Multifold photocyclization reactions of styrylcalix[4]arenes

Article abstract of DOI:10.1002/ejoc.201001108

A photochemical transannular [2+2] cycloaddition reaction is the main reaction pathway for 1,3-substituted styrylcalix[4]arenes, whereas 1,2-distyrylcalix[4]arenes give calix[4]diphenanthrenes. Oxidative cyclization to phenanthrenes and the transannular [2+2] cycloaddition reaction are observed as competing processes during the photolysis of distyryl- and tetrastyryl-substituted calix[4]arenes. Copyright

Full text of DOI:10.1002/ejoc.201001108

FULL PAPER
DOI: 10.1002/ejoc.201001108
Multifold Photocyclization Reactions of Styrylcalix[4]arenes
Wiebke Hüggenberg,[a] Annamaria Seper,[a] Iris M. Oppel,[b] and Gerald Dyker*[a]
Keywords: Photochemistry / Calixarenes / Fused-ring systems / Cycloaddition / Annulation
A photochemical transannular [2+2] cycloaddition reaction is
the main reaction pathway for 1,3-substituted styrylcalix-
[4]arenes, whereas 1,2-distyrylcalix[4]arenes give calix[4]di-
phenanthrenes.
calixarene 1 by Wittig reaction of diformylcalixarene[4]
3
Introduction
with benzyltriphenylphosphonium chloride (Scheme 2).
Product 4 was obtained in excellent yield as a mixture of
the three different E/Z isomers and the molecular mass was
verified by a peak at m/z = 796 in the FAB mass spectrum.
A 1:2 ratio of the E and Z stilbene units was determined
from the integrals of the bridging methylene proton signals
Calixarenes and resorcinarenes that provide well-defined
electron-rich cavities are favourite systems for studying
host–guest interactions.[1,2] Extending and functionalizing
the rims of the cavities should give access to tailor-made
hosts for molecular recognition.
We have previously reported optimized reaction condi-
tions for the oxidative photocyclization of monostyrylcalix-
arene 1 to the first calix[4]monophenanthrene 2 by the irra-
diation of 1 with iodine and potassium carbonate in ben-
zene (Scheme 1).[3] The presence of the base proved to be
crucial for inhibiting acid-catalysed ring cleavage at an in-
termediary enol ether moiety, giving rise to a linear tetra-
mer as the major product. Herein we describe the synthesis
of calixarenes with multiple stilbene units and their photo-
chemical cyclization reactions.
1
and in comparison with the published H NMR spectro-
scopic data for the pure (E,E)-distyrylcalixarene (prepared
by Horner–Wadsworth–Emmons reaction in 73% yield).[4]
We also succeeded in obtaining the sole E,E isomer by the
reported iodine-catalysed isomerization.[4]
The photochemical cyclization of calixarene 4 with a me-
dium-pressure Hg lamp (125 W) in the presence of iodine
and potassium carbonate in benzene yielded 90% of cycli-
1
zation products. In the H NMR spectrum the diagnostic
signal for the bay-region proton was registered at around
8.63 ppm, proving the formation of phenanthrene. How-
ever, HPLC clearly indicated the presence of three different
products, two of which were poorly resolved. The cyclo-
butane-bridged calixarene 6 was the only compound that
could be isolated analytically pure in a 37% yield
(Scheme 3). Clearly this product is a result of a transannu-
lar [2+2] cycloaddition reaction of the stilbene units, com-
parable to the synthesis of ladderanes from functionalized
[2.2]paracyclophanes described by Hopf et al.[5] The 13C
NMR spectrum exhibits diagnostic signals at δ = 45.0 and
48.7 ppm arising from cyclobutane carbons. The signals of
the corresponding protons appear at δ = 3.76 and 3.86 ppm
in the 1H NMR spectrum. In addition, a peak at m/z = 796
in the FAB mass spectrum confirms the molecular mass,
identical to the molecular mass of the starting material,
therefore excluding oxidative cyclization to the target ca-
lix[4]diphenanthrene 5. Notably, the extraordinary upfield
shift of the m-aryl protons of the substituted phenyl units
to δ = 5.50 and 5.86 ppm reveals that calixarene 6 is fixed
in a pinched cone conformation. The bridging cyclobutane
leads to the coplanarity of the opposite benzene rings,
whereas the unsubstituted units stick out. The 13C NMR
spectrum before crystallization clearly indicates a cone con-
formation as there are no signals at about 37 ppm for meth-
Scheme 1. Optimized reaction conditions for the synthesis of
calixarene 2.
Results and Discussion
As an approach to calixphenanthrene 5 we prepared di-
styrylcalixarene 4 in analogy to the synthesis of monostyryl-
[a] Fakultät für Chemie, Ruhr-Universität Bochum,
Universitätsstrasse 150, 44780 Bochum, Germany
Fax: +49-234-32-14353
E-mail: gerald.dyker@ruhr-uni-bochum.de
[b] Institut für Anorganische Chemie, RWTH Aachen,
Landoltweg 1, 52074 Aachen, Germany
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201001108.
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Multifold Photocyclization Reactions of Styrylcalixarenes
Scheme 2. Synthesis and photolysis of styrylcalix[4]arene 4.
ylene carbons, which would indicate an anti orientation of lecular peak at m/z = 794 in the FAB mass spectrum, and
the adjacent phenyl units in the calixarene ring.[6] However, the desired calixdiphenanthrene 5, unfortunately obtained
the crystal structure analysis of a randomly picked single as a minor by-product. Overall, a product ratio of 6:4:1 was
crystal surprisingly showed 6 in a partial cone conformation determined for compounds 6, 7 and 5.
(Figure 1). According to semi-empirical PM3 calculations
Photolysis of the four-fold stilbene 8 under the same re-
the partial cone conformation is minimally favoured by action conditions as for 4 gave a highly complex mixture of
0.8 kcalmol–1 compared with the cone conformation, but cyclization products, as observed by Mattay and Barton.[8]
interconversion between the two conformations is pre- After separation by HPLC we succeeded in isolating an
vented by the propyl groups.[7] Therefore we assume that analytically pure sample of the cyclobutane-bridged calix-
the crystals obtained do not represent the bulk material, [4]diphenanthrene diastereomer 9 in 1% yield (Scheme 3).
1
but a minor impurity not detectable in the NMR spectra. The H NMR spectrum exhibits a diagnostic signal of the
Two additional fractions isolated by HPLC showed diag- phenanthrene 5-H at δ = 8.51 ppm and diagnostic signals
1
nostic phenanthrene H NMR signals at around 8.6 ppm. for the cyclobutane ring in the 13C NMR spectrum appear
Based on the integration of the NMR signals we identified at δ = 44.3, 46.2, 47.7 and 47.9 ppm. The large upfield shift
these fractions as calixmonophenanthrene 7, with the mo- of the meta protons of the bridged phenyl units to δ = 5.01,
Scheme 3. [2+2] cycloaddition by photolysis of styrylcalix[4]arene 8.
