. Such prefabricated bisloop compounds 3 can be pre-
pared by conventional acylation of a tetramino-substituted
only adjacent alkenyl residues can be connected (see
Figure 3). Thus, under the conditions of the metathesis reac-
tion described above, the formation of a bis[2]catenane is
more or less quantitative. Consequently, after hydrogena-
tion, the bis[2]catenanes 4 were isolated in yields of up to
97% (see Table 2).
It should be mentioned that the sizes of the interlocking
residues can be easily made different, if the alkenyl groups
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Calix[4]arene-Based Bis[2]catenanes
FULL PAPER
Table 1. Survey on bisloop compounds 3, prepared by template synthesis
as shown in Figure 2.
Compound
Yield [%]
3
3
3
3
3
3
3
3
3
3
C
72
34
48
64
72
82
80
84
95
53
Figure 3. Schematic representation of the synthesis of bis[2]catenanes
4
A
U
raalkenyl derivatives 1 and bisloop compounds 3. The characterization of
the compounds follows the rules described above. Ether residues (YI/YII)
and loop sizes (nI/nII) can be different for both calixarenes. A single
letter/number indicates that they are identical.
b-connection between the two calix[4]arenes, but after a
first a-connection, the second connection must again be a.
As shown in Figure 4, the bis[2]catenane 7
ACHTREUNG
prepared in 41% yield, while in the case of 7
AHCTREUNG
pure product could be separated from a mixture of similar
or isomeric compounds.[24] The pathway via homodimers of
monoloop compounds 6 thus offers an interesting and com-
plementary possibility, but the reaction of heterodimers be-
tween tetraalkenyl compounds 1 and bisloop compounds 3
is the method of choice for the preparation of bis[2]cate-
nanes of type 4.
of the tetraureas 1 used for the synthesis of the bisloop com-
pound 3 in the first step and for the catenane 4 in the
second step are different, as demonstrated by the examples
5
R
C
ferent ether groups Y, or different connecting chains[20] can
also be achieved.
Characterization
While the pairs of interlocking rings are different in size
(n/n’), the pairs belonging to one calixarene are identical
(either nI or nII) in the examples described above. There is
another isomeric possibility in
NMR Spectroscopy: In apolar solvents, bisloop compounds
3 show broad spectra due to “irregular” association, but in
which the two calixarenes are
Table 2. Survey of bis[2]catenanes 4 and 5, prepared by template synthesis as shown in Figure 3, and bis[2]ca-
tenanes 7, prepared as shown in Figure 4.
identical but carry rings of dif-
ferent size n/n’. Bis[2]catenanes
of this type are available,
through the use of analogous
principles for the self-assembly.
Monoloop bisalkenyl ureas 6
are easily prepared in three
steps from a bis-Boc-protected
tetraamino-substituted calix[4]-
arene[21] by cyclization with an
activated bisurethane, deprotec-
tion and acylation with the acti-
vated urethane. In apolar sol-
vents they readily dimerize. Of
the two potentially possible re-
gioisomers exclusively one is
formed,[22] in which the two
loops do not overlap. For a
metathesis reaction restricted to
dimers 6·6 the number of wrong
connections is reduced in com-
parison to dimers 1·1. At first
Compound
Yield [%]
4
4
4
4
4
4
4
4
5
5
4
4
7
7
C
66
50
70
64
67
70[15]
78[16]
88
81
64
50
97
41
mixture
[a]One number means that all loops have the same size (e.g., eight CH 2 groups). [b]Two numbers separated
by “/” means different loops but identical within each calixarene (e.g., eight in one calixarene and 14 in the
second). [c]Two numbers separated by “ +” means identical calixarenes with different loops (e.g., eight and 14
glance there should be only one CH2 groups).
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V. Bçhmer et al.
Table 3. NMR data for bisloop compounds. Each signal is one doublet.
Solvent
Signals of the methylene bridges (ppm)
axial
equatorial
3
3
U
DMSO
Pyr
THF
DMSO
THF
THF
DMSO
DMSO
THF
THF
THF
4.26; 4.24
4.42; 4.36
4.33
4.26; 4.24
4.33; 4.32
4.34
4.23 (br)
4.34; 4.33
4.44
4.45; 4.44
4.43
3.19; 3.16
3.27; 3.04
3.14; 3.11
3.19; 3.17
3.12; 3.06
3.12; 3.11
3.18 (br)
3.12; 3.11
3.08; 3.06
3.08; 3.07
3.08
3
3
3
3
3
3
DMSO
THF
DMSO
4.33
4.44
4.32
3.11
3.08; 3.06
3.10
3
3
U
of two identical C2v-symmetrical calixarenes) have D2 sym-
metry, which is reduced to C2 symmetry by the directionality
of the hydrogen-bonded belt, which is kinetically stable.
This is expressed by four NH signals at low field (9.7–
10 ppm) for the strong hydrogen bonds of the a-NH groups
and four signals (7.3–6.9 ppm) for the b-NH groups,[22] which
are often overlapped by the signal of the solvent (CHCl3,
C6H6). The 16 aromatic protons of the calixarene skeletons
appear as eight m-coupled doublets, which are usually well
resolved (n=8, 10). Four singlets for methoxy groups are
Figure 4. Schematic representation of the synthesis of bis[2]catenanes
7
6
ACHTREUNG
ACHTREUNG
scribed above. Loop sizes (n/n’) are different within both (identical) cal-
ixarenes but identical for the interlocking pairs.[23]
polar, hydrogen bond-breaking solvents ([D8]THF,
[D6]DMSO, [D5]Pyr) the 1H NMR spectra reflect the ex-
pected C2v symmetry with two symmetry planes intersecting
opposite methylene bridges. Typically one pair of m-coupled
doublets for the aromatic protons of the calixarene part (in
the 7.2–6.5 ppm region) and two pairs of doublets (geminal
coupling) for the methylene bridges (4.6–4.2 ppm for the
axial and 3.2–3.0 ppm for the equatorial protons) are found.
Sometimes just one doublet appears for the axial protons
but two doublets for the equatorial ones, and the pentyl or
decyl ethers with larger loops (n=14, 20) show only one
pair of doublets (sometimes broad) for axial and equatorial
protons in the expected area (Table 3). As in the starting 1,
the aryl protons of the urea residues appear as two “dou-
blets of doublets” and two “triplets” reflecting the ortho
coupling and the meta coupling (not always well resolved).
The tetramethyl ethers of 3 are held in the cone confor-
mation, as attested to by the signals of the methylene
bridges. A remarkable exception, though, is the derivative
found around 3.5 ppm for compounds 4(M,n). Four pairs of
A
doublets with geminal coupling for the eight methylene
bridges also appear in the same region (4.5–3.0 ppm).
Bis[2]catenanes 5(Y,nI/nII), composed of two different
R
(C2v-symmetrical) calix[4]arenes with identical loops, have
C2 symmetry. The C2 axis is identical with the molecular axis
of the calixarenes, and the symmetry is retained for kineti-
cally stable hydrogen bonds. However, the directionality of
the H-bonded belt adds an independent element of chirality
in heterodimers (the two calixarenes are different!) and so
we observe two diastereomeric pairs of enantiomers (see
Figure 6).[25] This becomes evident through, for instance,
(4+4) NH signals at low field and partly overlapping in
Figure 7 (six signals, of which two have double intensity).
The situation is different again in 7(P,8+14), made up of
R
two identical, Cs-symmetrical calixarenes bearing different
loops. Bis[2]catenanes of this type have C2 symmetry, but
the twofold axis is perpendicular (!) to the molecular axis of
the two calixarenes. In other words, the two calixarenes are
symmetry-related by this C2 axis. The directionality of H-
bonds therefore reduces the symmetry to C1, but it is not an
independent element of chirality (we are dealing with a
homodimer!). As illustrated in Figure 7, one pair of enantio-
mers exists, though there is no symmetry element, which is
expressed by, for instance, eight low-field NH signals.
3(M,20), the spectrum of which in [D8]THF at 258C shows
T
the “normal” pattern with one doublet for the axial protons
and two doublets for the equatorial ones (Table 3, line 6),
while in [D6]DMSO at 258C just two very broad signals
appear at d 4.23 and 3.18 ppm. With increasing temperature
the two signals became broader and broader and around
1008C their coalescence temperature is reached, which indi-
cates a cone-to-cone inversion. The spectrum in pyridine is
even more complicated (see Figure 5). The number of the
signals marked suggests that the molecule adopts more then
one conformation.
A polar solvent such as [D6]DMSO disrupts the hydrogen
bonding between the urea groups and destroys the capsule
1
1
Before we discuss the H NMR spectra of bis[2]catenanes,
(see Figure 8). Even with the smallest loop size the H NMR
it is reasonable to deal with their symmetry properties.
spectrum resembles the spectrum of a C2v-symmetrical tet-
Bis[2]catenanes 4
A
raurea.
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Calix[4]arene-Based Bis[2]catenanes
FULL PAPER
Figure 6. Schematic representation of the symmetry properties of the cat-
enanes 4
A
G
N
rectionality of the hydrogen-bonded belt, and the mirror plane are indi-
cated.
A2 penetrates the “black” loop between B7 and B8, while
the loop connecting A3 and A4 passes through the one con-
necting B5 and B6.
Evidently the two calixarenes do not form a hydrogen-
bonded capsule any longer, the whole structure being
opened but held together by the catenated loops. The refer-
ence planes of the two calixarenes, defined by the carbon
atoms of the methylene bridges, which are (more or less)
parallel in a dimer, include an angle of 70.508. The distance
between the centers of the reference planes is 12.67 Š,
while in a hydrogen-bonded dimer it should beꢀ9.4–9.5 Š.
The two calixarenes each assume a pinched-cone confor-
mation in which two opposite aromatic units are almost par-
allel (units A2/A4, B6/B8). In fact, the angles between the
reference planes and the aromatic units are slightly less than
908 (d=87–898), with the exception of unit A2, which is ori-
ented more inside (d=798; see Table 4). Consequently the
four other phenolic units are bent outwards, forming angles
of d=141–1438 with the reference plane; again there is one
exception (unit B5, with d=1338).
Figure 5. Sections of the 1H NMR spectra ([D5]Pyr at different tempera-
tures) of a) 3
N
N
of the methoxy groups are indicated.
X-ray analysis: A good-quality crystal of the compound
4(P,10) was obtained from a chloroform/methanol mixture
E
(1:1). Its structure could be completely solved; Figure 8
shows the molecular structure of the catenane from two per-
spectives.
The pinched-cone conformation may also be character-
ized by the distances of the carbon atoms in the p-positions,
of A2/A4=4.778 Š and A1/A3=9.843 Š in the calixare-
ne A and B6/B8=5.55 Š and B5/B7=9.56 Š in the calixare-
Unlike in an earlier attempt,[16] all atoms of the four loops
were found and so their catenation/intertwining could be es-
tablished unambiguously. The “gray” loop between A1 and
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V. Bçhmer et al.
such as [2]catenanes,[27] [2]ro-
taxanes,[27b]
pretzelanes,[27b]
knots,[28] and knotaxanes,[29] and
also for one example (4(P,10))
G
of a bis[2]catenane.[30] Figure 9
shows a typical example of a
successful separation.
Since the first examples of
compounds 4 suggested some
general trends for the separa-
tion factors with respect to the
ether residues Y and the loop
size n, we decided to study all
the catenanes under the same
standard conditions (Table 5).
These trends were not con-
firmed for the whole series,
however, and unfortunately a
satisfactory separation was not
even possible in all cases. In the
series of compounds with the
(CH2)10 bridges/loops, for exam-
ple,
a is approximately the
same for the catenanes with
methyl (1.48, entry 2) or pentyl
(1.52, entry 7) ether groups,
while it drops down to “ꢀ1”
for the decyl ether (entry 15).
In the series of compounds pos-
Figure 7. Sections of the 1H NMR spectra (C6D6, 258C) of 4
marked with NH, protons of the calixarene skeletons with ArH. All the protons with ppm value higher than
9.7 are NH protons with stronger hydrogen bonds.
A
G
G
Table 4. Selected crystallographic data: I) Distances [Š]between carbon
atoms of the methylene bridges within one calixarene. II) Angles [8]be-
tween the planes of the aromatic units and the reference plane of the cal-
ixarene.
First calixarene
Second calixarene
I) reference planes
C5–C6
C1–C2
5.007
5.105
5.038
5.046
7.153
7.124
5.029
5.121
5.013
5.100
7.268
7.058
C2–C3
C3–C4
C1–C4
C1–C3
C2–C4
C6–C7
C7–C8
C5–C8
C5–C7
C6–C4
II) inclination of the aromatic units
1
2
3
4
140.79
79.39
143.2
88.94
5
6
7
8
133.13
87.13
141.61
88.27
Figure 8. Two different views of the X-ray structure of the compound 4-
(P,10). The two calixarene are colored in grey and black. Each aromatic
unit is numbered.
ACHTREUNG
ne B. This means that the calixarene A is more strongly
pinched then B.
sessing (CH2)14 loops,
a increases steadily from 1.39
(entry 3) through 1.92 (entry 9) to 2.36 (entry 16). For the
compounds with (CH2)8 and (CH2)20 loops, a is higher for
the methyl ethers (entries 1, 4) than for the pentyl ethers
(entries 5 and 10). Entries 11, 12, and 14 suggest that the
chiral resolution of catenanes containing different loops (in-
Optical resolution: The chiral resolution of the bis[2]cate-
nanes 4, 5, and 7 was studied by chromatography on the
chiral stationary phases Chiralpak AD-H (silica-bound amy-
lose with 3,5-dimethylphenylcarbamate units) and Chiralpa-
k OD (silica-bound cellulose with 3,5-dimethylphenylcarba-
mate units)[26] with mixtures of hexane and ethanol as elu-
ents. These stationary phases have been successfully used
for the resolution of various topologically chiral compounds
cluding the isomeric pair 5
N
N
difficult (at least under the “standard” conditions A), al-
though it was possible in one case through application of a
less polar eluent (entry 13).
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Calix[4]arene-Based Bis[2]catenanes
FULL PAPER
teraction involving enantioselectivity and nonstereoselective
interaction. Thus, if by changing the structure of a racemate
the nonstereoselective interaction is relatively reduced, the
resolution should be enhanced. If, however, the enantiose-
lective interaction is relatively reduced by a structural
change, the resolution should be decreased. In the case of
the catenanes, it is probable that both interactions are influ-
enced more or less similarly by changing of the ether chains
and/or the loops, so no clear effect on the chiral separation
has been observed. For a practical separation the optimum
conditions will obviously have to be elaborated individually
for each example.