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Therefore we developed an independent synthetic pro-
cedure for the synthesis of diformylcalixarene 15: Parent
calix[4]arene 10 was stirred with sodium hydride and benzyl
bromide in acetonitrile at room temperature[9] to yield the
proximally substituted dibenzylcalixarene 11 in up to 47%
yield. Tetrabenzylcalix[4]arene and monobenzylcalix[4]-
arene were isolated in yields of up to 32 and 6% along with
traces of the distally substituted dibenzylcalixarene and
starting material. Bromination of 11 was achieved accord-
ing to a literature procedure[9] by treatment with N-bromo-
succinimide in 2-butanone to give 86% of dibromo com-
pound 12. Removal of the benzyl groups with aluminium
chloride in toluene at 0 °C[8] led to 85% of the 5,11-dibro-
mocalixarene 13,[10] easily identified by the broad 1H NMR
signals of the methylene protons. Introduction of the propyl
groups under standard reaction conditions[11] resulted in an
excellent 94% yield of calixarene 14, which was transformed
into the diformylcalixarene 15[12] by lithiation with n-butyl-
lithium in THF and subsequent treatment with DMF in
45% yield. Wittig reaction of 14 with benzyltriphenylphos-
phonium chloride resulted in a 93% yield of the desired
distyrylcalixarene 16. Due to the formation of a mixture of
the possible E/Z isomers the signal pattern for the bridging
methylene protons in the 1H NMR spectrum was rather
complex: six signals for equatorial protons and seven for
axial protons. Again, isomerization with iodine led to a sim-
pler spectrum, especially in the aliphatic region, showing
only three doublets for equatorial protons and one at δ =
4.46 ppm for the axial ones. In the 13C NMR spectrum of
the unisomerized 16, eight different peaks appear between
Figure 1. Crystal structure of cyclobutane-bridged calixarene 6 in
the partial cone conformation.
5.2, 5.6 and 6.1 ppm reveals that this structure is also fixed
in a pinched cone conformation. The upfield shift is further
increased by the ring-current effect of the phenanthrene
units. The orientation of both phenanthrene moieties in the
same direction is verified by an anisotropic downfield shift
of two OCH2 groups to δ = 77.96 and 78.05 ppm in the 13
C
NMR spectrum, distinct from the signals of the other
OCH2 groups at δ = 76.4 and 76.5 ppm. A peak at m/z =
997 in the FAB mass spectrum also confirms the formation
of compound 9.
Because [2+2] cycloaddition should not take place be-
tween adjacent stilbene units in a calixarene, we decided
to synthesize the 1,2-distyrylcalix[4]arene 16 as a promising
model compound for oxidative bis-cyclization (Scheme 4).
Scheme 4. Synthesis of 5,11-distyrylcalix[4]arene (16).
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Multifold Photocyclization Reactions of Styrylcalixarenes
δ = 156.2 and 157.2 ppm for the tertiary aromatic carbon and the signal pattern of the propyl groups and bridging
1
atoms substituted by propoxy groups, which indicates that methylene groups in the H NMR spectrum as well as the
all possible isomers were formed. A signal at m/z = 796 in crystal structure confirm the chirality of 17a. Diagnostic
the FAB mass spectrum unambiguously identified styryl- signals for Phen-5-H appear at δ = 8.70 and 7.61 ppm. The
calixarene 16.
phenanthrene, tilted towards the cavity, experiences aniso-
The proximally disubstituted distyrylcalixarene was irra- tropic effects from the other phenanthrene. The upfield shift
diated in accord with our standard photolysis conditions of a singlet at δ = 6.00 ppm (Figure 3), assigned to one
with iodine and potassium carbonate in benzene; purifica- Phen-1-H, and the aryl protons of an unsubstituted aryl
tion by flash chromatography yielded the cyclization prod- unit prove that these units are tilted towards each other
ucts in 67% yield. From 235 mg of the material subjected (rings B and D).
to HPLC three different compounds were isolated, all of
which showed a molecular signal at m/z = 792 in the FAB
mass spectra, as expected for the three diastereoisomers of
the desired calixphenanthrenes (Scheme 5). Semi-empirical
PM3 calculations revealed that the diastereoisomer 17c
should be favoured over structures 17b and 17a by about
3.4 and 10.6 kcalmol–1, respectively. However, we were able
to clearly identify the main product as structure 17a by one-
and two-dimensional NMR experiments as well as by crys-
tal structure analysis (Figure 2). These findings suggest that
attractive π–π interactions predominate over steric repul-
sion in the first cyclization. Although the configuration of
17a is that of a meso compound, the steric demands of the
phenanthrene units pointing towards each other result in
an asymmetric conformation of the molecule. The large
Figure 2. Crystal structure of the proximal substituted calix[4]di-
number of signals, both in the H and 13C NMR spectra, phenanthrene 17a.
1
Scheme 5. Photolysis of 5,11-distyrylcalix[4]arene 16.
1
Figure 3. Partial H NMR spectrum of 17a, recorded at 600 MHz in CDCl3.
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W. Hüggenberg, A. Seper, I. M. Oppel, G. Dyker
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Thus, the meta proton facing the phenanthrene unit exhi- dition by steric hindrance. First, the modified benzyltri-
bits the strongest paratropic shift to δ = 5.30 ppm. This unit phenylphosphonium bromide 20 had to be prepared as de-
exhibits a 1.03 ppm upfield shift for its Phen-5-H as well as picted in Scheme 6. The first step involved the hydrobromi-
an even stronger paratropic shift for the corresponding nation of styrene (18) by a literature procedure[13] to give
Phen-6-H, which is found as a triplet at δ = 5.71 ppm. No- (1-bromoethyl)benzene (19) in 88–99% yield after distil-
tably, the two methylene protons at the bridge between the lation in vacuo. Subsequent conversion to compound 20,
phenanthrene units exhibit an extremely large downfield involving procedures described in the literature,[14,15] re-
shift of about 2 ppm, especially in the case of the equatorial sulted in yields lower than 50%, which prompted us to opti-
proton, appearing at δ = 5.76 and 5.81 ppm. In addition, mize the reaction conditions (Table 1). Benzyltriphenyl-
they exhibit a somewhat enlarged geminal coupling con- phosphonium bromide 20 was finally obtained in 88% yield
stant of J = 15.9 Hz compared with the normal 13.5 Hz.
by heating 19 at reflux with triphenylphosphane in toluene
The number of signals in the NMR spectra exhibited by for 3 days in a screw-capped flask.
the second compound isolated by HPLC indicates a plane
of symmetry, which can only be in agreement with structure
17b. Indeed, there are only two peaks for both the propoxy
carbons and the phenyl carbons attached to the oxygen
atoms in the 13C NMR spectrum, which confirms two dif-
ferent sets of aryl units. In addition, the three signals for
the bridging methylene carbons at δ = 30.5, 30.9 and
31.3 ppm as well as the three sets of doublets, identified by
coupling in the two-dimensional NMR spectra, confirm the
highly symmetric proximal difunctionalization of the ca-
lixarene. The diagnostic phenanthrene signal at δ =
1
8.78 ppm in the H NMR spectrum integrates to two pro-
tons, further evidence that two phenanthrene units have
been formed. The broad signals assigned to the m-aryl pro-
tons, at δ = 5.80 and 6.20 ppm, and the m-Phen protons at
δ = 7.06 ppm suggest a dynamic process. The relative up-
field shift of the aryl protons is indicative of a pinched cone
Scheme 6. Synthesis of benzyltriphenylphosphonium bromide 20.
conformation whereas the peak-broadening implies an
equilibrium of the two conformations with coalescence at
room temperature.
The third compound obtained by HPLC shows rather
complicated NMR spectra; the number of signals again im-
plies high asymmetry. On the basis of the peak in the FAB
mass spectrum at m/z = 792 and the diagnostic signal for
the phenanthrene-5-H at δ = 8.73 ppm with an integration
of two protons, it is probably the third expected stereoiso-
mer 17c with both phenanthrene units pointing in the same
direction. Regarding the missing symmetry in this isomer,
which should exist in a racemic mixture with its enantiomer,
complicated NMR spectra are of no surprise. For the bridg-
Table 1. Reaction conditions for the synthesis of (1-phenylethyl)-
triphenylphosphonium bromide 20.
Entry
Solvent
Time
Yield [%]
1
2
3
4
benzene
ethyl acetate
toluene
24 h
24 h
24 h
3 d
44[a]
45[b]
62
toluene
88
[a] Yield of 80% according to the literature.[14] [b] Yield of 78%
according to the literature.[15]
1
ing methylene units four sets of doublets appear in the H
NMR spectrum. The signals at δ = 4.52 and 4.66 ppm exhi-
bit the large downfield shifts expected for the equatorial
methylene protons in the bay region of the phenanthrene
Diformylcalixarene 3[16] was then transformed into the
units with their axial partners appearing at δ = 4.94 and corresponding distyrylcalixarene 21 in 42% yield under
5.31 ppm. The 13C NMR spectrum shows four signals for Wittig conditions (Scheme 7). Its 1H NMR spectrum is
both the propyl carbons attached to the oxygen atoms and much less complicated than that of the corresponding dis-
the bridging methylene carbon atoms and three signals for tyrylcalixarene 4 without the additional methyl groups on
the aryl carbons attached to the oxygen, one of which con- the styryl moiety as compound 21 seems to be formed al-
sists of two superimposed peaks for the PhenC–O. Broad most exclusively as the E,E isomer. Signals of the bridging
signals at δ = 6.39 and 7.49 ppm might indicate again a methylene protons of the minor isomers exhibit an upfield
dynamic process of the different pinched cone conforma- shift compared with the E,E isomer and indicate a 1:10 ra-
tions.
tio. In addition, the product is identified by its FAB mass
After successfully synthesizing the calix[4]diphenanthrenes spectrum, which shows a signal at m/z = 824. Consequently,
17a–c, we decided to introduce an additional methyl group distyrylcalixarene 21 was submitted to photolysis and
at the stilbene moiety in order to suppress [2+2] cycload- yielded after HPLC an inseparable mixture of calix[4]di-
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Multifold Photocyclization Reactions of Styrylcalixarenes
Scheme 7. Synthesis and irradiation of styrylcalixarene 21 and calix[4]diphenanthrene 22a and 22b.
phenanthrenes 22a (Figure 4) and 22b in 20% yield
(Scheme 7). The FAB mass spectrum shows a peak at m/z
= 820 and diagnostic signals for the Phen-5-H moiety ap-
1
pear as doublets at δ = 8.57 and 8.60 ppm in the H NMR
1
spectrum. Although the H NMR spectrum of the mixture
is rather complicated, some signals could be assigned to
either of the diastereomers (Figure 5). Thus, the m-aryl pro-
tons of 22a appear as doublets at δ = 5.33 and 6.03 ppm
with the p-ArH triplet at δ = 5.94 ppm. The signal at δ
= 5.33 ppm exhibits the expected anisotropic upfield shift
caused by the adjacent phenanthrene unit. The correspond-
ing m-ArH protons of the diastereomer 22b appear at δ =
5.12 ppm as a doublet, exhibiting an even larger shift,
which indicates that both phenanthrene units point towards
one aryl ring. The proton at the para position of this aryl
unit appears at δ = 5.64 ppm, whereas the protons of the
opposite aryl ring appear as a multiplet at lower field be-
tween 6.26–6.31 ppm, clearly not influenced by the phen-
Figure 4. Crystal structure of calix[4]diphenanthrene 22a with both
enantiomers in the unit cell.
anthrenes. Integration of the two different sets of signals bromide 20 in 64% yield (Scheme 8). The peak at m/z =
reveals a ratio of the two diastereomers 22a/22b of roughly 1056 in the FAB mass spectrum identifies compound 24.
1:1.1. Crystals of 22a, with both enantiomers in the unit The relatively simple NMR spectrum suggests that one con-
cell, were obtained from α,α,α-trifluorotoluene/methanol, formation of the stilbene units is preferred. Irradiation of
and crystal analysis confirmed the pinched cone conforma- tetrastyrylcalixarene 24 resulted in a complex mixture of
1
tion of the molecules (Figure 4).
products. The H NMR spectrum obtained from one iso-
The successful suppression of the [2+2] cycloaddition en- lated fraction after HPLC shows diagnostic phenanthrene
couraged us to test a four-fold oxidative cyclization. We pre- signals above 8 ppm. However, a peak at m/z = 1052 in
pared tetrastyrylcalixarene 24 by Wittig reaction of the the FAB mass spectrum indicates that a maximum of two
tetraformylcalixarene 23 with benzyltriphenylphosphonium phenanthrene units are formed.
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1
Figure 5. Partial H NMR spectrum of a mixture of diasteromers 22a and 22b in a ratio of 1:1.1, recorded at 400 MHz in CDCl3.
Scheme 8. Synthesis of tetrastyrylcalixarene 24.
with a Bruker Equinox 55 FT-IR spectrometer (KBr, ν in cm–1).