Conclusions and Outlook
Through the use of a tetratosylurea (e.g., 2) as template, it
is possible to convert the tetraalkenyl calix[4]arenes 1 by
olefin metathesis into the corresponding bisloop derivatives
3, sometimes in excellent yields, which have not even been
optimized yet for the special examples. While the results re-
ported here were obtained under high-dilution conditions
(c=0.5 mm), first results at
Figure 9. Separation of the compound 4(P,14). a) Column Chiralpak AD-
H, hexane/ethanol 9:1; b) CD spectra of both fractions: hexane/ethanol
9:1, cell length: 25 mm.
A
higher concentrations show no
drop in the yields. This suggests
Table 5. Resolution of enantiomers of bis[2]catenanes 4, 5, and 7.
[b]
[b]
Entry
Conditions[a]
t0 [min]
t1 [min]
t2 [min]
k’1
k’2
a[c]
that even larger quantities
should be available in a single
experiment. The fact that bi-
sloop compounds 3 cannot form
homodimers can be used to
convert their heterodimers with
1 into bis[2]catenanes 4 under
similar reaction conditions,
again in excellent yields. This
1
2
3
4
5
6
7
8
4
4
4
4
4
4
4
4
4
4
5
5
5
7
4
U
A
A
A
A
A
B
6.47
6.77
6.47
6.77
6.77
6.83
6.77
5.77
6.47
6.77
6.77
6.77
7.08
6.97
6.97
6.88
22.57
32.17
17.55
10.08
8.38
12.03
9.13
14.13
7.76
7.59
7.73
7.27
14.93
8.28
31.49
44.35
21.79
11.79
ꢀ8.38
12.73
10.38
22.99
8.95
2.49
3.75
1.71
0.49
0.24
0.76
0.35
1.45
0.20
0.12
0.14
0.07
1.11
0.19
0.15
0.063
3.87
5.55
2.37
0.74
1.55
1.48
1.39
1.51
ꢀ1
ꢀ0.24
0.86
1.13
1.52
2.06
1.92
1.67
ꢀ1
A
C
0.53
2.98
0.38
0.20
ꢀ0.14
ꢀ0.07
1.47
ꢀ0.19
ꢀ0.15
0.14
9
A
A
A
A
D
A
A
A
10
11
12
13
14
15
16
8.11
ꢀ7.73
ꢀ7.27
17.52
ꢀ8.28
ꢀ7.99
7.91
opens
a preparatively useful
ꢀ1
pathway to a variety of such
chiral capsular compounds, in
which the rate of guest ex-
change might be controllable
through the lengths and the
structures of these intertwining
1.33
ꢀ1
7.99
7.32
ꢀ1
4
A
2.36
[a]A: Column Chiralpak AD-H, hexane/ethanol 9:1, flow rate 0.5 mLmin ꢁ1
;
B: column Chiralpak OD,
hexane/ethanol 100:1, flow rate 0.5 mLminꢁ1
; C: column Chiracel OD, hexane/ethanol 9:1, flow rate
0.5 mLminꢁ1; D: column Chiralpak AD-H, hexane/ethanol 1000:1, flow rate 0.5 mLminꢁ1. [b] k’1 =(t1ꢁt0)/t0;
k’2 =(t2ꢁt0)/t0. [c] a=k’2/k’1.
rings. Bis[2]catenanes
4
are
chiral. How this chirality can be
used for the discrimination of
chiral guests (kinetically or
It is not easy to give a rational explanation for the resolu-
tion data. Of course, without retention a compound cannot
be resolved or recognized, and so a compound (a large mol-
ecule) that is strongly retained is often better resolved than
a compound (a small molecule) that is weakly retained. Un-
fortunately this is not always true. In general, the retention
times for compounds 4 decrease in the order methyl@
pentyl>decyl ether, while no clear order is seen for the
loop size (the retention time shows a maximum for (CH2)10).
thermodynamically) is one of the open questions awaiting
answer by future studies.
Experimental Section
General procedure for the synthesis of tetraureacalix[4]arenes 1: A solu-
tion of tetraaminocalix[4]arene[31] (1 mmol), active urethane (5 mmol),
and triethylamine (5 mmol) in DMF (50 mL) was stirred for two days at
room temperature. The solution was then diluted with dichloromethane
(400 mL), a solution of K2CO3 (1m, 300 mL) was added, the biphasic
mixture was stirred for 1 hour at room temperature, and the organic
layer was washed with a solution of K2CO3 (0.3m, 3”300 mL). After
However, 4(D,14) with the lowest k’1 has the highest a value
A
of all bis[2]catenanes studies (entry 16).
The interactions between a chiral stationary phase and a
racemate may be roughly separated into two categories: in-
Chem. Eur. J. 2007, 13, 6157 – 6170
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6163

V. Bçhmer et al.
drying over MgSO4, the solvent was evaporated and the desired tetraurea
was purified by column chromatography on silica gel.
CH), 6.92 (m, 1H; -CH=CH2), 4.99 (ddd, 2J=1.7, 3J=17.0, 4J=1.7 Hz,
1H; -CH=CH2), 4.92 (ddd, 2J=1.7, 3J=10.2, 4J=1.0 Hz, 1H; -CH=CH2),
3.93 (t, 3J=6.5 Hz, 2H; OCH2), 2.15 (s, 3H; C(O)CH3), 2.03 (m, 2H;
-CH2CH=CH2), 1.75 (m, 2H; -CH2-), 1.50–1.20 (m, 12H; -CH2-); elemen-
tal analysis (%) calcd for C19H29NO2: C 75.21, H 9.63, N 4.62; found: C
75.14, H 9.50, N 4.72.
3-(Oct-7’-enyloxy)acetanilide: Yield 81%; m.p. 708C; 1H NMR (CDCl3,
400 MHz, 258C): d=7.70 (s, 1H; NH), 7.26 (overlapped with solvent
signal, brt, 1H; CH), 7.15 (t, 3J=8.2 Hz, 1H; CH), 6.95 (brdd, 3J=
7.9 Hz, 1H; CH), 6.62, 6.60 (dd, 3J=8.2, 4J=1.7 Hz, 1H; CH), 5.82–5.74
(m, 1H; -CH=CH2), 4.99 (m, 1H; -CH=CH2), 3.90 (t, 3J=6.5 Hz, 2H;
OCH2), 2.13 (s, 3H; C(O)CH3), 2.06 (m, 2H; -CH2CH=CH2), 1.75 (m,
2H; -CH2-), 1.45–1.32 ppm (m, 6H; -CH2-); 13C NMR (CDCl3, 100 MHz,
258C): d=168.56, 159.61, 139.14, 138.97, 129.48, 114.21, 111.81, 110.53,
106.23, 67.91, 33.64, 29.12, 28.78, 25.81, 24.55 ppm; FD-MS: m/z: calcd
for C16H23N1O2: 261.3; found: 261.6 [M]+.
3-(Undec-10’-enyloxy)aniline: Yield 99%; yellow oil; 1H NMR (CDCl3,
400 MHz, 258C): d=7.04 (t, 3J=8.2 Hz, 1H; CH), 6.33 (dd, 3J=8.2, 4J=
2.4 Hz, 1H; CH), 6.28 (dd, 3J=7.8, 4J=2.0 Hz, 1H; CH), 6.25 (t, 4J=
2.0 Hz, 1H; CH), 5.81 (m, 1H; -CH=CH2), 4.99 (m, 2H; -CH=CH2), 3.90
(t, 3J=6.8 Hz, 2H; OCH2-), 3.90–3.60 (brs, 2H; -NH2), 2.04 (m, 2H;
-CH2-CH=CH2), 1.74 (m, 2H; -OCH2CH2-), 1.50–1.20 (m, 12H; -CH2-);
elemental analysis (%) calcd for C12H27NO: 78.11, H 10.41, N 5.36;
found: C 78.06, H 9.97, N 5.31.
An alternative procedure, starting from the active urethane of calix[4]ar-
ene and the corresponding aniline,[32] was also used and has been de-
scribed previously.[16]
General procedure for the synthesis of bisloop derivatives 3: A mixture
of the tetratosyl urea 2 (1.15 mmol) and an open chain tetraalkenyl urea
1(Y,m) (1 mmol) in benzene (500 mL) was heated at reflux for 2–3 mi-
T
nutes. During this period a clear solution was usually formed. The reac-
tion mixture was allowed to cool to room temperature and the complete
formation of the heterodimer was checked with an evaporated sample
1
(ꢀ2 mL) by H NMR ([D6]C6H6). The reaction mixture was purged with
nitrogen for 30 minutes and a solution of the Grubbsꢁ catalyst (0.2 mmol)
in benzene (3 mL) was added in one portion. After the mixture had been
stirred at 208C for two days, triethylamine (1.5 mL) was added and the
reaction mixture was stirred for 1 hour, the solvent was then evaporated,
and the residue was dissolved in THF (50 mL), heated to reflux, and al-
lowed to cool to room temperature. After evaporation under reduced
pressure, hydrogenation of the crude product was carried out in THF
(20 mL) at normal pressure in the presence of platinum dioxide (83%,
0.9 mmol). The desired product was purified by column chromatography
(silica gel, THF/hexane 2:3). The pure product was finally crystallized
from THF/methanol.
General procedure for the synthesis of bis[2]catenanes 4: A mixture of a
3-(Oct-7’-enyloxy)aniline: Yield 95%; yellow oil; 1H NMR (CDCl3,
400 MHz, 258C): d=7.04 (t, 3J=8.2 Hz, 1H; CH), 6.31 (dd, 3J=8.2, 4J=
1.5 Hz, 1H; CH), 6.27 (dd, 3J=7.8, 4Jꢀ1.0 Hz, 1H; CH), 6.25 (brt, 1H;
CH), 5.85–5.75 (m, 1H; -CH=CH2), 5.01–4.91 (m, 2H; -CH=CH2), 3.90
(t, 3J=6.6 Hz, 2H; OCH2-), 3.62 (brs, 2H; -NH2), 2.04 (m, 2H; -CH2-
CH=CH2), 1.74 (m, 2H; -CH2-), 1.44–1.38 ppm (m, 6H; -CH2-).
tetraalkenyl urea
1 (1 mmol) and the corresponding bisloop 3
(1.05 mmol) in benzene (200 mL) was heated at reflux until a clear solu-
tion had been formed, which usually requires 10 to 60 minutes. After the
mixture had cooled to room temperature the formation of the heterodi-
mer was checked by 1H NMR (C6D6). The reaction mixture was then
purged with nitrogen for 30 minutes and a solution of the Grubbsꢁ cata-
lyst (0.2 mmol) in benzene (5 mL) was added in one portion. After the
system had been stirred at 208C for two days, triethylamine (1 mL) was
added, the reaction mixture was stirred for a further hour, and the sol-
vent was evaporated. The crude product was purified by column chroma-
tography (silica gel) and then dissolved in THF (50 mL) and hydrogenat-
ed (1 atm) in the presence of platinum dioxide (83%, 0.9 mmol). After
filtration and evaporation, the product was finally crystallized from THF/
methanol.
General procedure for the synthesis of urethanes from the corresponding
anilines (Scheme 1): A solution of the aniline (13.3 mmol) and 4-nitro-
phenyl chloroformate (14 mmol) in a mixture of chloroform (30 mL) and
tetrahydrofuran (20 mL) was heated at reflux for 12 h. The solvents were
evaporated and the residue was dissolved in chloroform and precipitated
with diethyl ether. The pure compound was recrystallized from acetoni-
trile as white to yellowish crystals.
4-Nitrophenyl-N-[3’-(undec-10’’-enyloxy)phenyl]carbamate: Yield 51%;
The bis[2]catenane 6 was synthesized from the monoloop derivatives 5
(2 mmol) by the procedure for bis[2]catenanes 4.
3
m.p. 104.38C; 1H NMR (CDCl3, 400 MHz, 258C): d=8.28 (d, J=9.0 Hz,
2H; CH), 7.38 (d, 3J=9.0 Hz, 2H; CH), 7.23 (t, 3J=8.2 Hz, 1H; CH),
7.15 (brs, 1H; CH), 6.95 (brs, 1H; NH), 6.90 (dd, 3J=7.8, 4J=1.7 Hz,
1H; CH), 6.68 (dd, 3J=8.2, 4J=2.0 Hz, 1H; CH), 5.80 (m, 1H; -CH=
Syntheses and characterization: The 1H and 13C NMR spectra were re-
corded with Bruker Avance DRX 400 (400 MHz) and Bruker 300
(300 MHz) spectrometers with use of the solvent signals as internal refer-
ence. FD mass spectra were recorded with a Finnigan MAT 90 (5 kV/
10 mAminꢁ1) machine. ESI-MS spectra were obtained on a Q-TOF
Ultima3 (Micromass) instrument. Melting points were determined with a
MEL TEMP 2 capillary melting point apparatus and are uncorrected.
Acetanilides and anilines were obtained by a described procedure.[32] For
acetanilide, aniline m=5 and acetanilide, aniline, urethane m=6 see
refs. [32]and [15].
3
CH2), 4.98–4.92 (m, 1H; -CH=CH2), 3.95 (t, J=6.5 Hz, 2H; OCH2), 2.03
(m, 2H; -CH2-CH=CH2), 1.76 (m, 2H; -CH2-), 1.43 (m, 2H; -CH2-),
1.40–1.20 ppm (m, 10H; -CH2-).
4-Nitrophenyl-N-[3’-(oct-7’’-enyloxy)phenyl]carbamate: Yield 90%. m.p.
101–1028C (decomp); 1H NMR (CDCl3, 400 MHz, 258C): d=8.26 (d,
3J=9.1 Hz, 2H; CH), 7.37 (d, 3J=9.1 Hz, 2H; CH), 7.22 (t, 3J=8.2 Hz,
3
4
1H; CH), 7.14 (brs, 1H; CH), 7.03 (brs, 1H; NH), 6.89 (dd, J=7.9, J=
1.5 Hz, 1H; CH), 6.67 (dd, 3J=8.2, 4J=2.1 Hz, 1H; CH), 5.80 (m, 1H;
-CH=CH2), 5.01–4.91 (m, 2H; -CH=CH2), 3.94 (t, 3J=6.6 Hz, 2H;
OCH2), 2.05 (m, 2H; -CH2-CH=CH2), 1.77 (m, 2H; -CH2-), 1.48–
1.10 ppm (m, 6H; -CH2-); 13C NMR (CDCl3, 100 MHz, 258C): d=159.95,
155.31, 150.01, 145.06, 138.97, 137.75, 129.93, 125.19, 122.12, 114.27, 110.9,
110.80, 105.30, 68.04, 33.66, 29.11, 28.79, 28.78, 25.84 ppm; FD-MS: m/z:
calcd for C21H24N2O5: 384.4; found: 384.8 [M]+; elemental analysis (%)
calcd for C21H24N2O5: C 65.61, H 6.29, N 7.29; found: C 65.26, H 6.17, N
7.25.
3-(Undec-10’-enyloxy)acetanilide (see Scheme 1): Yield 83%; m.p.