˜
Conclusions
UV/Vis spectra were recorded with a Varian Cary 1 (λmax in nm, ε
in cm2 mmol–1). 1H and 13C NMR spectra were recorded with a
The photolysis of 1,3-substituted styrylcalixarenes led to
cyclobutane-bridged calixarenes by transannular [2+2] Bruker DPX 200, DPX 400 or DRX 600 spectrometer. The spectra
were calibrated relative to the internal solvent peak [δ(CHCl3) =
7.26 (1H) and 77.16 ppm (13C); δ(CH2Cl2) = 5.32 (1H) and
54.00 ppm (13C)]. Mass spectrometry was performed with a Varian
MAT CH5 or VG Autospec spectrometer. FAB mass spectra were
recorded in NBA as matrix. For TLC, SiO2 plates (Polygram SIL
G/UV 254) from Macherey–Nagel & Co were used. All compounds
were purified by flash chromatography on Kieselgel 60 (Merck,
0.030–0.060 mm). Light petroleum ether (PE) was used for flash
chromatography. HPLC was performed with a Knauer HPLC
pump 64, a Knauer differential refractometer and a LiChrospher
cycloaddition reaction. Introducing steric hindrance at the
styryl moiety suppressed the photocyclization to give a mix-
ture of the calix[4]diphenanthrene stereoisomers 22a and
22b. In the case of proximal disubstitution, the photocycli-
zation proceeded smoothly to yield all the possible dia-
stereoisomeric calixdiphenanthrenes, but favouring the
sterically overcrowded and thermodynamically unfavoured
isomer. According to the NMR spectroscopic data as well
as X-ray crystal structure data the calixphenanthrenes pre-
fer a pinched cone conformation with the phenanthrene Si 60 (5 μ) column from Merck. All commercially available chemi-
cals were used without further purification. Solvents were dried by
common methods. The calixarenes 3,[16] 8,[3] 10,[17] 11,[9,18] 12,[9]
23[11b] and compound 19[13] were synthesized according to literature
procedures.
units sticking out. We are currently testing palladium-cata-
lysed annulation[8] reactions as a route to calixphenan-
threnes and -fluorenes.
cone-(E,Z)-5,17-Bis[2-phenylethenyl]-25,26,27,28-tetra-n-propoxy-
calix[4]arene (4): nBuLi (1.63 mL, 15% in hexane, 2.60 mmol) was
added to a cooled (–78 °C) suspension of benzyltriphenylphospho-
nium chloride (863 mg, 2.22 mmol) in dry THF (20 mL). The reac-
tion mixture was stirred for 45 min at –78 °C and for 30 min at
Experimental Section
General: Melting points were determined with a Kofler instrument,
model Reichert Thermovar. Elemental analyses were performed
with a Vario EL instrument. Infrared spectroscopy was performed
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Multifold Photocyclization Reactions of Styrylcalixarenes
room temperature. A solution of diformylcalixarene 3 (555 mg,
860 μmol) in dry THF (20 mL) was added to the dark-red suspen-
sion at –78 °C. The reaction mixture was stirred overnight while
warming up to room temperature. The orange solution was hydro-
lysed with water (20 mL) and extracted with dichloromethane
(100 mL). The organic layer was washed with water (4ϫ50 mL)
and brine (100 mL) and dried with MgSO4. The solvent was evapo-
rated and the residue (1.29 g) was submitted to flash chromatog-
raphy (silica, PE/EtOAc, 20:1, Rf = 0.50) to yield 632 mg of a
colourless solid, which was further purified by diffusion of meth-
anol into a dichloromethane solution to yield 618 mg (91%) of the
(E,Z)-calixarene 4 after drying in vacuo (0.2 mbar, 50–75 °C, 2 h).
Isomerization to the E,E isomer was achieved by adding a crystal
of iodine to the NMR sample and subsequent heating with a heat
OCH2), 121.5 (d, p-ArCH), 125.1 (d, m-ArCH), 125.5 (d, PhCH),
127.7 (d, PhCH), 128.3 (d, o-PhCH), 128.7 (m-ArCH), 129.4 (d,
m-ArCH), 129.6 (d, m-ArCH), 133.9 (s, ArCCH2Ar, p-ArC), 134.3
(ArCCH2Ar), 138.0, 138.1 (both s, ArCCH2Ar), 141.7 (PhC),
154.4, 159.4, 159.5 (all s, ArCO) ppm. MS (FAB): m/z (%) = 796
(100) [M]+. C56H60O4 (797.07): calcd. C 84.38, H 7.59; found C
83.98, H 7.22. 1H NMR spectra of other HPLC fractions indicated
the formation of compounds 5 and 7 in minor amounts and purity:
approximate yields were determined from NMR spectra to be
about 6% for the desired diphenanthrene 5 and about 25% for
compound 7.
Transannular Cyclization-Product (cone) 9: In three parallel reac-
tions, a suspension of calixarene 8 (90 mg, 90 μmol; 110 mg,
110 μmol; 140 mg, 140 μmol), iodine (110–180 mg, 0.43–
0.71 mmol) and potassium carbonate (1.90–3.03 g, 13.7–
21.9 mmol) in benzene (200 mL) was degassed with argon (30 min)
and irradiated for 18 h (125 W medium-pressure lamp, quartz fil-
ter). During the reaction a constant stream of argon was bubbled
through the solution. Benzene was removed in vacuo, the residue
was suspended in dichloromethane (10 mL) and insoluble material
was filtered off. The solvent was evaporated and the combined
black residue was purified by flash chromatography [silica, PE/EA,
100:1 to 50:1, Rf (100:1) = 0.44, 0.39, 0.09 (9), 0.05]. The fraction
with Rf = 0.09 yields 81 mg (24%) of slightly impure cyclization
products after drying in vacuo (0.73 mbar, 50 °C, 1 h). By HPLC
(n-hexane/EtOAc, 80:1, p = 1.6–1.7 MPa) and subsequent drying
in vacuo, 4 mg (1%) of analytically pure 9 were isolated as a colour-
less solid. 1H NMR (400 MHz, CDCl3): δ = 0.91 und 0.93 (2 t,
superimposed, both J = 7.3 Hz, 6 H, CH3), 1.24 and 1.26 (2 t,
superimposed, both J = 7.1 Hz, 6 H, CH3), 1.84–2.06 (m, 8 H,
CH2), 3.38 and 3.39 (m, 2 H, ArCH2Ar, cyclobutane-H), 3.50 (m,
2 H, ArCH2Ar, cyclobutane-H), 3.62 (m, 1 H, cyclobutane-H), 3.69
(m, 1 H, cyclobutane-H), 3.76–3.85 (m, 4 H, OCH2), 4.06–4.15 (m,
2 H, OCH2), 4.37–4.47 (m, 2 H, OCH2), 4.60 (d, J = 13.9 Hz, 1 H,
ArCH2Ar), 4.66 (d, J = 13.6 Hz, 1 H, ArCH2Ar), 4.69 (d, J =
14.1 Hz, 2 H, ArCH2Ar), 4.90 and 4.91 (2 d, superimposed, J =
14.6, J = 14.9 Hz, 2 H, ArCH2Ar), 5.01 (s, 1 H, m-ArH), 5.18 (s,
1 H, m-ArH), 5.56 (s, 1 H, m-ArH), 6.14 (s, 1 H, m-ArH), 6.44–
6.46 (m, 2 H, ArH), 6.75–6.79 (m, 5 H, ArH), 6.88–6.96 (m, 3 H,
ArH), 7.52–7.57 (m, 4 H, Phen-6/7-H), 7.62 (s, 1 H, Phen-1-H),
7.68 and 7.70 (2 d, superimposed, J = 9.1, J = 9.6 Hz, 2 H, Phen-
9-H), 7.76 (s and d, J = 8.6 Hz, 2 H, Phen-1-H, Phen-10-H), 7.84
(d, J = 8.8 Hz, 1 H, Phen-10-H), 7.90 (m, 2 H, Phen-8-H), 8.51 (m,
2 H, Phen-5-H) ppm. 13C{1H} NMR (100 Hz, CDCl3): δ = 10.1,
10.2, 11.2 (all q, CH3), 23.5, 23.6, 23.89, 23.93 (all t, CH2), 31.0,
31.3, 31.5, 31.7 (all t, ArCH2Ar), 44.3, 46.2, 47.7, 47.9 (all d, cyclo-
butane-C), 76.4, 76.5, 77.96, 78.04 (all t, OCH2), 124.2 (d), 124.89
(d), 124.91 (d), 124.97 (s), 125.3 (d), 125.4 (s), 125.47 (d), 125.49
(d), 125.9 (s), 127.3 (d), 127.4 (d), 127.5 (d), 127.7 (d), 127.9 (s),
128.2 (d), 128.27 (d), 128.32 (d), 128.4 (d), 128.5 (d), 128.7 (d),
130.3 (s), 130.4 (s), 132.1 (s), 132.4 (s), 132.6 (s), 133.4 (s), 133.5
(s), 133.76 (s), 133.80 (s), 133.9 (s), 134.5 (s), 135.2 (s), 136.96 (s),
137.02 (s), 140.7 (s), 141.2 (s), 153.7 (s, ArCO), 154.0 (s, ArCO),
160.1 (s, PhenCO), 160.2 (s, PhenCO) ppm. MS (FAB): m/z (%) =
997 (82) [M + H]+.