53.78C; 1H NMR (CDCl3, 400 MHz, 258C): d=7.20 (overlapped with sol-
vent signal, brt, 1H; CH), 7.16 (brs, 1H; NH), 7.17 (t, 3J=8.2 Hz, 1H;
CH), 6.92 (brd, 3J=7.8 Hz, 1H; CH), 6.63 (dd, 3J=8.2, 4J=1.7 Hz, 1H;
4-Nitrophenyl-N-[3’-(pent-4’’-enyloxy)phenyl]carbamate: Yield 85%;
m.p. 1068C; 1H NMR (CDCl3, 400 MHz, 258C): d=8.27 (d, 3J=8.8 Hz,
2H; CH), 7.37 (d, 3J=8.8 Hz, 2H; CH), 7.23 (t, 3J=8.8 Hz, 1H; CH),
7.15 (brs, 1H; CH), 7.01 (brs, 1H; NH), 6.90 (dd, 3J=7.8, 4J=1.7 Hz,
1H; CH), 6.68 (dd, 3J=7.8, 4J=2.0 Hz, 1H; CH), 5.84 (m, 1H; -CH=
CH2), 5.05–4.99 (m, 2H; -CH=CH2), 3.96 (t, 3J=6.4 Hz, 2H; OCH2-),
2.22 (m, 2H; -CH2-CH=CH2), 1.87 ppm (m, 2H; -CH2-); 13C NMR
(CDCl3, 100 MHz, 258C): d=159.89, 155.32, 150.02, 145.08, 137.77,
137.70, 129.96, 125.20, 122.12, 115.23, 110.99, 110.79, 105.36, 67.27, 30.03,
Scheme 1. a) Corresponding alkenyl bromide m
DMF or acetonitrile, 808C; b) NaOH, ethanol/H2O, reflux, 6 h; c) 4-ni-
trophenylchloroformate, THF, 12 h.
= 3, 4, 6, 9, K2CO3,
6164
www.chemeurj.org
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 6157 – 6170

Calix[4]arene-Based Bis[2]catenanes
FULL PAPER
28.34 ppm; elemental analysis (%) calcd for C18H18N2O5: C 63.15, H 5.30,
N 8.18; found: C 63.05, H 5.25, N 8.17.
ArCH2Areq), 2.02 (m, 16H; -CH2-CH=CH2), 1.68 (m, 16H; -CH2-), 1.40–
1.10 ppm (m, 48H; -CH2-); 13C NMR (CDCl3, 100 MHz, 258C): d=
160.57, 154.19, 152.47, 140.63, 139.19, 134.83, 134.44, 133.41, 130.43,
117.62, 116.24, 114.09, 109.84, 109.69, 103.78, 67.98, 60.96, 33.80, 30.83,
29.48, 29.42, 29.36, 29.21, 29.12, 28.92, 25.91 ppm; ESI-MS: m/z (%):
calcd for C104H136N8O12: 1689.02; found: 1713.03 (100) [M+Na]+.
Tetraurea 1(M,5): Yield 76%; m.p. 145–150 (phase transition), 170–
R
1
1738C; H NMR (C6D6, 400 MHz, 258C): d=9.78 (s, 8H; NH), 8.00 (brt,
8H; Ar-H), 7.99 (d, 4J=2.6 Hz, 8H; Arcalix-H), 7.66 (dd, 3J=8.2, 4J=
3
0.9 Hz, 8H; Ar-H), 7.28 (s, 8H; NH), 7.10 (t, J=8.2 Hz, 8H; Ar-H), 6.56
(dd, 3J=8.2, 4J=2.1 Hz, 8H; Ar-H), 6.14 (d, 4J=2.6 Hz, 8H; Arcalix-H),
5.61 (m, 8H; -CH=CH2), 4.95–4.85 (m, 16H; -CH=CH2), 4.24 (d, 2J=
11.7 Hz, 8H; ArCH2Arax), 3.85–3.60 (m, 16H; -OCH2-), 3.57 (s, 24H;
Tetraurea
1
(P,5): Yield 73%; m.p. 225–2278C; 1H NMR (CDCl3,
U
-
3
3
H), 7.55 (brt, 8H; Ar-H), 7.38 (brdd, J=7.6 Hz, 8H; Ar-H), 7.24 (t, J=
8.2 Hz, 8H; Ar-H), 6.90 (s, 8H; NH), 6.57 (dd, 3J=8.2, 4J=1.8 Hz, 8H;
2
-OCH3), 3.16 (d, J=11.7 Hz, 8H; ArCH2Areq), 1.96 (m, 16H; -CH2-CH=
1
4
CH2), 1.58 ppm (m, 16H; -CH2-); H NMR (CDCl3, 400 MHz, 258C): d=
Ar-H), 5.86 (d, J=2.2 Hz, 8H; Arcalix-H), 5.73 (m, 8H; -CH=CH2), 4.94–
9.25 (s, 8H; NH), 7.63 (d, 4J=1.8 Hz, 8H; Arcalix-H), 7.50 (brt, 8H; Ar-
H), 7.37 (brdd, 3J=8.2 Hz, 8H; Ar-H), 7.24 (t, 3J=8.2 Hz, 8H; Ar-H),
7.08 (s, 8H; NH), 6.58 (dd, 3J=8.2, 4J=1.8 Hz, 8H; Ar-H), 5.80 (d, 4J=
1.8 Hz, 8H; Arcalix-H), 5.75 (m, 8H; -CH=CH2), 4.96–4.91 (m, 16H;
-CH=CH2), 4.07 (d, 2J=11.7 Hz, 8H; ArCH2Arax), 4.00–3.80 (m, 16H;
-OCH2-), 3.72 (s, 24H; -OCH3), 2.83 (d, 2J=11.7 Hz, 8H; ArCH2Areq),
2.10 (m, 16H; -CH2-CH=CH2), 1.79 ppm (m, 16H; -CH2-); 13C NMR
(CDCl3, 100 MHz, 258C): d=160.18, 154.19, 152.51, 140.64, 137.76,
134.83, 134.45, 133.39, 130.48, 117.64, 116.24, 115.01, 110.00, 109.56,
103.98, 67.14, 60.98, 30.82, 29.97, 28.34 ppm; ESI-MS: m/z (%): calcd for
C80H88N8O12: 1352.65; found: 1375.68 (100) [M+Na]+.
4.90 (m, 16H; -CH=CH2), 4.22 (d, 2J=11.7 Hz, 8H; ArCH2Arax), 3.95–
3.75 (m, 16H; OCH2), 3.70–3.55 (m, 16H; OCH2), 2.85 (d, 2J=11.7 Hz,
8H; ArCH2Areq), 2.08 (m, 16H; -CH2-CH=CH2), 1.92 (m, 16H; -CH2-),
1.77 (m, 16H; -CH2-), 1.37 (m, 16H; -CH2-), 1.27 (m, 16H; -CH2-),
0.94 ppm (t, J=7.0 Hz, 24H; -CH3); 13C NMR (CDCl3, 100 MHz, 258C):
3
d=160.17, 154.24, 151.30, 140.64, 137.73, 135.23, 134.77, 133.04, 130.48,
117.61, 116.43, 114.98, 109.91, 109.59, 103.81, 75.63, 67.12, 30.35, 29.96,
29.80, 28.36, 28.11, 22.80, 14.17 ppm; ESI-MS: m/z (%): calcd for
C96H120N8O12: 1576.90; found: 1600.91 (100) [M+Na]+.
Tetraurea
1
(P,11): Yield 68%; m.p. 150–1528C; 1H NMR (CDCl3,
N
-
3
3
Tetraurea 1
C
H), 7.59 (brt, 8H; Ar-H), 7.35 (brdd, J=7.9 Hz, 8H; Ar-H), 7.23 (t, J=
8.2 Hz, 8H; Ar-H), 6.90 (s, 8H; NH), 6.56 (dd, 3J=7.9, 4J=1.8 Hz, 8H;
Ar-H), 5.86 (d, J=2.4 Hz, 8H; Arcalix-H), 5.56 (m, 8H; -CH=CH2), 4.98–
4
8H; Arcalix-H), 7.66 (brdd, J=8.2 Hz, 8H; Ar-H), 7.29 (s, 8H; NH), 7.12
(t, 3J=8.2 Hz, 8H; Ar-H), 6.58 (dd, 3J=8.2, 4J=1.8 Hz, 8H; Ar-H), 6.15
(d, 4J=2.4 Hz, 8H; Arcalix-H), 5.60 (m, 8H; -CH=CH2), 4.95–4.85 (m,
16H; -CH=CH2), 4.24 (d, 2J=11.7 Hz, 8H; ArCH2Arax), 3.85–3.65 (m,
16H; -OCH2-), 3.57 (s, 24H; -OCH3), 3.15 (d, 2J=11.7 Hz, 8H;
ArCH2Areq), 1.84 (m, 16H; -CH2-CH=CH2), 1.51 (m, 8H; -CH2-),
1.29 ppm (m, 16H; -CH2-); 1H NMR (CDCl3, 400 MHz, 258C): d=9.26
(s, 8H; NH), 7.64 (d, 4J=2.0 Hz, 8H; Arcalix-H), 7.52 (brt, 8H; Ar-H),
7.37 (brdd, 3J=7.6 Hz, 8H; Ar-H), 7.24 (t, 3J=8.1 Hz, 8H; Ar-H), 7.07
(s, 8H; NH), 6.58 (dd, 3J=6.8, 4J=1.5 Hz, 8H; Ar-H), 5.81 (d, 4J=
2.0 Hz, 8H; Arcalix-H), 5.75 (m, 8H; -CH=CH2), 4.96–4.92 (m, 16H;
-CH=CH2), 4.07 (d, 2J=12.0 Hz, 8H; ArCH2Arax), 4.00–3.80 (m, 16H;
-OCH2-), 3.72 (s, 24H; -OCH3), 2.84 (d, 2J=12.0 Hz, 8H; ArCH2Areq),
2.02 (m, 16H; -CH2-CH=CH2), 1.72 (m, 8H; -CH2-), 1.43 ppm (m, 16H;
-CH2-); 13C NMR (CDCl3, 100 MHz, 258C): d=160.21, 154.18, 152.49,
140.63, 138.50, 134.83, 134.45, 133.39, 130.47, 117.63, 116.24, 114.57,
109.91, 109.63, 103.84, 67.72, 60.99, 33.34, 30.81, 28.60, 25.17 ppm; ESI-
MS: m/z (%): calcd for C84H96N8O12: 1408.71; found: 1431.73 (100)
[M+Na]+.
4.92 (m, 16H; -CH=CH2), 4.22 (d, 2J=11.7 Hz, 8H; ArCH2Arax), 3.95–
3.75 (m, 16H; OCH2), 3.70–3.55 (m, 16H; OCH2), 2.85 (d, 2J=11.7 Hz,
8H; ArCH2Areq), 2.02 (m, 16H; -CH2-CH=CH2), 1.93 (m, 16H; -CH2-),
1.67 (m, 16H; -CH2-), 1.50–1.05 (m, 128H; -CH2-), 0.95 ppm (t, 3J=
7.3 Hz, 24H; -CH3); 13C NMR (CDCl3, 100 MHz, 258C): d=160.27,
154.25, 151.28, 140.64, 139.18, 135.24, 134.76, 133.06, 130.40, 117.60,
116.44, 114.09, 109.83, 109.76, 103.53, 75.59, 67.99, 33.81, 30.36, 29.81,
29.45, 29.39, 29.21, 29.14, 28.94, 28.15, 25.86, 22.82, 14.18 ppm; ESI-MS:
m/z (%): calcd for
C120H168N8O12: 1913.27; found: 1937.30 (100)
[M+Na]+.
Tetraurea
1
(D,6): Yield 85%; m.p. 207–2098C; 1H NMR (C6D6,
C
-
H), 8.09 (brt, 8H; Ar-H), 7.70 (brdd, 3J=7.8 Hz, 8H; Ar-H), 7.21 (s,
8H; NH), 7.12 (t, 3J=8.2 Hz, 8H; Ar-H), 6.59 (dd, 3J=8.6, 4J=2.0 Hz,
8H; Ar-H), 6.31 (d, 4J=2.4 Hz, 8H; Arcalix-H), 5.75 (m, 8H; -CH=CH2),
5.05–4.90 (m, 16H; -CH=CH2), 4.60 (d, 2J=11.7 Hz, 8H; ArCH2Arax),
3.90–3.60 (m, 32H; OCH2), 3.30 (d, 2J=11.7 Hz, 8H; ArCH2Areq), 2.14
(m, 16H; -CH2-), 1.86 (m, 16H; -CH2-CH=CH2), 1.55–1.10 (m, 144H;
3
1
Tetraurea 1
A
-CH2-), 0.96 ppm (t, J=6.7 Hz, 24H; -CH3); H NMR (CDCl3, 400 MHz,
1H NMR (C6D6, 400 MHz, 258C): d=9.83 (s, 8H; NH), 8.11 (brt, 8H;
Ar-H), 8.04 (d, 4J=2.4 Hz, 8H; Arcalix-H), 7.67 (brdd, 3J=8.2 Hz, 8H;
Ar-H), 7.33 (s, 8H; NH), 7.12 (t, 3J=8.2 Hz, 8H; Ar-H), 6.65 (dd, 3J=
8.5, 4J=1.8 Hz, 8H; Ar-H), 6.19 (d, 4J=2.4 Hz, 8H; Arcalix-H), 5.81 (m,
8H; -CH=CH2), 5.07–5.03 (m, 16H; -CH=CH2), 4.28 (d, 2J=11.4 Hz,
8H; ArCH2Arax), 3.85–3.65 (m, 16H; -OCH2-), 3.60 (s, 24H; -OCH3),
3.20 (d, 2J=11.7 Hz, 8H; ArCH2Areq), 1.97 (m, 16H; -CH2-CH=CH2),
258C): d=9.43 (s, 8H; NH), 7.66 (d, J=2.4 Hz, 8H; Arcalix-H), 7.58 (brt,
4
8H; Ar-H), 7.35 (brdd, 3J=7.9 Hz, 8H; Ar-H), 7.23 (t, 3J=7.9 Hz, 8H;
Ar-H), 6.90 (s, 8H; NH), 6.55 (dd, 3J=8.2, 4J=1.8 Hz, 8H; Ar-H), 5.85
(d, 4J=2.4 Hz, 8H; Arcalix-H), 5.72 (m, 8H; -CH=CH2), 4.94–4.91 (m,
16H; -CH=CH2), 4.21 (d, 2J=11.7 Hz, 8H; ArCH2Arax), 3.95–3.75 (m,
16H; OCH2), 3.70–3.55 (m, 16H; OCH2), 2.84 (d, 2J=11.7 Hz, 8H;
ArCH2Areq), 2.00 (m, 16H; -CH2-CH=CH2), 1.91 (m, 16H; -CH2-), 1.69
(m, 16H; -CH2-), 1.40 (m, 16H; -CH2-), 1.29 (m, 112H; -CH2-), 0.89 ppm
(t, 3J=6.8 Hz, 24H; -CH3); 13C NMR (CDCl3, 100 MHz, 258C): d=
160.22, 154.25, 151.32, 140.64, 138.46, 135.24, 134.76, 133.04, 130.45,
117.62, 116.45, 114.60, 109.83, 109.79, 103.59, 75.67, 67.70, 33.35, 32.00,
30.35, 30.26, 30.05, 30.02, 29.81, 29.47, 28.59, 26.12, 25.12, 22.72,
14.12 ppm; ESI-MS: m/z (%): calcd for C120H168N8O12: 1913.27; found:
1937.28 (100) [M+Na]+.
1
1.60 (m, 16H; -CH2-), 1.40–1.10 ppm (m, 48H; -CH2-); H NMR (CDCl3,
400 MHz, 258C): d=9.25 (s, 8H; NH), 7.63 (d, 4J=2.4 Hz, 8H; Arcalix
-
3
3
H), 7.52 (brt, 8H; Ar-H), 7.34 (brdd, J=7.9 Hz, 8H; Ar-H), 7.23 (t, J=
8.1 Hz, 8H; Ar-H), 7.06 (s, 8H; NH), 6.56 (dd, 3J=8.2, 4J=1.8 Hz, 8H;
4
Ar-H), 5.81 (d, J=2.0 Hz, 8H; Arcalix-H), 5.75 (m, 8H; -CH=CH2), 4.96–
4.90 (m, 16H; -CH=CH2), 4.06 (d, 2J=11.7 Hz, 8H; ArCH2Arax), 4.00–
3.80 (m, 16H; -OCH2-), 3.71 (s, 24H; -OCH3), 2.83 (d, 2J=11.7 Hz, 8H;
ArCH2Areq), 1.98 (m, 16H; -CH2-CH=CH2), 1.68 (m, 16H; -CH2-), 1.40–
Tetraurea
1
(D,8): Yield 80%; m.p. 205–2078C; 1H NMR (CDCl3,
A
1.10 ppm (m, 48H; -CH2-); ESI-MS: m/z (%): calcd for C92H112N8O12
:
400 MHz, 258C): d=9.43 (s, 8H; NH), 7.66 (brd, 8H; Arcalix-H), 7.60
(brt, 8H; Ar-H), 7.32 (brdd, 3J=8.0 Hz, 8H; Ar-H), 7.22 (t, 3J=8.1 Hz,
8H; Ar-H), 6.89 (s, 8H; NH), 6.55 (brdd, 3J=7.9 Hz, 8H; Ar-H), 5.85
(brd, 8H; Arcalix-H), 5.76 (m, 8H; -CH=CH2), 4.96–4.90 (m, 16H; -CH=
CH2), 4.20 (d, 2J=11.7 Hz, 8H; ArCH2Arax), 3.95–3.75 (2”m, 16H;
-OCH2-), 2.84 (d, 2J=11.7 Hz, 8H; ArCH2Areq), 1.98 (m, 16H; -CH2-
CH=CH2), 1.95–1.70 (m, 32H; -CH2-), 1.66 (m, 16H; -CH2-), 1.50–1.20
(m, 160H; -CH2-), 0.89 ppm (t, 3J=6.9 Hz, 24H; -CH3); 13C NMR
(CDCl3, 100 MHz, 258C): d=160.26, 154.24, 151.31, 140.64, 138.98,
1520.83; found: 1544.87 (100) [M+Na]+.
Tetraurea
1
(M,11): Yield 69%; m.p. 169–1738C; 1H NMR (CDCl3,
C
-
3
3
H), 7.51 (brt, 8H; Ar-H), 7.35 (brdd, J=7.4 Hz, 8H; Ar-H), 7.23 (t, J=
7.2 Hz, 8H; Ar-H), 7.06 (s, 8H; NH), 6.56 (dd, 3J=8.2, 4J=1.70 Hz, 8H;
Ar-H), 5.79 (d, 4J=1.70 Hz, 8H; Arcalix-H), 5.79 (m, 8H; -CH=CH2),
4.98–4.91 (m, 16H; -CH=CH2), 4.06 (d, 2J=11.9 Hz, 8H; ArCH2Arax),
3.88 (m, 16H; -OCH2-), 3.71 (s, 24H; -OCH3), 2.83 (d, 2J=11.9 Hz, 8H;
Chem. Eur. J. 2007, 13, 6157 – 6170
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6165

V. Bçhmer et al.
135.24, 134.76, 133.04, 130.40, 117.60, 116.44, 114.20, 109.86, 109.77,
103.46, 75.65, 67.92, 33.68, 32.00, 30.35, 30.25, 30.06, 30.02, 29.82, 29.48,
29.13, 28.83, 28.74, 26.14, 25.69, 22.72, 14.12 ppm; ESI-MS: m/z (%):
calcd for C128H184N8O12: 2025.40; found: 2049.44 (100) [M+Na]+.
1H NMR ([D8]THF, 400 MHz, 258C): d=7.64 (s, 4H; NH), 7.63 (s, 4H;
NH), 7.19 (t, 4J=2.1 Hz, 4H; Armeta-H), 6.99 (d, 4J=2.6 Hz, 4H; Arcalix
-
3
4
H), 6.95 (t, J=8.1 Hz, 4H; Armeta-H), 6.64 (d, J=2.4 Hz, 4H; Arcalix-H),
6.62 (dd, 3J=8.0, 4Jꢀ1 Hz, 4H; Armeta-H), 6.41 (dd, 3J=8.0, 4J=2.1 Hz,
4H; Armeta-H), 4.43 (d, 2J=13.1 Hz, 2H; Ar-CH2-Arax), 4.42 (d, 2J=
12.9 Hz, 2H; Ar-CH2-Arax), 3.93–3.80 (m, 16H; OCH2-), 3.09 (d, 2J=
13.3 Hz, 2H; Ar-CH2-Areq), 3.05 (d, 2J=13.3 Hz, 2H; Ar-CH2-Areq), 1.94
(m, 8H; -CH2-), 1.50–1.25 (m, 40H; -CH2-), 0.96 ppm (t, 3J=7.0 Hz,
12H; -CH3); ESI-MS (THF+MeOH+HCO2H 90:7:2): m/z (%): calcd for
Bisloops and bis[2]catenanes
Bisloop
3
(M,8): Yield 72%; m.p. >2858C (decomp); 1H NMR
A
([D6]DMSO, 400 MHz, 258C): d=8.37 (s, 4H; NH), 8.25 (s, 4H; NH),
7.25 (brt, 4Jꢀ1 Hz, 4H; Armeta-H), 7.17 (d, 4J=2.1 Hz, 4H; Arcalix-H),
7.09 (t, 3J=8.1 Hz, 4H; Armeta-H), 6.64 (d, 4J=2.1 Hz, 4H; Arcalix-H),
6.60 (brdd, 3J=8.5 Hz, 4H; Armeta-H), 6.48 (dd, 3J=8.2, 4J=2.1 Hz, 4H;
Armeta-H), 4.26 (d, 2J=12.3 Hz, 2H; Ar-CH2-Arax), 4.24 (d, 2J=12.0 Hz,
2H; Ar-CH2-Arax), 3.90 (t, 3J=6.2 Hz, 8H; OCH2-), 3.78 (s, 12H;
OCH3), 3.19 (d, 2J=12.0 Hz, 2H; Ar-CH2-Areq), 3.16 (d, 2J=12.3 Hz,
2H; Ar-CH2-Areq), 1.68 (m, 8H; -CH2-), 1.40 (m, 8H; -CH2-), 1.33 ppm
(m, 8H; -CH2-); ESI-MS: m/z (%): calcd for C76H84N8O12: 1300.62;
found: 1323.71 (100) [M+Na]+.
C92H116N8O12
:
1525.87; found: 1526.97 (100) [M+H]+, 1548.95 (73)
[M+Na]+.
1
Bisloop 3
A
400 MHz, 258C): d=7.53 (s, 4H; NH), 7.48 (s, 4H; NH), 7.10 (t, 4J=
2.0 Hz, 4H; Armeta-H), 6.98 (t, 3J=8.2 Hz, 4H; Armeta-H), 6.87 (d, 4J=
2.4 Hz, 4H; Arcalix-H), 6.81 (dd, 3J=6.76, 4J=1.0 Hz, 4H; Armeta-H), 6.76
(d, 4J=2.4 Hz, 4H; Arcalix-H), 6.41 (dd, 3J=8.2, 4J=2.0 Hz, 4H; Armeta
H), 4.444 (d, 2J=13.3 Hz, 2H; Ar-CH2-Arax), 4.440 (d, 2J=12.9 Hz, 2H;
Ar-CH2-Arax), 3.89–3.86 (m, 16H; OCH2-), 3.08 (d, 2J=13.3 Hz, 2H; Ar-
CH2-Areq), 3.07 (d, 2J=12.9 Hz, 2H; Ar-CH2-Areq), 1.95 (m, 8H; -CH2-),
1.50–1.25 (m, 64H; -CH2-), 0.96 (t, 3J=6.9 Hz, 12H; -CH3) ppm; ESI-
MS: m/z (%): calcd for C104H140N8O12: 1693.06; found: 1717.14 (100)
[M+Na]+.
Bisloop
3
(M,10): Yield 57%; m.p. >2458C (decomp); 1H NMR
A
([D6]DMSO, 400 MHz, 258C): d=8.34 (s, 4H; NH), 8.26 (s, 4H; NH),
7.15–7.00 (m, 12H; Armeta-H, Arcalix-H), 6.80–6.70 (m, 8H; Armeta-H,
Arcalix-H), 6.48 (dd, 3J=8.2, 4J=1.8 Hz, 4H; Armeta-H), 4.26 (d, 2J=
11.7 Hz, 2H; Ar-CH2-Arax), 4.24 (d, 2J=12.3 Hz, 2H; Ar-CH2-Arax), 3.90
(t, 3J=6.2 Hz, 8H; OCH2-), 3.78 (s, 12H; OCH3), 3.19 (d, 2J=12.0 Hz,
Bisloop
3
(P,20): Yield 84%; m.p. >2458C (decomp); 1H NMR
A
2
2H; Ar-CH2-Areq), 3.17 (d, J=12.3 Hz, 2H; Ar-CH2-Areq), 1.67 (m, 8H;
-CH2-), 1.39 (m, 8H; -CH2-), 1.28 ppm (m, 16H; -CH2-); 1H NMR
([D8]THF, 400 MHz, 258C): d=7.66 (s, 4H; NH), 7.62 (s, 4H; NH), 7.14
(brt, 4H; Armeta-H), 7.02 (brd, 4H; Arcalix-H), 6.99 (t, 3J=8.1 Hz, 4H;
([D6]DMSO, 400 MHz, 258C): d=8.31 (s, 4H; NH), 8.16 (s, 4H; NH),
7.07 (t, 3J=7.9 Hz, 4H; Armeta-H), 6.95 (brt, 4Jꢀ2 Hz, 4H; Armeta-H),
4
6.90–6.80 (m, 8H; Armeta-H, Arcalix-H), 6.75 (d, J=2.4 Hz, 4H; Arcalix-H),
6.46 (dd, 3J=8.2, 4J=2.0 Hz, 4H; Armeta-H), 4.33 (d, 2J=12.3 Hz, 4H;
Ar-CH2-Arax), 3.85 (t, 3J=6.6 Hz, 8H; OCH2-), 3.82 (t, 3J=7.5 Hz, 8H;
OCH2-), 3.11 (d, 2J=12.0 Hz, 4H; Ar-CH2-Areq), 1.91 (m, 8H; -CH2-),
Armeta-H), 6.78 (brd, 4H; Arcalix-H), 6.76 (brdd, 3Jꢀ8.0 Hz, 4H; Armeta
-
H), 6.41 (dd, 3J=8.2, 4J=2.1 Hz, 4H; Armeta-H), 4.33 (d, 2J=13.1 Hz,
4H; Ar-CH2-Arax), 3.89 (t, 3J=6.2 Hz, 8H; OCH2-), 3.78 (s, 12H;
OCH3), 3.14 (d, 2J=12.5 Hz, 2H; Ar-CH2-Areq), 3.11 (d, 2J=12.3 Hz,
2H; Ar-CH2-Areq), 1.45 (m, 8H; -CH2-), 1.40–1.20 ppm (m, 24H; -CH2-);
ESI-MS: m/z (%): calcd for C80H92N8O12: 1356.68; found: 1379.70 (100)
[M+Na]+.
3
1.66 (m, 8H; -CH2-), 1.50–1.10 (m, 80H; -CH2-), 0.94 ppm (t, J=6.9 Hz,
12H; -CH3); 1H NMR ([D8]THF, 400 MHz, 258C): d=7.69 (s, 4H; NH),
7.66 (s, 4H; NH), 7.08 (t, 4J=2.0 Hz, 4H; Armeta-H), 6.98 (t, 3J=8.1 Hz,
4H; Armeta-H), 6.86 (d, 4J=2.4 Hz, 4H; Arcalix-H), 6.82 (dd, 3J=8.2 Hz,
4H; 4J=1.0 Hz, Armeta-H), 6.79 (d, 4J=2.4 Hz, 4H; Arcalix-H), 6.41 (dd,
3J=8.1, 4J=2.0 Hz, 4H; Armeta-H), 4.43 (d, 2J=13.1 Hz, 4H; Ar-CH2-
Arax), 3.87 (t, 3J=6.2 Hz, 8H; OCH2-), 3.85 (t, 3J=6.2 Hz, 8H; OCH2-),
3.08 (d, 2J=12.9 Hz, 2H; Ar-CH2-Areq), 3.07 (d, 2J=12.9 Hz, 2H; Ar-
CH2-Areq), 1.94 (m, 8H; -CH2-), ꢀ1.70 (m, under the solv. signal; -CH2-),
1.50–1.25 (2”m, 80H; -CH2-), 0.96 ppm (t, 3J=7.1 Hz, 12H; -CH3);
13C NMR (CDCl3, 100 MHz, 258C): d=160.70, 153.31, 152.67, 142.49,
135.83, 134.91, 129.76, 119.44, 119.38, 111.03, 108.31, 105.24, 75.91, 67.97,
32.12, 30.89, 30.20, 30.07, 29.98, 29.50, 26.86, 23.77, 14.60 ppm.