1
gun. H NMR (200 MHz, CDCl3, E,Z isomer): δ = 0.88–1.08 (m,
12 H, CH3), 1.80–2.01 (m, 8 H, CH2), 2.99 and 3.18 (both d, both
J = 13.4 Hz, 4 H, ArCH2Ar), 3.63–3.78 (m, 4 H, OCH2), 3.92–4.00
(m, 4 H, OCH2), 4.36 and 4.46 (both d, J = 13.1, J = 13.4 Hz, 4 H,
1
ArCH2Ar), 6.19–7.49 (m, 20 H, ArH) ppm. H NMR (200 MHz,
CDCl3, E,E isomer): δ = 0.93 (t, J = 7.4 Hz, 6 H, CH3),1.09 (t, J
= 7.5 Hz, 6 H, CH3), 1.82–2.02 (m, 8 H, CH2), 3.18 (d, J = 13.4 Hz,
4 H, ArCH2Ar), 3.75 (t, J = 7.1 Hz, 4 H, OCH2), 3.99 (t, J =
8.0 Hz, 4 H, OCH2), 4.46 (d, J = 13.4 Hz, 4 H, ArCH2Ar), 6.37
(br. s, 6 H, ArH), 6.93 (d, J = 14 Hz, 2 H, alkene-H), 7.02 (d, J =
15 Hz, 2 H, alkene-H), 7.11 (s, 4 H, m-ArH), 7.19–7.46 (m, 6,
ArH), 7.44 (d, J = 6.8 Hz, 4 H, ArH) ppm. MS (FAB): m/z (%) =
796 (100) [M]+. The NMR spectroscopic data for the E,E isomer
are in agreement with the literature.[4]
Transannular Cyclization Product (cone) 6: In three parallel reac-
tions, a suspension of calixarene 4 (124, 126 and 127 mg, 16 μmol),
iodine (91–99 mg, 0.36–0.38 mmol) and potassium carbonate
(1.199–1.202 g, 8.68–8.70 mmol) in benzene (200 mL) was degassed
with argon (30 min) and irradiated for 15 h (medium-pressure
lamp, 125 W, quartz filter) while a permanent stream of argon was
bubbled through the solution. Benzene was removed in vacuo and
the combined residues were suspended in dichloromethane
(600 mL) and insoluble material was filtered off. The solvent was
evaporated and the black residue (ca. 600 mg) was purified by flash
chromatography [silica, PE to PE/EtOAc, 10:1, Rf (20:1) = 0.42] to
yield 339 mg (90%) of cyclization products. By HPLC (n-hexane/
EtOAc, 80:1, p = 1.6–1.7 MPa, flow = 10 mL/ min) and subsequent
drying in vacuo (0.31 mbar, 50 °C, 1.5 h), 141 mg (37%) of 6 were
isolated as a colourless solid with m.p. 266–268 °C. Crystals suit-
able for X-ray crystallography were obtained by crystallization
from CH Cl /MeOH. IR (KBr): ν = 3056 (w), 3026 (w), 2962 (m),
˜
2
2
2930 (m), 2874 (m), 1601 (w), 1584 (w), 1463 (s), 1383 (w), 1278
(w), 1214 (m), 1172 (w), 1128 (w), 1073 (w), 1037 (w), 1008 (m),
966 (m), 920 (w), 890 (w), 870 (w), 833 (w), 799 (w), 768 (w), 721
(w) cm–1. UV/Vis (n-hexane): λmax [log(ε/cm2 mmol–1)] = 271 [3.4],
1
225 [4.8, sh] nm. H NMR (400 MHz, CDCl3): δ = 0.85 und 0.86
(t, superimposed, both J = 7.4 Hz, 6 H, CH3), 1.12 (t, J = 7.4 Hz,
6 H, CH3), 1.75–1.88 (m, 8 H, CH2), 3.15 (d, J = 14.4 Hz, 2 H,
ArCH2Ar), 3.21 (d, J = 14.3 Hz, 2 H, ArCH2Ar), 3.69 (t, J =
6.4 Hz, 4 H, OCH2), 3.76 (“d”, AAЈBBЈ, “J” = 7.0 Hz, 2 H, cyclo-
butane-H), 3.86 (“d”, AAЈBBЈ, “J” = 7.0 Hz, 2 H, cyclobutane-H),
3.89–3.93 (m, 4 H, OCH2), 4.45 and 4.49 (both d, superimposed,
both J = 13.9 Hz, 4 H, ArCH2Ar), 5.50 (d, J = 2.0 Hz, 2 H, m-
ArH), 5.86 (d, 3J = 2.0 Hz, 2 H, m-ArH), 6.87–6.89 (m, 4 H, o-
cone-5,11-Dibromo-25,26,27,28-tetrahydroxycalix[4]arene
(13):
Calixarene 12 (2.89 g, 3.79 mmol) was dissolved in dry toluene
(200 mL) and anhydrous AlCl3 (1.01 g, 7.52 mmol) was added at
PhH), 6.94–7.05 (m, 8 H, PhH, p-ArH), 7.13 (d, J = 7.3 Hz, 2 H, 0 °C. The mixture was stirred at 0 °C for 45 min and for an ad-
m-ArH), 7.21 (d, J = 7.4 Hz, 2 H, m-ArH) ppm. 13C{1H} NMR ditional 20 min at room temperature. The reaction was quenched
(100 Hz, CDCl3): δ = 10.00, 10.02, 11.1 (all q, CH3), 23.2, 23.3,
23.7 (all t, CH2), 31.4, 31.6 (both t, ArCH2Ar), 45.0 (d, cyclobu- tracted twice with dichloromethane (40 mL). The combined or-
tane-C-Ph), 48.7 (d, cyclobutane-C), 76.26, 76.31, 76.34 (all t, ganic layers were washed with water (50 mL), dried with MgSO4
with HCl (1 n, 50 mL) and the separated aqueous layer was ex-
Eur. J. Org. Chem. 2010, 6786–6797
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6793

W. Hüggenberg, A. Seper, I. M. Oppel, G. Dyker
FULL PAPER
and the solvents were removed in vacuo. The residue was treated
with CH2Cl2/MeOH (1:1), concentrated to 25% of the volume and
the resulting precipitate was filtered off and dried in vacuo (0.82–
1.7 mbar, 100 °C, 3 h) to give 1.88 g (85%) of calixarene 13 as a
colourless solid with m.p. Ͼ300 °C (ref.[10] m.p. Ͼ300 °C). 1H