Bisloop
3
(M,14): Yield 48%; m.p. >2508C (decomp); 1H NMR
A
([D8]THF, 400 MHz, 258C): d=7.56 (s, 4H; NH), 7.45 (s, 4H; NH), 7.11
(brt, 4H; Armeta-H), 7.00 (t, 3J=8.1 Hz, 4H; Armeta-H), 6.95 (d, 4J=
1.7 Hz, 4H; Arcalix-H), 6.82 (brdd, 3Jꢀ8.0 Hz, 4H; Armeta-H), 6.817 (brd,
4H; Arcalix-H), 6.43 (dd, 3J=8.0, 4J=2.0 Hz, 4H; Armeta-H), 4. 33 (d, 2J=
12.6 Hz, 2H; Ar-CH2-Arax), 4.32 (d, 2J=12.9 Hz, 2H; Ar-CH2-Arax), 3.89
(t, 3J=6.2 Hz, 8H; OCH2-), 3.78 (s, 12H; OCH3), 3.12 (d, 2J=12.9 Hz,
2
2H; Ar-CH2-Areq), 3.06 (d, J=13.0 Hz, 2H; Ar-CH2-Areq), 1.46 (m, 8H;
-CH2-), 1.40–1.20 ppm (m, 40H; -CH2-); ESI-MS: m/z (%): calcd for
C88H108N8O12: 1468.80; found: 1492.82 (100) [M+Na]+.
Bisloop
3
(D,10): Yield 95%; m.p. >2508C (decomp); 1H NMR
A
3
(M,20): Yield 64%; m.p. >2608C (decomp); 1H NMR
A
([D8]THF, 400 MHz, 258C): d=7.49 (s, 4H; NH), 7.47 (s, 4H; NH), 7.10
(t, 4J=2.0 Hz, 4H; Armeta-H), 6.98 (t, 3J=8.2 Hz, 4H; Armeta-H), 6.91 (d,
4J=2.4 Hz, 4H; Arcalix-H), 6.78 (dd, 3J=8.2, 4J=1.2 Hz, 4H; Armeta-H),
6.74 (brd, 4J=2.4 Hz, 4H; Arcalix-H), 6.41 (dd, 3J=8.2, 4J=2.0 Hz, 4H;
Armeta-H), 4.44 (d, 2J=12.9 Hz, 4H; Ar-CH2-Arax), 3.86 (m, 16H; OCH2-
), 3.08 (d, 2J=12.9 Hz, 2H; Ar-CH2-Areq), 3.06 (d, 2J=13.3 Hz, 2H; Ar-
CH2-Areq), 1.95 (m, 8H; -CH2-), 1.50–1.10 (2”m, 88H; -CH2-), 0.89 ppm
Bisloop
([D6]DMSO, 400 MHz, 258C): d=8.31 (s, 4H; NH), 8.28 (s, 4H; NH),
7.09 (t, 3J=7.9 Hz, 4H; Armeta-H), 6.97, 6.87 (2”brm, 16H; Armeta-H,
Arcalix-H), 6.47 (dd, 3J=8.5, 4J=2.0 Hz, 4H; Armeta-H), 4.23 (very broad
signal, 4H; Ar-CH2-Arax), 3.90 (t, 3J=5.9 Hz, 8H; OCH2-), 3.78 (brs,
12H; OCH3), 3.18 (very broad signal, 4H; Ar-CH2-Areq), 1.66 (m, 8H;
-CH2-), 1.37 (m, 8H; -CH2-), 1.21 ppm (m, 56H; -CH2-); 1H NMR
([D8]THF, 400 MHz, 258C): d=7.58 (s, 4H; NH), 7.45 (s, 4H; NH), 7.12
(brt, 4H; Armeta-H), 7.00 (t, 3J=8.1 Hz, 4H; Armeta-H), 6.93 (brd, 4H;
(t, 3J=7.0 Hz, 12H; -CH3); ESI-MS: m/z (%): calcd for C116H164N8O12
1861.25; found: 1863.33 (100) [M+H]+, 1885.30 (43) [M+Na]+.
:
Arcalix-H), 6.85 (brd, 4H; Arcalix-H), 6.81 (brdd, 3Jꢀ7.9 Hz, 4H; Armeta
-
Bisloop
3
(D,14): Yield 53%; m.p. >2608C (decomp); 1H NMR
A
H), 6.43 (brdd, 3J=8.0 Hz, 4H; Armeta-H), 4.34 (d, 2J=12.8 Hz, 4H; Ar-
CH2-Arax), 3.87 (t, 3J=6.2 Hz, 8H; OCH2-), 3.78 (s, 12H; OCH3), 3.11
(d, 2J=12.6 Hz, 2H; Ar-CH2-Areq), 3.11 (d, 2J=12.9 Hz, 2H; Ar-CH2-
Areq), 1.65 (m, 8H; -CH2-), 1.37–1.21 (m, 64H; -CH2-) ppm; ESI-MS: m/z
(%): calcd for C100H132N8O12: 1636.99; found: 1660.99 (100) [M+Na]+.
([D6]DMSO, 400 MHz, 258C): d=8.24 (s, 4H; NH), 8.08 (s, 4H; NH),
7.06 (t, 3J=8.0 Hz, 4H; Armeta-H), 6.97 (brt, unresolved coupling, 4H;
Armeta-H), 6.89 (d, 4J=2.0 Hz, 4H; Arcalix-H), 6.85 (brdd, 3J=6.8 Hz, un-
resolved coupling, 4H; Armeta-H), 6.69 (brd, 4J=2.0 Hz, 4H; Arcalix-H),
6.46 (dd, 3J=7.9, 4J=1.7 Hz, 4H; Armeta-H), 4.34 (d, 2J=12.9 Hz, 2H;
Ar-CH2-Arax), 4.33 (d, 2J=12.9 Hz, 2H; Ar-CH2-Arax), 3.88 (t, 3J=
Bisloop
3
(P,8): Yield 72%; m.p. >2508C (decomp); 1H NMR
A
3
6.3 Hz, 8H; OCH2-), 3.82 (t, J=6.6 Hz, 8H; OCH2-), 3.20–3.15 (overlap
([D6]DMSO, 400 MHz, 258C): d=8.37 (s, 4H; NH), 8.14 (s, 4H; NH),
7.29 (t, 4J=2.1 Hz, 4H; Armeta-H), 7.09 (d, 4J=2.6 Hz, 4H; Arcalix-H),
7.06 (t, 3J=8.2 Hz, 4H; Armeta-H), 6.53 (dd, 3J=8.2, 4J=1.2 Hz, 4H;
Armeta-H), 6.49 (d, 4J=2.4 Hz, 4H; Arcalix-H), 6.47 (dd, 3J=8.2, 4J=
2.1 Hz, 4H; Armeta-H), 4.34 (d, 2J=12.6 Hz, 2H; Ar-CH2-Arax), 4.33 (d,
2J=12.6 Hz, 2H; Ar-CH2-Arax), 3.90 (t, 3J=6.0 Hz, 8H; OCH2-), 3.85–
3.75 (m, 8H; OCH2-), 3.12 (d, 2J=12.9 Hz, 2H; Ar-CH2-Areq), 3.11 (d,
2J=12.9 Hz, 2H; Ar-CH2-Areq), 1.89 (m, 8H; -CH2-), 1.68 (m, 8H;
-CH2-), 1.50–1.20 (m, 32H; -CH2-), 0.93 ppm (t, 3J=6.9 Hz, 12H; -CH3);
with the solvent signal, 4H; Ar-CH2-Areq), 3.10 (d, 2J=12.3 Hz, 4H; Ar-
CH2-Areq), 1.90 (m, 8H; -CH2-), 1.66 (m, 8H; -CH2-), 1.50–1.10 (m, 96H;
-CH2-), 0.85 ppm (t, 3J=6.9 Hz, 12H; -CH3); 1H NMR ([D8]THF,
400 MHz, 258C): d=7.52 (s, 4H; NH), 7.46 (s, 4H; NH), 7.10 (brt, 4J
ꢀ2 Hz, 4H; Armeta-H), 6.99 (t, 3J=7.8 Hz, 4H; Armeta-H), 6.88 (brd, 4J
ꢀ2 Hz, 4H; Arcalix-H), 6.81 (brdd, 3J=7.8 Hz, 4H; Armeta-H), 6.76 (brd,
4Jꢀ2 Hz, 4H; Arcalix-H), 6.42 (brdd, 3J=7.2 Hz, 4H; Armeta-H), 4.44 (d,
2J=12.9 Hz, 4H; Ar-CH2-Arax), 3.88 (m, 16H; OCH2-), 3.08 (d, 2J=
6166
www.chemeurj.org
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 6157 – 6170

Calix[4]arene-Based Bis[2]catenanes
FULL PAPER
12.3 Hz, 2H; Ar-CH2-Areq), 3.07 (d, 2J=12.3 Hz, 2H; Ar-CH2-Areq), 1.96
(m, 8H; -CH2-), 1.50–1.10 (2”m, 104H; -CH2-), 0.90 ppm (t, 3J=6.8 Hz,
12H; -CH3); ESI-MS: m/z (%): calcd for C124H180N8O12: 1973.37; found:
1997.45 (100) [M+Na]+.
6H; NH and two signals of Armeta-H), 7.36 (brt, unresolved coupling,
2H; Armeta-H), 7.33 (s, 2H; NH), 7.20 (s, 2H; NH), 7.20–7.15 (m, overlap
with the solvent signal, 4H; NH and Armeta-H), 7.07 (t, 3J=7.5 Hz, 2H;
Armeta-H), 7.06 (t, 3J=7.0 Hz, 2H; Armeta-H), 7.05 (t, 3J=8.2 Hz, 2H;
Armeta-H), 6.57 (dd, 3J=8.2, 4J=1.7 Hz, 2H; Armeta-H), 6.54 (dd, 3J=8.2,
4J=1.7 Hz, 2H; Armeta-H), 6.48 (dd, 3J=8.5, 4J=2.0 Hz, 2H; Armeta-H),
6.44 (dd, 3J=8.2, 4J=2.0 Hz, 2H; Armeta-H), 6.15 (d, 4J=2.7 Hz, 2H;
Arcalix-H), 6.13 (d, 4J=2.7 Hz, 2H; Arcalix-H), 6.12 (d, 4J=2.7 Hz, 2H;
Arcalix-H), 6.07 (d, 4J=2.4 Hz, 2H; Arcalix-H), 4.27 (d, 2J=11.2 Hz, 2H;
Ar-CH2-Arax), 4.23 (d, 2J=11.9 Hz, 2H; Ar-CH2-Arax), 4.22 (d, 2J=
11.9 Hz, 2H; Ar-CH2-Arax), 4.18 (d, 2J=11.9 Hz, 2H; Ar-CH2-Arax),
3.90–3.70 (m, 16H; -OCH2-), 3.615 (s, 6H; -OCH3), 3.610 (s, 6H;
-OCH3), 3.58 (s, 6H; -OCH3), 3.56 (s, 6H; -OCH3), 3.24 (d, 2J=11.9 Hz,
2H; Ar-CH2-Areq), 3.19 (d, 2J=11.6 Hz, 2H; Ar-CH2-Areq), 3.16 (d, 2J=
11.6 Hz, 2H; Ar-CH2-Areq), 3.12 (d, 2J=12.3 Hz, 2H; Ar-CH2-Areq),
1.80–1.00 ppm (6”m, 96H; -CH2-); ESI-MS: m/z (%): calcd for
C176H216N16O24: 2937.61; found: 1492.93 (100) [M+2Na]2+, 2962.83 (95)
[M+Na]+.
Bis[2]catenane 4
N
N
and tetraurea 1
ACHTREUNG
(C6D6, 400 MHz, 258C): d=10.00 (s, 2H; NH), 9.83 (s, 2H; NH), 9.75 (s,
2H; NH), 9.74 (s, 1H; NH), 9.73 (s, 1H; NH), 8.56 (brt, unresolved cou-
pling, 2H; Armeta-H), 8.35 (brt, unresolved coupling, 2H; Armeta-H), 8.31
3
3
(d, J=8.2 Hz, 2H; Armeta-H), 8.24 (d, J=8.2 Hz, 2H; Armeta-H), 8.04 (d,
4J=2.4 Hz, 2H; Arcalix-H), 7.96 (d, 4J=2.4 Hz, 2H; Arcalix-H), 7.94 (d,
4J=2.4 Hz, 2H; Arcalix-H), 7.74 (d, 4J=2.4 Hz, 2H; Arcalix-H), 7.54 (brt,
unresolved coupling, 2H; Armeta-H), 7.47 (s, 2H; NH), 7.39 (brt, unre-
solved coupling, 2H; Armeta-H), 7.36 (s, 2H; NH), 7.35 (d, 3J=6.5 Hz,
2H; Armeta-H), 7.21 (t, 3J=8.2 Hz, 2H; Armeta-H), 7.20–7.15 (d, overlap
3
with the solvent signal, 2H; Armeta-H), 7.13 (t, J=8.5 Hz, 2H; Armeta-H),
3
3
7.10 (t, J=7.8 Hz, 2H; Armeta-H), 7.01 (t, J=8.2 Hz, 2H; Armeta-H), 6.53
(s, 2H; NH), 6.82 (s, 2H; NH), 6.78 (dd, 3J=8.2, 4J=1.7 Hz, 2H; Armeta
-
H), 6.72 (dd, 3J=8.5, 4J=2.0 Hz, 2H; Armeta-H), 6.67 (dd, 3J=8.2, 4J=
2.0 Hz, 2H; Armeta-H), 6.60 (brdt, 3J=7.5, 4Jꢀ1 Hz, 2H; Armeta-H), 6.18
Bis[2]catenane
4
ACHTREUNG
3
A
ACHTREUNG
1H NMR (C6D6, 400 MHz, 258C): d=9.82 (s, 2H; NH), 9.82 (s, 2H; NH),
9.81 (s, 2H; NH), 9.80 (s, 2H; NH), 8.17 (dd, 3J=7.8, 4J=1.0 Hz, 2H;
Armeta-H), 8.14 (dd, 3J=7.8, 4J=1.0 Hz, 2H; Armeta-H), 8.07 (d, 4J=
2.4 Hz, 2H; Arcalix-H), 8.06 (d, 4J=2.7 Hz, 2H; Arcalix-H), 8.01 (d, 4J=
(d, 4J=2.4 Hz, 2H; Arcalix-H), 6.09 (d, J=2.4 Hz, 2H; Arcalix-H), 5.97 (d,
4
4J=2.4 Hz, 2H; Arcalix-H), 5.94 (d, 4J=2.4 Hz, 2H; Arcalix-H), 4.26 (d,
2J=11.6 Hz, 2H; Ar-CH2-Arax), 4.23 (d, 2J=11.9 Hz, 2H; Ar-CH2-Arax),
2
4.20–4.00 (m, 8H; -OCH2-), 4.16 (d, J=13.9 Hz, 2H; Ar-CH2-Arax), 4.07
(d, 2J=11.6 Hz, 2H; Ar-CH2-Arax), 3.91 (m, 2H; -OCH2-), 3.85–3.70 (m,
6H; -OCH2-), 3.60 (s, 6H; -OCH3), 3.53 (s, 6H; -OCH3), 3.52 (s, 6H;
-OCH3), 3.43 (s, 6H; -OCH3), 3.19 (d, 2J=11.9 Hz, 2H; Ar-CH2-Areq),
3.11 (d, 2J=11.9 Hz, 2H; Ar-CH2-Areq), 3.03 (d, 2J=11.9 Hz, 2H; Ar-
CH2-Areq), 2.85 (d, 2J=11.9 Hz, 2H; Ar-CH2-Areq), 1.90–1.60 (m, 8H;
-CH2-), 1.50–1.30 (m, 8H; -CH2-), 1.30–1.05 (m, 24H; -CH2-), 1.05–
2.7 Hz, 2H; Arcalix-H), 8.01 (brt, unresolved coupling, 2H; Armeta-H), 7.98
4
(d, J=2.7 Hz, 2H; Arcalix-H), 7.93 (brt, unresolved coupling, 2H; Armeta
-
H), 7.78 (dd, 3J=8.0, 4J=1.0 Hz, 2H; Armeta-H), 7.71 (dd, 3J=8.2, 4J=
1.0 Hz, 2H; Armeta-H), 7.63 (brt, unresolved coupling, 2H; Armeta-H),
7.57 (brt, unresolved coupling, 2H; Armeta-H), 7.25 (s, 2H; NH), 7.21 (s,
2H; NH), 7.18–7.00 (2”s and 4”t, overlap with the solvent signal, 12H;
NH and Armeta-H), 6.62 (dd, 3J=8.2, 4J=1.7 Hz, 2H; Armeta-H), 6.59 (dd,
3J=8.2, 4J=1.7 Hz, 2H; Armeta-H), 6.55 (dd, 3J=8.9, 4J=2.0 Hz, 2H;
Armeta-H), 6.53 (dd, 3J=8.5, 4J=1.7 Hz, 2H; Armeta-H), 6.12 (brd, unre-
solved coupling, 4H; Arcalix-H), 6.08 (d, 4J=1.4 Hz, 2H; Arcalix-H), 4.30
(d, 2J=11.9 Hz, 2H; Ar-CH2-Arax), 4.28 (d, 2J=12.3 Hz, 2H; Ar-CH2-
Arax), 4.26 (d, 2J=11.9 Hz, 2H; Ar-CH2-Arax), 4.24 (d, 2J=12.3 Hz, 2H;
Ar-CH2-Arax), 3.90–3.72 (m, 16H; -OCH2-), 3.70 (s, 6H; -OCH3), 3.69 (s,
6H; -OCH3), 3.61 (s, 6H; -OCH3), 3.60 (s, 6H; -OCH3), 3.26 (d, 2J=
11.6 Hz, 2H; Ar-CH2-Areq), 3.22 (d, 2J=11.0 Hz, 2H; Ar-CH2-Areq), 3.19
(d, 2J=11.0 Hz, 2H; Ar-CH2-Areq), 3.15 (d, 2J=11.9 Hz, 2H; Ar-CH2-
Areq), 1.59 (m, 8H; -CH2-), 1.53 (m, 8H; -CH2-), 1.45–1.10 ppm (m,
128H; -CH2-); ESI-MS: m/z (%): calcd for C200H264N16O24: 3273.99;
0.90 ppm (m, 8H; -CH2-); ESI-MS: m/z (%): calcd for C152H168N16O24
2601.24; found: 2753.40 (100) [M+CHCl3+MeOH]+.