NMR (200 MHz, CDCl3): δ = 3.49 (br. s, 4 H, ArCH2Ar), 4.18
(br. s, 4 H, ArCH2Ar), 6.77 (t, J = 7.5 Hz, 2 H, p-ArH), 7.02–7.11
(m, 4 H, m-ArH), 7.14 (d, J = 2.4 Hz, 2 H, BrArH), 7.19 (d, J =
2.4 Hz, 2 H, BrArH), 10.04 (s, 4 H, OH) ppm. 13C{1H} NMR
(50 Hz, CDCl3): δ = 31.5, 31.6, 31.7 (all t, all ArCH2Ar), 114.1 (s),
122.7 (d), 127.4 (s), 128.3 (s), 129.2 (d), 129.5 (d), 129.6 (s), 130.6
(s), 131.6 (d), 131.9 (d), 148.2, 148.7 (both s) ppm. The NMR spec-
troscopic data are in accord with the literature.[10]
671 (80) [M + Na]+, 648 (100) [M]+. The NMR spectroscopic data
are in accord with the literature.[12]
cone-5,11-Bis(2-phenylethenyl)-25,26,27,28-tetra-n-propoxycalix[4]-
arene (16): nBuLi (1.78 mL, 15% in hexane, 2.85 mmol) was added
to a cooled (–78 °C) suspension of benzyltriphenylphosphonium
chloride (939 mg, 2.42 mmol) in dry THF (20 mL). The reaction
mixture was stirred for 45 min at –78 °C and for 30 min at room
temperature, during which time the colour changed from yellow to
orange and finally to dark red. The reaction mixture was cooled to
3
3
–78 °C and
a solution of diformylcalixarene 15 (607 mg,
0.94 mmol) in dry THF (25 mL) was added. The reaction was
warmed to room temperature overnight. After hydrolysing with
water (20 mL) the aqueous layer was extracted with dichlorometh-
ane (2ϫ50 mL), the organic layers were washed with water
(4ϫ50 mL) and brine (100 mL) and then dried with MgSO4. The
solvents were removed in vacuo and the resulting solid (1.463 g)
was purified by flash chromatography (silica, PE/EtOAc, 20:1, Rf =
0.35) and dried in vacuo (1.0–5.2 mbar, 50 °C, 2.5 h) to give 691 mg
(93%) of distilbene 16 as a colourless solid with m.p. 79–81 °C.
Isomerization to the E,E isomer was achieved by adding a crystal
of iodine to the NMR sample and subsequent heating with a heat
cone-5,11-Dibromo-25,26,27,28-tetra-n-propoxycalix[4]arene (14):
NaH (60% in mineral oil, 2.47 g, 61.7 mmol) was washed three
times with hexane (15 mL), suspended in dry DMF (80 mL) and
after the addition of calixarene 13 (1.80 g, 3.09 mmol) the mixture
was heated at 60 °C for 30 min. Then propyl iodide was added and
after stirring at room temperature for 30 min the reaction mixture
was heated for an additional 2 h at 60–70 °C. The reaction was
quenched with ice-cold water (110 mL) and the aqueous layer was
extracted with dichloromethane (3ϫ30 mL). The organic layer was
washed twice with aqueous ammonium chloride (1 n, 50 mL), once
with water (50 mL) and brine (50 mL), dried with MgSO4 and the
solvent was evaporated. The residue was purified by flash
chromatography [silica, PE/CH2Cl2, 8:1, Rf (PE/CH2Cl2, 2.5:1) =
0.51] and dried in vacuo (1.4–3.9 mbar, 100 °C, 2 h) to give 1.66 g
(94%) of calixarene 14 as a colourless solid with m.p. 80–82 °C
(ref.[10] 117–119 °C). 1H NMR (200 MHz, CDCl3): δ = 0.97 and
0.98 (both t, superimposed, J = 7.4, J = 7.5 Hz, 12 H, OCH3),
1.77–1.97 (m, 8 H, CH2), 3.04, 3.11 and 3.17 (all d, J = 13.9, J =
13.6, J = 13.0 Hz, 4 H, ArCH2Ar), 3.75–3.86 (m, 8 H, OCH2),
4.35, 4.39 and 4.44 (all d, J = 13.6, J = 13.6, J = 13.4 Hz, 4 H,
ArCH2Ar), 6.56–6.72 (m, 10 H, ArH) ppm. 13C{1H} NMR (50 Hz,
CDCl3): δ = 10.4, 10.5 (both q, CH3), 23.27, 23.28 (both t, CH2),
30.9, 31.0, 31.1 (all t, ArCH2Ar), 76.8, 76.9 (both t, OCH2), 114.8,
122.4, 128.1, 128.7, 130.6, 131.2, 134.4, 135.4, 136.7, 137.8, 156.0,
156.7 (all s, ArCO) ppm. MS (FAB): m/z (%) = 750 (82) [M]+. The
NMR spectroscopic data are in accord with the literature.[9,10]
gun. IR (KBr): ν = 3055 (w), 3020 (w), 2959 (s), 2930 (s), 2872 (s),
˜
2735 (w), 1631 (w), 1594 (w), 1492 (w), 1461 (s), 1401 (w), 1383
(m), 1304 (w), 1280 (w), 1246 (m), 1216 (s), 1193 (m), 1159 (w),
1125 (m), 1083 (w), 1068 (w), 1037 (m), 1005 (s), 963 (s), 916 (w),
888 (w), 836 (w), 807 (w), 763 (s) cm–1. UV/Vis (n-hexane): λmax
[log(ε/cm2 mmol–1)]
=
296 [4.5] nm. E,Z isomer: 1H NMR
(400 MHz, CDCl3): δ = 0.96–1.04 (m, 12 H, CH3), 1.85–1.96 (m,
8 H, CH2), 2.89, 2.98, 2.99, 3.03, 3.16, 3.19 (all d, J = 13.3, J =
13.4, J = 14.0, J = 14.0, J = 13.4, J = 13.4 Hz, 4 H, ArCH2Ar),
3.76–3.93 (m, 8 H, OCH2), 4.31, 4.36, 4.37, 4.39, 4.45, 4.46, 4.47
(all d, J = 13.2, J = 13.1, J = 13.3, J = 12.9, J = 13.4, J = 13.4, J
= 13.4 Hz, 4 H, ArCH2Ar), 6.27–6.85 (m, 14 H, ArH, alkene-H),
7.08–7.25 (m, 8 H, ArH), 7.32 (t, J = 7.6 Hz, 1 H, ArH), 7.42–7.54
(m, 1 H, ArH) ppm. 13C{1H} NMR (100 Hz, CDCl3): δ = 10.37,
10.46, 10.48, 10.50, 10.60 (all q, CH3), 23.36, 23.38, 23.45 (all t,
CH2), 31.0, 31.1, 31.2, 31.3 (all t, ArCH2Ar), 76.8 (t, OCH2), 122.0,
122.1, 122.2, 126.3, 126.4, 126.5, 126.6, 126.62, 126.66, 126.75,
126.83, 126.9, 127.06, 127.10, 128.0, 128.17, 128.22, 128.35, 128.41,
128.5, 128.6, 128.7, 128.9, 129.2, 129.4, 129.47, 129.53, 130.77,
130.81, 130.9, 131.3, 134.5, 134.7, 134.8, 134.9, 135.0, 135.2,
135.26, 135.33, 135.38, 135.41, 135.60, 135.64, 135.7, 135.9, 137.95,
138.00, 138.12, 138.13, 156.2, 156.3, 156.55, 156.58, 156.64, 156.8,
157.0, 157.2 ppm. MS (FAB): m/z (%) = 796 (100) [M]+. C56H60O4
(797.07): calcd. C 84.38, H 7.59; found C 84.37, H 7.82. E,E isomer:
1H NMR (200 MHz, CDCl3): δ = 0.99 and 1.00 (2 t, superimposed,
J = 7.3, J = 7.4 Hz, 12 H, CH3), 1.82–2.01 (m, 8 H, CH2), 3.15,
3.17 and 3.19 (3 d, superimposed, J = 13.6, J = 13.5, J = 13.6 Hz,
4 H, ArCH2Ar), 3.81–3.91 (m, 8 H, OCH2), 4.46 (d, J = 13.5 Hz,
4 H, ArCH2Ar), 6.48–6.64 (m, 6 H, ArH), 6.73 and 6.77 (d and s,
superimposed, J = 16.2 Hz, 6 H, alkene-H, m-ArH), 6.87 (d, J =
16.3 Hz, 2 H, alkene H), 7.16–7.24 (m, 2 H, p-ArЈH), 7.32 (“t”,
“J” = 7.7 Hz, 4 H, m-ArЈH), 7.45 (“d”, “J” = 7.8 Hz, 4 H, o-
ArЈH) ppm.
cone-5,11-Diformyl-25,26,27,28-tetra-n-propoxycalix[4]arene (15):
nBuLi (2.77 mL, 15% in hexane, 4.41 mmol) was added to a cooled
(–78 °C) solution of calixarene 14 (1.24 g, 1.65 mmol) in dry THF.
The reaction mixture was stirred for 45 min at –78 °C and after the
addition of DMF (2.52 mL, 15.5 mmol) for 2 h at room tempera-
ture. The reaction was hydrolysed with HCl (1 n, 40 mL), the aque-
ous layer was extracted with dichloromethane (3ϫ30 mL), the or-
ganic layers were washed with water (3ϫ30 mL) and brine (30 mL)
and then dried with MgSO4. The solvent was evaporated and the
residue purified by flash chromatography [silica, PE/EtOAc, 20:1
to 10:1, Rf (PE/EtOAc, 5:1) = 0.28] to give 15 after drying in vacuo
(1.8 mbar, 50 °C, 2.5 h) in 632 mg (45%) yield as a colourless solid.
1H NMR (200 MHz, CDCl3): δ = 0.99 and 1.01 (2 t, superimposed,
both J = 7.4 Hz, 12 H, CH3), 1.81–1.99 (m, 8 H, CH2), 3.16 (d, J
= 13.6 Hz, 1 H, ArCH2Ar), 3.25 (d, J = 14.0 Hz, 2 H, ArCH2Ar),
Proximal cone-Calix[4]bisphenanthrenes 17a–c: In four parallel re-
3.32 (d, J = 14.7 Hz, 1 H, ArCH2Ar), 3.77–4.10 (m, 8 H, OCH2), actions, a suspension of calixarene 16 (108, 109, 111 and 126 mg,
4.42 (d, J = 13.4 Hz, 1 H, ArCH2Ar), 4.47 (d, J = 13.6 Hz, 2 H,
ArCH2Ar), 4.52 (d, J = 13.6 Hz, 1 H, ArCH2Ar), 6.47–6.61 (m, 6
H, ArH), 7.12 and 7.14 (2 d, both J = 1.9 Hz, 4 H, m-ArH), 9.65
135–158 μmol), iodine (79–92 mg, 0.31–0.36 mmol) and potassium
carbonate (1.05–1.30 g, 7.60–9.41 mmol) in benzene (200 mL) was
degassed with argon (30 min) and irradiated for 17 h (medium-
pressure Hg lamp, 125 W, quartz filter). During the reaction a per-
manent stream of argon was bubbled through the solution. Benzene
was removed in vacuo and the residue was suspended in dichloro-
methane and insoluble material was filtered off. The filtrate was
3
(s, 2 H, ArCHO) ppm. 13C{1H} NMR (50 Hz, CDCl3): δ = 10.4,
10.5 (both q, CH3), 23.4, 23.5 (both t, CH2), 31.1 (t, ArCH2Ar),
76.9 (t, OCH2), 122.4, 128.2, 128.8, 130.0, 130.8, 131.2, 134.3,
135.5, 135.6, 136.7, 156.6, 162.4, 191.7 ppm. MS (FAB): m/z (%) =
6794
www.eurjoc.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 6786–6797

Multifold Photocyclization Reactions of Styrylcalixarenes
washed with aqueous Na2S2O3 (10%, 60 mL) and dried with
MgSO4 to give 573 mg of a brown residue. Successive flash
chromatography [silica, PE/EtOAc, 50:1 and PE/EtOAc, 20:1, Rf
(PE/EtOAc, 20:1) = 0.32] gave 301 mg (67%) of a mixture of cycli-
zation products. A portion of this mixture (235 mg) was subjected
to HPLC (PE/EtOAc, 200:1, p = 1.1–1.2 MPa) and the isolated
compounds dried in vacuo (1.1–1.8 mbar, 75–100 °C, 1.5 h).