:
Bis[2]catenane
4(M,10): This compound was obtained from bisloop
A
3
C
1(M,6); yield 50%; m.p. >2408C (decomp);
G
3
8.31 (brt, unresolved coupling, 2H; Armeta-H), 8.28 (brdd, J=8.2 Hz, un-
4
resolved coupling, 2H; Armeta-H), 8.06 (d, J=2.0 Hz, 2H; Arcalix-H), 8.05
(d, 4J=2.0 Hz, 2H; Arcalix-H), 7.92 (d, J=2.0 Hz, 2H; Arcalix-H), 7.91 (d,
4
4J=2.0 Hz, 2H; Arcalix-H), 7.55 (brt, unresolved coupling, 2H; Armeta-H),
found: 1661.03 (100) [M+2Na]2+
Bis[2]catenane 4(P,8): This compound was obtained from bisloop 3
and tetraurea
(P,5); yield 67%; m.p. >2568C (decomp); 1H NMR
(C6D6, 400 MHz, 258C): d =10.20 (s, 2H; NH), 9.98 (s, 2H; NH), 9.94 (s,
2H; NH), 9.93 (s, 2H; NH), 8.59 (brt, unresolved coupling, 2H; Armeta
.
7.43 (brt, unresolved coupling, 2H; Armeta-H), 7.40 (s, 2H; NH), 7.35
3
(brdd, J=6.8 Hz, unresolved coupling, 2H; Armeta-H), 7.25–7.13 (overlap
A
N
with the solvent signal, 2”s, 4H; NH, d and 2”t, 6H; Armeta-H), 7.10 (t,
1
ACHTREUNG
3
3J=8.2 Hz, 2H; Armeta-H), 7.03 (t, J=8.2 Hz, 2H; Armeta-H), 6.93 (s, 2H;
NH), 6.74 (dd, 3J=7.8, 4J=1.4 Hz, 2H; Armeta-H), 6.68 (dd, 3J=8.2, 4J=
1.0 Hz, 2H; Armeta-H), 6.58 (dd, 3J=8.2, 4J=1.7 Hz, 2H; Armeta-H), 6.50
-
3
H), 8.36 (brdd, J=8.2 Hz, unresolved coupling, 2H; Armeta-H), 8.31 (brt,
unresolved coupling, 2H; Armeta-H), 8.26 (d, 3J=7.8 Hz, unresolved cou-
pling, 2H; Armeta-H), 8.21 (d, 4J=2.4 Hz, 2H; Arcalix-H), 8.15 (d, 4J=
2.7 Hz, 2H; Arcalix-H), 8.03 (d, 4J=2.4 Hz, 2H; Arcalix-H), 7.78 (d, 4J=
2.4 Hz, 2H; Arcalix-H), 7.65 (brt, unresolved coupling, 2H; Armeta-H), 7.47
(brt, unresolved coupling, 2H; Armeta-H), 7.45 (brdd, overlapped with
the next signal, 2H; Armeta-H), 7.44 (s, 2H; NH), 7.39 (s, 2H; NH), 7.24
(t, 3J=7.8 Hz, 2H; Armeta-H), 7.20–7.12 (d, overlap with the solvent
signal, 2H; Armeta-H), 7.12 (t, 3J=8.3 Hz, 2H; Armeta-H), 7.06 (t, 3J=
8.2 Hz, 2H; Armeta-H), 7.00 (t, 3J=8.2 Hz, 2H; Armeta-H), 6.82 (s, 2H;
NH), 6.76 (dd, 3J=8.5, 4J=1.7 Hz, 2H; Armeta-H), 6.71 (dd, 3J=8.2, 4J=
1.7 Hz, 2H; Armeta-H), 6.68 (dd, 3J=8.5, 4J=2.0 Hz, 2H; Armeta-H), 6.63
(s, 2H; NH), 6.61 (dd, 3J=8.2, 4J=1.4 Hz, 2H; Armeta-H), 6.39 (d, 4J=
2.7 Hz, 2H; Arcalix-H), 6.29 (d, 4J=2.4 Hz, 2H; Arcalix-H), 6.11 (d, 4J=
2.7 Hz, 2H; Arcalix-H), 6.12 (d, 4J=2.4 Hz, 2H; Arcalix-H), 4.58 (d, 2J=
11.6 Hz, 2H; Ar-CH2-Arax), 4.56 (d, 2J=12.3 Hz, 2H; Ar-CH2-Arax), 4.53
(d, 2J=11.6 Hz, 2H; Ar-CH2-Arax), 4.41 (d, 2J=11.9 Hz, 2H; Ar-CH2-
Arax), 4.25–3.95 (m, 8H; -OCH2-), 3.90 (m, 2H; -OCH2-), 3.85–3.65 (m,
(dd, 3J=8.2, 4J=1.7 Hz, 2H; Armeta-H), 6.22 (d, 4J=2.3 Hz, 2H; Arcalix
-
4
4
H), 6.18 (d, J=2.4 Hz, 2H; Arcalix-H), 6.11 (d, J=2.7 Hz, 2H; Arcalix-H),
6.09 (d, 4J=2.7 Hz, 2H; Arcalix-H), 4.24 (d, 2J=11.9 Hz, 2H; Ar-CH2-
Arax), 4.19 (d, 2J=11.9 Hz, 2H; Ar-CH2-Arax), 4.17 (d, 2J=11.6 Hz, 2H;
Ar-CH2-Arax), 4.12 (d, 2J=11.6 Hz, 2H; Ar-CH2-Arax), 4.05–3.70 (m,
16H; -OCH2-), 3.58 (s, 6H; -OCH3), 3.56 (s, 6H; -OCH3), 3.47 (s, 6H;
-OCH3), 3.44 (s, 6H; -OCH3), 3.24 (d, 2J=11.9 Hz, 2H; Ar-CH2-Areq),
3.13 (d, 2J=11.9 Hz, 2H; Ar-CH2-Areq), 3.06 (d, 2J=11.9 Hz, 2H; Ar-
CH2-Areq), 2.97 (d, 2J=11.9 Hz, 2H; Ar-CH2-Areq), 1.70 (m, 4H; -CH2-),
1.64 (m, 4H; -CH2-), 1.55–0.95 ppm (4”m, 56H; -CH2-); ESI-MS: m/z
(%): calcd for
C
160H184N16O24
:
2713.36; found: 2810.42 (100)
[M+THF+Na]+.
Bis[2]catenane
4(M,14): This compound was obtained from bisloop
A
3
C
1(M,8); yield 70%; m.p. >2358C (decomp);
G
solved coupling, 2H; Armeta-H), 8.07 (d, 4J=2.4 Hz, 2H; Arcalix-H), 8.04
(d, J=2.4 Hz, 2H; Arcalix-H), 8.01 (brt, unresolved coupling, 2H; Armeta
H), 7.82 (d, J=2.4 Hz, 2H; Arcalix-H), 7.78 (d, J=2.4 Hz, 2H; Arcalix-H),
7.55 (brdd, J=8.2 Hz, unresolved coupling, 2H; Armeta-H), 7.50–7.45 (m,
2
20H; -OCH2-), 3.60 (m, 2H; -OCH2-), 3.34 (d, J=11.9 Hz, 2H; Ar-CH2-
4
Areq), 3.24 (d, 2J=11.9 Hz, 2H; Ar-CH2-Areq), 3.19 (d, 2J=11.6 Hz, 2H;
Ar-CH2-Areq), 2.96 (d, 2J=11.6 Hz, 2H; Ar-CH2-Areq), 2.18 (m, 4H;
-CH2-), 2.10–1.95 (m, 8H; -CH2-), 1.95–1.75 (m, 10H; -CH2-), 1.73–1.60
-
4
4
3
Chem. Eur. J. 2007, 13, 6157 – 6170
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6167

V. Bçhmer et al.
3
(m, 2H; -CH2-), 1.55–1.30 (m, 36H; -CH2-), 1.30–1.05 (m, 36H; -CH2-),
H), 7.78 (brt, unresolved coupling, 1H; Armeta-H), 7.72 (brdd, J=8.2 Hz,
0.99 (t, 3J=7.2 Hz, 6H; -CH3), 0.96 (t, 3J=7.2 Hz, 6H; -CH3), 0.95 (t,
unresolved coupling, 1H; Armeta-H), 7.71, 7.60, 7.53 (3”brt, unresolved
coupling, each 1H; Armeta-H), 7.49, 7.40 (2”brdd, J=8.2 Hz, unresolved
3
3
3J=7.5 Hz, 6H; -CH3), 0.94 ppm (t, J=7.7 Hz, 6H; -CH3); ESI-MS: m/z
coupling, 1H; Armeta-H), 7.39, 7.33, 7.27, 7.25, 7.24 (5”s, each 1H; NH),
7.20–7.00 (8”t, overlapping with the solvent signal, 8H; Armeta-H), 6.73
(%): calcd for
[M+C6D6+2Na]2+, 3158.88 (100) [M+C6D6+Na]+.
Bis[2]catenane (P,20): This compound was obtained from bisloop
(P,20) and tetraurea (P,11); yield 88%; m.p. >2478C (decomp);
C
184H232N16O24
:
3049.74; found: 1590.97 (62)
3
4
(dd, J=8.5, J=1.7 Hz, 1H; Armeta-H), 6.72 (s, 1H; NH), 6.70, 6.68, 6.66,
6.63, 6.59 (5”dd, 3J=8.5, 4J=1.7 Hz, 4”1H; 2H; Armeta-H), 6.51 (s, 1H;
NH), 6.50 (dd, 3J=8.5, 4J=1.7 Hz, 1H; Armeta-H), 6.35 (d, 4J=2.4 Hz,
1H; Arcalix-H), 6.31 (brd, unresolved coupling, 3H; Arcalix-H), 6.28, 6.25,
4
ACHTREUNG
3
A
1
ACHTREUNG
1H NMR (C6D6, 400 MHz, 258C): d=10.02 (s, 2H; NH), 10.00 (s, 2H;
NH), 9.99 (s, 4H; NH), 8.21 (d, 4J=2.4 Hz, 2H; Arcalix-H), 8.20–8.15 (4”
m, 8H; Armeta-H, Arcalix-H), 8.10 (brd and brt, 4H; Arcalix-H, Armeta-H),
8.04 (d, 4J=2.4 Hz, 2H; Arcalix-H), 7.74 (brt, unresolved coupling, 2H;
Armeta-H), 7.67 (brdd, 3Jꢀ7.8 Hz, unresolved coupling, 2H; Armeta-H),
7.66 (brt, unresolved coupling, 2H; Armeta-H), 7.59 (dd, 3J=7.8, 4J
ꢀ1.0 Hz, 2H; Armeta-H), 7.30 (s, 2H; NH), 7.20–7.10 (2”s and 4”t, over-
lap with the solvent signal, 12H; NH and Armeta-H), 7.04 (s, 2H; NH),
4
6.11 (3”d, J=2.4 Hz, 2”1H; 2H; Arcalix-H), 4.65–4.52 (m, 6H; Ar-CH2-
Arax), 4.50, 4.46 (2”d, 2J=11.6 Hz, each 1H; Ar-CH2-Arax), 4.19, 4.08
(2”m, each 2H; -OCH2-), 3.95–3.50 (m, 28H; -OCH2-), 3.40, 3.35, 3.31,
3.264, 3.261, 3.20, 3.12, 3.04 (8”d, 2J=11.6 Hz, each 1H; Ar-CH2-Areq),
2.25–1.85 (several m, 16H; -OCH2CH2-), 1.80–0.90 ppm (m, 150H; -CH2-
, -CH3); ESI-MS: m/z (%): calcd for C208H280N16O24: 3386.11; found:
1717.08 (100) [M+2Na]2+
.
3
4
3
4
6.64 (dd, J=8.2, J=2.0 Hz, 2H; Armeta-H), 6.60 (dd, J=8.2, J=2.0 Hz,
3
4
3
Bis[2]catenane (D,10): This compound was obtained from bisloop
4
ACHTREUNG
2H; Armeta-H), 6.55 (dd, J=8.5, J=1.7 Hz, 2H; Armeta-H), 6.52 (dd, J=
8.5, 4J=1.7 Hz, 2H; Armeta-H), 6.29 (brd, unresolved coupling, 4H;
Arcalix-H), 6.25 (d, 4J=2.0 Hz, 2H; Arcalix-H), 4.58 (d, 2Jꢀ11.0 Hz, 2H;
Ar-CH2-Arax), 4.56 (d, 2Jꢀ11.0 Hz, 4H; Ar-CH2-Arax), 4.54 (d, 2J=
11.0 Hz, 2H; Ar-CH2-Arax), 3.95–3.65 (m, 32H; -OCH2-), 3.36 (d, 2J=
11.6 Hz, 2H; Ar-CH2-Areq), 3.31 (d, 2J=11.9 Hz, 2H; Ar-CH2-Areq), 3.30
(d, 2J=11.9 Hz, 2H; Ar-CH2-Areq), 3.25 (d, 2J=11.6 Hz, 2H; Ar-CH2-
Areq), 2.15 (m, 8H; -CH2-), 2.04 (m, 8H; -CH2-), 1.61 (m, 8H; -CH2-),
1.55–1.10 (m, 168H; -CH2-), 1.04 (brt, 3Jꢀ6.0 Hz, 6H; -CH3), 1.03 (brt,
3Jꢀ6.0 Hz, 6H; -CH3), 0.96 ppm (t, 3J=7.2 Hz, 12H; -CH3); ESI-MS:
3
N
1(D,6); yield 50%; m.p. >2468C (decomp);
G
NH), 9.93 (s, 2H; NH), 8.46 (brt, unresolved coupling, 2H; Armeta-H),
3
8.37 (m, 4H; Armeta-H), 8.29 (brdd, J=7.8 Hz, unresolved coupling, 2H;
Armeta-H), 8.20 (d, 4J=2.0 Hz, 2H; Arcalix-H), 8.18 (d, 4J=2.0 Hz, 2H;
Arcalix-H), 8.04 (d, 4J=2.4 Hz, 2H; Arcalix-H), 7.99 (d, 4J=2.4 Hz, 2H;
Arcalix-H), 7.62 (brt, unresolved coupling, 2H; Armeta-H), 7.51 (brt, unre-
solved coupling, 2H; Armeta-H), 7.42 (brd, 3J=7.8 Hz, unresolved cou-
pling, 2H; Armeta-H), 7.37 (s, 2H; NH), 7.36 (s, 2H; NH), 7.21 (t, 3J=
8.2 Hz, 2H; Armeta-H), 7.20–7.12 (d, overlap with the solvent signal, 2H;
Armeta-H), 7.11 (t, 3J=8.2 Hz, 2H; Armeta-H), 7.10 (t, 3J=7.8 Hz, 2H;
Armeta-H), 7.02 (t, 3J=8.2 Hz, 2H; Armeta-H), 6.96 (s, 2H; NH), 6.85 (s,
2H; NH), 6.75 (dd, 3J=8.2, 4J=2.0 Hz, 2H; Armeta-H), 6.68 (dd, 3J=8.2,
4J=1.2 Hz, 2H; Armeta-H), 6.57 (dd, 3J=8.2, 4J=1.6 Hz, 2H; Armeta-H),
6.50 (dd, 3J=8.2, 4J=1.6 Hz, 2H; Armeta-H), 6.40 (d, 4J=2.0 Hz, 2H;
Arcalix-H), 6.38 (d, 4J=2.4 Hz, 2H; Arcalix-H), 6.26 (d, 4J=2.4 Hz, 2H;
Arcalix-H), 6.24 (d, 4J=2.4 Hz, 2H; Arcalix-H), 4.58 (d, 2J=12.9 Hz, 2H;
Ar-CH2-Arax), 4.55 (d, 2J=11.7 Hz, 2H; Ar-CH2-Arax), 4.53 (d, 2J=
12.9 Hz, 2H; Ar-CH2-Arax), 4.50 (d, 2J=12.5 Hz, 2H; Ar-CH2-Arax),
4.10–3.50 (m, 32H; -OCH2-), 3.36 (d, 2J=12.1 Hz, 2H; Ar-CH2-Areq),
3.25 (d, 2J=11.4 Hz, 2H; Ar-CH2-Areq), 3.22 (d, 2J=11.4 Hz, 2H; Ar-
CH2-Areq), 3.11 (d, 2J=11.7 Hz, 2H; Ar-CH2-Areq), 2.30–1.90 (m, 16H;
-CH2-),1.80–1.50 (m, 8H; -CH2-), 1.50–1.00 (m, 168H; -CH2-), 0.96 ppm
m/z (%): calcd for
[M+2Na]2+
Bis[2]catenane 5
(P,8) and tetraurea 1(P,8); yield 81%; m.p. >2428C (decomp); H NMR
C232H328N16O24: 3722.49; found: 1885.47 (100)
.
A
1
3
A
(C6D6, 400 MHz, 258C): d=10.04 (s, 2H; NH), 10.00 (s, 1H; NH), 9.96
(s, 1H; NH), 9.95 (s, 2H; NH), 9.89 (s, 1H; NH), 9.83 (s, 1H; NH), 8.47
(brt, unresolved coupling, 1H; Armeta-H), 8.42 (brdd, 3J=7.8 Hz, unre-
solved coupling, 1H; Armeta-H), 8.40 (brt, unresolved coupling, 1H;
Armeta-H), 8.29 (brdd, 3J=7.8 Hz, unresolved coupling, 1H; Armeta-H),
8.28 (brt, unresolved coupling, 2H; Armeta-H), 8.27–8.22 (m, 2H; Armeta
-
H, 1H; Arcalix-H), 8.15 (d, 4J=2.4 Hz, 1H; Arcalix-H), 8.13 (brd, 3J=
7.8 Hz, unresolved coupling, 1H; Armeta-H), 8.12 (m, 2H; Arcalix-H), 8.01
4
4
(d, J=2.4 Hz, 1H; Arcalix-H), 7.84 (m, 2H; Arcalix-H), 7.81 (d, J=2.4 Hz,
1H; Arcalix-H), 7.61 (brdd, 3J=8.2 Hz, unresolved coupling, 1H; Armeta
(t, 3J=6.7 Hz, 24H; -CH3); ESI-MS: m/z (%): calcd for C232H328N16O24
3722.49; found: 1885.38 (100) 1921.42 (54)
[M+2Na]2+
[M+THF+2Na]2+
Bis[2]catenane (D,14): This compound was obtained from bisloop
(D,14) and tetraurea (D,8); yield 97%; m.p. >2508C (decomp);
:
-
H), 7.57(brt, unresolved coupling, 1H; Armeta-H), 7.55 (brt, unresolved
coupling, 1H; Armeta-H), 7.52, 7.43, 7.427, 7.418, (4”s, each 1H; NH),
,
.
3
7.40 (brt, unresolved coupling, 1H; Armeta-H), 7.37 (brdd, J=8.2 Hz, un-
4
ACHTREUNG
resolved coupling, 1H; Armeta-H), 7.30, 7.28 (2”s, each 1H; NH), 7.25 (t,
3J=8.2 Hz, 1H; Armeta-H), 7.20–7.00 (m, overlapping with the solvent
signal, 6H; Armeta-H), 6.73 (s, 1H; NH), 6.72, 6.70, 6.68, 6.63, 6.61, 6.55,
6.50 (7”dd, 3J=8.2, 4J=1.7 Hz, each 1H; Armeta-H), 6.44 (s, 1H; NH),
6.39 (dd, 3J=8.2, 4J=1.7 Hz, 1H; Armeta-H), 6.37 (d, 4J=2.4 Hz, 1H;
Arcalix-H), 6.36 (d, 4J=2.4 Hz, 1H; Arcalix-H), 6.35 (d, 4J=2.4 Hz, 1H;
3
A
1
ACHTREUNG
1H NMR (C6D6, 400 MHz, 258C): d=10.02 (s, 2H; NH), 9.95 (s, 2H;
NH), 9.93 (s, 2H; NH), 9.87 (s, 2H; NH), 8.34 (brdd, 3J=7.8 Hz, unre-
solved coupling, 2H; Armeta-H), 8.31 (brt, unresolved coupling, 2H;
Armeta-H), 8.20 (brdd, 3J=8.2 Hz, unresolved coupling, 2H; Armeta-H),
4
8.18–8.16 (m, 4H; Armeta-H, Arcalix-H), 8.15 (d, J=2.0 Hz, 2H; Arcalix-H),
4
Arcalix-H), 6.29 (m, 2H; Armeta-H), 6.27 (d, J=2.4 Hz, 1H; Arcalix-H), 6.12
7.96 (d, 4J=2.0 Hz, 2H; Arcalix-H), 7.94 (d, 4J=2.4 Hz, 2H; Arcalix-H),
7.55–7.50 (brdd and brt, 4H; Armeta-H), 7.45 (brt, unresolved coupling,
2H; Armeta-H), 7.42 (brd, 3Jꢀ8 Hz, unresolved coupling, 2H; Armeta-H),
4
(d, 4J=2.4 Hz, 1H; Arcalix-H), 6.06 (d, J=2.4 Hz, 1H; Arcalix-H), 4.62 (d,
2J=11.6 Hz, 1H; Ar-CH2-Arax), 4.55 (d, 2J=11.6 Hz, 2H; Ar-CH2-Arax),
4.54, 4.52, 4.49, 4.46, 4.41 (5”d, 2J=11.6 Hz, each 1H; Ar-CH2-Arax),
4.17, 4.07 (2”m, each 2H; -OCH2-), 3.95–3.50 (m, 28H; -OCH2-), 3.41,
3.34, 3.28, 3.25, 3.22, 3.20, 3.08, 2.97 (8”d, 2J=11.9 Hz, each 1H; Ar-
CH2-Areq), 2.20–1.80 (2”m, 16H; -CH2-), 1.80–0.90 ppm (m, 126H;
7.41 (s, 2H; NH), 7.35 (s, 2H; NH), 7.25 (s, 2H; NH), 7.20–7.12 (t, over-
3
lap with the solvent signal, 2H; Armeta-H), 7.11 (t, J=8.2 Hz, 2H; Armeta
-
3
3
H), 7.05 (t, J=8.2 Hz, 2H; Armeta-H), 7.01 (t, J=8.2 Hz, 2H; Armeta-H),
6.95 (s, 2H; NH), 6.63 (dd, 3J=8.2, 4J=2.0 Hz, 2H; Armeta-H), 6.47 (dd,
3J=8.2, 4J=1.7 Hz, 2H; Armeta-H), 6.45 (dd, 3J=8.2, 4J=1.76 Hz, 2H;
Armeta-H), 6.43 (dd, 3J=8.2, 4J=1.7 Hz, 2H; Armeta-H), 6.36 (d, 4J=
2.4 Hz, 2H; Arcalix-H), 6.33 (d, 4J=2.4 Hz, 2H; Arcalix-H), 6.30 (d, 4J=
2.4 Hz, 2H; Arcalix-H), 6.26 (d, 4J=2.4 Hz, 2H; Arcalix-H), 4.61 (d, 2J=
11.6 Hz, 2H; Ar-CH2-Arax), 4.57 (d, 2J=12.6 Hz, 2H; Ar-CH2-Arax), 4.54
(d, 2J=12.3 Hz, 2H; Ar-CH2-Arax), 4.51 (d, 2J=11.6 Hz, 2H; Ar-CH2-
Arax), 4.10–3.50 (m, 32H; -OCH2-), 3.36 (d, 2J=11.6 Hz, 2H; Ar-CH2-
Areq), 3.29 (d, 2J=11.2 Hz, 4H; Ar-CH2-Areq), 3.23 (d, 2J=11.9 Hz, 2H;
Ar-CH2-Areq), 2.30–2.00 (m, 16H; -CH2-), 1.80–1.05 (2”m, 8H; -CH2-),
1.50–1.00 (m, 208H; -CH2-), 0.97 (t, 3J=6.7 Hz, 24H; -CH3) ppm; ESI-
MS: m/z (%): calcd for C248H360N16O24: 3946.74; found: 1632.99 (100)
[M+2Na]2+, 3242.97 (90) [M+Na]+.
-CH2-, -CH3); ESI-MS: m/z (%): calcd for C196H256N16O24
found: 1632.99 (100) [M+2Na]2+, 3242.97 (90) [M+Na]+.
: 3217.93;
Bis[2]catenane 5
ACHTREUNG
3
A
1
ACHTREUNG
1H NMR (C6D6, 400 MHz, 258C): d=10.08, 10.06, 10.05, 10.02, 9.98, 9.95
(6”s, each 1H; NH), 9.93 (s, 2H; NH), 8.45 (brt, unresolved coupling,
1H; Armeta-H), 8.39 (brt, unresolved coupling, 1H; Armeta-H), 8.28 (brdd,
3J=8.2 Hz, unresolved coupling, 1H; Armeta-H), 8.26–8.20 (m, 4H;
Armeta-H, 2H; Arcalix-H), 8.16 (d, 4J=2.4 Hz, 1H; Arcalix-H), 8.14 (d, 4J=
2.4 Hz, 1H; Arcalix-H), 8.12 (brt, unresolved coupling, 1H; Armeta-H), 8.07
(d, 4J=2.4 Hz, 1H; Arcalix-H), 8.05 (brdd, 3J=8.2 Hz, unresolved cou-
pling, 1H; Armeta-H), 7.94, 7.93, 7.92 (3”d, 4J=2.4 Hz, each 1H; Arcalix
-
6168
www.chemeurj.org
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 6157 – 6170

Calix[4]arene-Based Bis[2]catenanes
FULL PAPER
Monoloop-diBoc: A solution of bisurethane (0.5 g, 0.73 mmol) in DMF
(50 mL) and a solution of 1,2-diBoc-protected tetraaminocalix[4]arene
(0.54 g, 0.56 mmol, and 3–5 drops of triethylamine) in DMF (50 mL)
were dropped over 12 h into a 250 mL round-bottomed flask. After the
mixing of the two solutions, the yellow reaction mixture was stirred for
24 h. The solvent was then evaporated to dryness and the residue was dis-
solved in dichloromethane (250 mL) and washed with K2CO3 solution
(3–5”200 mL, until the water layer was colorless) and once with water
(200 mL). The organic layer was dried over MgSO4 and the solvent was
removed at reduced pressure to give a final volume of 4–5 mL. The pure
product was obtained after column chromatography (ethyl acetate/
Bis[2]catenane 7
G
5
ACHTREUNG
258C): d=10.07 (s, 1H; NH), 10.04 (s, 1H; NH), 10.01 (s, 1H; NH), 9.97
(s, 1H; NH), 9.916 (s, 1H; NH), 9.912 (s, 1H; NH), 9.86 (s, 1H; NH),
9.79 (s, 1H; NH), 8.47 (t, 4J=2.0 Hz, 1H; Armeta-H), 8.42 (t, 4J=1.9 Hz,
1H; Armeta-H), 8.36, 8.34 (brdd, 3J=8.0 Hz, unresolved coupling, 1H;
Armeta-H), 8.35, 8.33 (dd, 3J=7.8, 4J=1.4 Hz, 1H; Armeta-H), 8.31–8.28
(m, 2H; Armeta-H, 1H; Arcalix-H), 8.23 (d, J=2.4 Hz, 1H; Arcalix-H), 8.20
(t, 4J=2.0 Hz, 2H; Armeta-H), 8.11 (brdd, 3J=7.8 Hz, unresolved cou-
pling, 1H; Armeta-H), 8.06 (d, 4J=2.4 Hz, 1H; Arcalix-H), 8.04 (d, 4J=
2.7 Hz, 1H; Arcalix-H), 7.98 (d, 4J=2.4 Hz, 1H; Arcalix-H), 7.90 (d, 4J=
2.7 Hz, 1H; Arcalix-H), 7.89 (d, 4J=2.7 Hz, 1H; Arcalix-H), 7.74 (d, 4J=
2.7 Hz, 1H; Arcalix-H), 7.63 (t, 4J=2.0 Hz, 1H; Armeta-H), 7.57–7.54 (m,
2H; Armeta-H, 1H; NH), 7.48 (s, 1H; NH), 7.47 (s, 1H; NH), 7.43, 7.41
(brdd, 3Jꢀ8, 4Jꢀ1 Hz, 1H; Armeta-H), 7.41, 7.39 (brdd, 3Jꢀ8, 4Jꢀ1 Hz,
1H; Armeta-H), 7.36 (t, 4J=2.0 Hz, 1H; Armeta-H), 7.33 (brt, unresolved
coupling, 1H; Armeta-H), 7.32 (s, 1H; NH), 7.22 (t, 3J=8.0 Hz, 1H;
Armeta-H), 7.20 (t, 3J=8.0 Hz, 1H; Armeta-H), 7.18–7.08 (m, overlapping
with the solvent signal, 2H; Armeta-H, 4H; NH), 7.08 (t, 3J=7.7 Hz, 1H;
Armeta-H), 7.05 (t, 3J=8.2 Hz, 1H; Armeta-H), 7.00 (t, 3J=8.3 Hz, 1H;
1
hexane 1:4). Yield 50%; H NMR ([D6]DMSO, 400 MHz, 608C): d =8.44
4
(s, 2H; NH), 8.19 (s, 2H; NH), 8.00 (s, 2H; NH), 7.23 (t, J=2.1 Hz, 2H;
Armeta-H), 7.09 (t, 3J=8.1 Hz, 2H; Armeta-H), 7.00 (d, 4J=2.2 Hz, 2H;
Arcalix-H), 6.79 (brs, 4H; Arcalix-H), 6.69, 6.67 (dd, 3J=8.1, 4J=1.2 Hz,
2H; Armeta-H), 6.49 (d, 4J=2.2 Hz, 2H; Arcalix-H), 6.49, 6.47 (dd, 3J=8.1,
4J=2.4 Hz, 2H; Armeta-H), 4.37 (d, 2J=12.7 Hz, 1H; Ar-CH2-Arax), 4.35
(d, 2J=12.9 Hz, 2H; Ar-CH2-Arax), 4.34 (d, 2J=12.5 Hz, 1H; Ar-CH2-
Arax), 3.94 (t, 3J=6.2 Hz, 4H; OCH2-), 3.86–3.81 (m, 8H; OCH2-), 3.08–
3.02 (m, 4H; Ar-CH2-Areq), 1.90–1.85 (m, 8H; -CH2-), 1.69 (m, 4H;
-CH2-), 1.44–1.38 (m, 40H; tBu+-CH2-), 0.93 ppm (m, 12H; -CH3);
13C NMR ([D6]DMSO, 100 MHz, 608C): d=159.09, 152.82, 152.24,
151.35, 151.17, 140.95, 134.32, 134.14, 134.03, 133.97, 133.10, 133.00,
129.06, 118.99, 118.83, 118.74, 118.33, 110.36, 107.59, 104.83, 78.27, 74.49,
67.20, 30.88, 30.79, 30.60, 29.08, 28.32, 28.25, 27.78, 25.15, 22.00,
13.62 ppm; ESI-MS: m/z (%): calcd for C80H108N6O12: 1344.80; found:
1368.00 (100) [M+Na]+.
Armeta-H), 6.99 (t, J=8.2 Hz, 1H; Armeta-H), 6.78 (s, 1H; NH), 6.77, 6.75
(dd, 3J=8.2, 4J=1.7 Hz, 1H; Armeta-H), 6.72, 6.70 (dd, 3J=8.2, 4J=
1.7 Hz, 1H; Armeta-H), 6.697 and 6.67 (dd, 3J=8.2, 4J=1.7 Hz, 1H;
Armeta-H), 6.63, 6.61 (dd, 3J=8.2, 4J=1.4 Hz, 1H; Armeta-H), 6.62, 6.60
(dd, 3J=8.2, 4J=2.0 Hz, 1H; Armeta-H), 6.57, 6.55 (dd, 3J=8.2, 4J=
2.0 Hz, 1H; Armeta-H), 6.46, 6.44 (dd, 3J=8.2, 4J=2.0 Hz, 1H; Armeta-H),
6.41 (s, 1H; NH), 6.39, 6.37 (dd, 3J=8.2, 4J=1.9 Hz, 1H; Armeta-H), 6.37
(d, 4J=2.7 Hz, 1H; Arcalix-H), 6.34 (d, J=2.4 Hz, 2H; Arcalix-H), 6.31 (d,
Monoloop bisalkenyl 6(P,8): The compound was synthesized from the
E
4J=2.4 Hz, 1H; Arcalix-H), 6.29 (d, 4J=2.7 Hz, 1H; Armeta-H), 6.28 (d,
4J=2.7 Hz, 1H; Arcalix-H), 6.08 (d, 4J=2.4 Hz, 1H; Arcalix-H), 6.07 (d,
4J=2.4 Hz, 1H; Arcalix-H), 4.61 (d, 2J=11.6 Hz, 2H; Ar-CH2-Arax), 4.56,
4.55, 4.48, 4.47, 4.46, 4.38 (6”d, 2J=11.6 Hz, each 1H; Ar-CH2-Arax),
4.28–4.07 (2”m, each 2H; -OCH2-), 3.90–3.55 (m, 28H; -OCH2-), 3.38,
3.35, 3.27, 3.26, 3.24, 3.17, 3.14, 2.91 (8”d, 2J=11.9 Hz, each 1H; Ar-
CH2-Areq), 2.5–1 ppm unresolved multiplets; ESI-MS: m/z (%): calcd for
monoloop-diBoc derivative by the described procedure.[15] Yield 86%;
m.p. >1908C (decomposition without melting); 1H NMR ([D6]DMSO,
400 MHz, 608C): d=8.25 (s, 2H; NH), 8.19 (s, 2H; NH), 8.01 (s, 2H;
NH), 8.00 (s, 2H; NH), 7.21 (t, 3J=2.1 Hz, 2H; Armeta-H), 7.08–7.04 (m,
6H; Armeta-H), 7.02 (d, 4J=2.4 Hz, 2H; Arcalix-H), 6.86 (d, 4J=2.4 Hz,
2H; Arcalix-H), 6.81, 6.79 (dd, 3J=8.0, 4J=1.5 Hz, 2H; Armeta-H), 6.74 (d,
4J=2.4 Hz, 2H; Arcalix-H), 6.67, 6.65 (dd, 3J=7.0, 4Jꢀ1.0 Hz, 2H; Armeta
-
C196H256N16O24: 3217.93; found: 1633.07 (100) [M+2Na]2+
4
3
4
H), 6.59 (d, J=2.4 Hz, 2H; Arcalix-H), 6.49, 6.47 (dd, J=8.0, J=1.9 Hz,
4H; Armeta-H), 5.85–5.75 (m, 2H; =C-H), 5.01–4.91 (m, 4H, =CH2), 4.386
(d, 2J=12.9 Hz, 2H; Ar-CH2-Arax), 4.382 (d, 2J=12.9 Hz, 2H; Ar-CH2-
Arax), 4.0–3.88 (m, 16H; OCH2-), 3.15 (overlapping with the signal of the
solvent, 4H; Ar-CH2-Areq), 2.01 (m, 4H; -CH2-), 1.90 (m, 8H; -CH2-),
1.57–1.51 (m, 8H; -CH2-), 1.51–1.30 (m, 36H; -CH2-), 0.95 ppm (t, 3J=
6.9 Hz, 12H; -CH3); 13C NMR ([D6]DMSO, 100 MHz, 608C): d=158.79,
152.03, 150.92, 140.70, 140.65, 138.30, 134.07, 134.02, 133.99, 133.96,
132.98, 132.93, 128.82, 118.21, 118.12, 117.80, 114.04, 110.13, 110.02,
107.34, 107.28, 104.48, 104.32, 74.28, 67.04, 66.93, 32.55, 30.60, 30.46,
30.26, 28.86, 28.26, 28.02, 27.97, 27.78, 27.76, 27.54, 24.89, 24.85, 21.76,
13.37 ppm; ESI-MS: m/z (%): calcd for C100H130N8O12: 1634.98; found:
1637.10 (100) [M+H]+, 1659.08 (84) [M+Na]+.
X-raystructure analysis : Single crystals of 4(P,10) suitable for X-ray anal-
AHCTREUNG
ysis were obtained from chloroform/methanol. The structure could be
completely resolved; it clearly shows the open capsule and all four C10H20
chains.
2(C96H124N8O12)·2CHCl3·5CH3OH, formula weight 3563.01, trigonal,
3
¯
space group R3, a=76.875(2), c=18.5091(7) Š, V=94730(5) Š , Z=18,
colorless, block-shaped crystal, STOE-IPDS-II two-circle diffractometer,
T=173 K, MoKa radiation, 2q range=2.74–50.088, 261400 reflections
collected, 36746 independent reflections (Rint =0.1021), empirical absorp-
tion correction (MULABS, Blessing, 1995), structure solution with
SHELXS-90 (Sheldrick, 1990), refinement on F2 with SHELXL-97 (Shel-
drick, 1997), R1[I>2s(I)]=0.219, GOF=1.67. The methylene chains
G
were refined with restraints of 1.50(1) Š for 1–2 and 2.4(1) Š for 1–3 dis-
Monoloop bisalkenyl 6(P,11): The compound was synthesized from the
G
monoloop-diBoc derivative by the described procedure.[15] Yield 77%;
m.p. >1908C (decomposition without melting); 1H NMR ([D6]DMSO,
400 MHz, 608C): d=8.25 (s, 2H; NH), 8.19 (s, 2H; NH), 8.02 (s, 2H;
NH), 8.00 (s, 2H; NH), 7.21 (brt, unresolved coupling, 2H; Armeta-H),
7.07–7.04 (m, 6H; Armeta-H), 7.02 (d, 4J=2.4 Hz, 2H; Arcalix-H), 6.86 (d,
4J=2.2 Hz, 2H; Arcalix-H), 6.78 (brdd, 3J=8.0 Hz, unresolved coupling,
ꢁ
tances. The methanol C O distances were restrained to 1.40(1) Š and
ꢁ
the C Cl distances to 1.70(1) Š.
CCDC-637006 contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
4
3
2H; Armeta-H), 6.73 (d, J=2.4 Hz, 2H; Arcalix-H), 6.65 (brdd, J=7.0 Hz,
unresolved coupling, 2H; Armeta-H), 6.59 (d, 4J=2.4 Hz, 2H; Arcalix-H),
6.48, 6.46 (dd, 3J=8.0, 4J=1.9 Hz, 4H; Armeta-H), 5.84–5.73 (m, 2H,=C-
H), 5.00–4.90 (m, 4H, =CH2), 4.37 (d, 2J=12.9 Hz, 4H; Ar-CH2-Arax),
3.95–3.85 (m, 16H; OCH2-), 3.08 (overlapping with the signal of the sol-
vent, 4H; Ar-CH2-Areq), 2.01 (m, 4H; -CH2-), 1.90 (m, 8H; -CH2-), 1.57–
Acknowledgements
These studies were supported by the Deutsche Forschungsgemeinschaft
(Bo523/14).
3
1.51 (m, 8H; -CH2-), 1.51–1.43 (m, 48H; -CH2-), 0.96 ppm (t, J=7.0 Hz,
12H; -CH3); 13C NMR ([D6]DMSO, 100 MHz, 258C): d=158.79, 152.02,
150.91, 150.89, 140.69, 140.64, 138.36, 134.07, 134.02, 133.99, 132.98,
132.93, 128.81, 118.20, 118.11, 118.08, 118.06, 117.79, 113.98, 110.12,
110.01, 107.35, 107.29, 104.49, 104.30, 74.28, 67.05, 66.92, 32.61, 30.25,
28.86, 28.42, 28.31, 28.28, 28.25, 27.99, 27.82, 27.54, 25.04, 24.85, 21.76,
13.38 ppm; ESI-MS: m/z (%): calcd for C106H142N8O12: 1719.07; found:
1743.17 (100) [M+Na]+.
[1] Molecular Catenanes, Rotaxanes, and Knots (Eds.: J.-P. Sauvage, C.
Dietrich-Buchecker), Wiley-VCH, Weinheim, 1999.
[2]For an actual review on “Templated Synthesis of Interlocked Mole-
cules” see: F. Aricó, J. D. Badjic, S. J. Cantrill, A. H. Flood, K. C.-F.
Leung, Y. Liu, F. Stoddart, Top. Curr. Chem. 2005, 249, 203–259.
Chem. Eur. J. 2007, 13, 6157 – 6170
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6169

V. Bçhmer et al.
[3]E. Wassermann, J. Am. Chem. Soc. 1960, 82, 4433–4434; H. L.
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ꢁ
an additional dependence on the torsion angle around the NH Ar
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A
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Received: December 18, 2006
Published online: April 30, 2007
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