2 H, OCH2) 4.28 (d and m, superimposed, J = 14.2 Hz, 3 H, Ar-
CH2Ar, OCH2), 4.73 (d, J = 14.3 Hz, 2 H, ArCH2Ar), 4.94 and
4.98 (both d, superimposed, J = 14.4, J = 14.6 Hz, 3 H, ArCH2Ar),
5.84 (br. s, 2 H, m-ArH), 6.07 (t, J = 7.3 Hz, 2 H, p-ArH), 6.26
(br. s, 2 H, m-ArH), 7.04 (br. s, 2 H, Phen-H), 7.38 (s, 2 H, Phen-
H), 7.44–7.56 (m, 6 H, Phen-H), 7.78 (d, J = 7.3 Hz, 2 H, Phen-H),
8.78 (d, J = 8.0 Hz, 2 H, Phen-5-H) ppm. 13C{1H} NMR (100 Hz,
CDCl3): δ = 10.5, 10.7 (both q, CH3), 23.3, 23.7 (both t, CH2),
30.5, 30.9, 31.3 (all d, ArCH2Ar), 76.4, 78.3 (both t, OCH2), 121.3
(d, p-ArCH), 124.3, 124.7, 125.6 (all d, Phen-C), 127.6 (d, Phen-C,
m-ArCH), 128.1 (d, m-ArCH, Phen-C), 128.5 (d, m-Phen-C, Phen-
C-5), 129.0, 130.5, 130.7, 133.0 (all s, Phen-C), 134.2 (s,
PhenCCH2Phen), 134.5 (s, ArCCH2Phen), 134.7 (s, ArCCH2Ar),
156.3 (s, ArCO), 159.0 (s, PhenCO) ppm. MS (FAB): m/z (%) =
792 (100) [M]+.
First Fraction: 123 mg (27%) of 17a were isolated as a colourless
solid with m.p. 243–245 °C. Crystals suitable for X-ray crystal-
lography were obtained from chloroform/ethanol. IR (KBr): ν =
˜
3048 (w), 2959 (s), 2918 (m), 2872 (m), 1590 (w), 1511 (w), 1452
(s), 1442 (s), 1412 (w), 1377 (w), 1330 (w), 1285 (m), 1252 (m), 1206
(m), 1166 (w), 1137 (w), 1096 (w), 1083 (w), 1062 (w), 1033 (w),
1001 (s), 966 (s), 885 (w), 868 (w), 838 (w), 805 (m), 765 (m), 745
(m) cm–1. UV/Vis (n-hexane): λmax [log(ε/cm2 mmol–1)] = 309 [4.0,
1
sh], 259 [4.7], 221 [4.6, sh] nm. H NMR (600 MHz, CDCl3): δ =
Third Fraction: 63 mg (14%) of 17c were isolated as a colourless
0.79 (t, J = 7.5 Hz, 3 H, CH3), 0.94 (t, J = 7.4 Hz, 3 H, CH3), 1.06
(t, J = 7.4 Hz, 3 H, CH3), 1.33 (t, J = 7.4 Hz, 3 H, CH3), 1.72–
2.14 (m, 8 H, CH2), 3.04 (d, J = 14.3 Hz, 1 H, ArCH2Ar), 3.25 (d,
J = 13.3 Hz, 1 H, ArCH2Ar), 3.31 (d, J = 14.0 Hz, 1 H, ArCH2Ar),
3.56–3.63 (m, 2 H, OCH2), 3.90–3.97 (m, 2 H, OCH2), 4.03–4.07
(m, 1 H, OCH2), 4.16–4.29 and 4.26 (m and d, superimposed, J =
12.9 Hz, 3 H, OCH2, ArCH2Ar), 4.49 (d, J = 13.2 Hz, 1 H, Ar-
CH2Ar), 4.79 (d, J = 13.8 Hz, 1 H, ArCH2Ar), 5.30 (d, J = 7.3 Hz,
1 H, m-ArH), 5.71 (t, J = 7.2 Hz, 1 H, Phen-6-H), 5.76 (d, J =
15.8 Hz, ArCH2Ar), 5.81 (d, J = 15.9 Hz, 1 H, ArCH2Ar), 6.00 (s,
1 H, Phen-1-H), 6.16 (t, J = 7.5 Hz, 1 H, p-ArH), 6.23 (d, J =
7.2 Hz, 1 H, m-ArH), 6.80 (d, J = 8.6 Hz, 1 H, Phen-10-H), 6.84
(t, J = 7.3 Hz, 1 H, Phen-7-H), 7.04 (s, 1 H, Phen-1-H), 7.07 (d, J
= 8.6 Hz, 1 H, Phen-9-H), 7.09 (t, J = 7.5 Hz, 1 H, p-ArH), 7.24–
7.26 (m, 3 H, m-ArH, Phen-8-H, Phen-10-H), 7.54 (d, J = 8.7 Hz,
1 H, Phen-9-H), 7.61 (d, J = 8.4 Hz, 1 H, Phen-5-H), 7.66 (t, J =
7.3 Hz, 1 H, Phen-7-H), 7.71 (t, J = 7.5 Hz, 1 H, Phen-6-H), 8.00
(d, J = 7.5 Hz, 1 H, Phen-8-H), 8.70 (d, J = 8.2 Hz, 1 H, Phen-5-
H) ppm. 13C{1H} NMR (150 Hz, CDCl3): δ = 9.8, 10.1, 11.0, 11.3
(all q, CH3), 22.2, 23.1, 23.7, 23.9 (all t, CH2), 30.7, 31.0, 31.5, 31.6
(all t, ArCH2Ar), 77.0, 77.2 (both t, OCH2), 122.1 (d, p-ArCH),
122.5 (d, Phen-C-6), 123.3 (d, p-ArCH), 123.9 (d, Phen-C-9), 124.3
(d, Phen-C-7), 124.6 (d, Phen-C-9), 124.9 (d, Phen-C-6), 125.8 (d,
Phen-C-7), 125.9 (d, m-ArCH), 126.6, 126.8, 127.0 (3 d, Phen-C-8,
Phen-C-10, m-ArCH), 127.3 (d, Phen-C-5), 127.4 (s, Phen-C), 127.8
(d, Phen-C-5), 128.0 (d, Phen-C-1), 128.2 (d, Phen-C-8), 128.3 (s,
Phen-C), 128.5, 128.6 (both d, both Phen-C), 129.0 (s, Phen-C),
129.1 (d, m-ArCH), 129.5 (s, Phen-C), 129.8 (d, m-ArCH), 130.6
(s, PhenCCH2Phen), 131.1 (s, Phen-C), 131.5 (s, PhenCCH2Phen),
132.0 (s, Phen-C), 132.86 (s, ArCCH2Phen), 132.87 (s,
ArCCH2Phen), 133.47, 133.49, 133.6 (3 s, PhenCCH2Ar, two Phen-
C), 135.7 (s, PhenCCH2Ar), 137.0 (s, ArCCH2Phen), 138.3 (s,
ArCCH2Ar), 155.0 (s, ArCO), 156.9 (s, PhenCO), 158.7 (s, ArCO),
159.8 (s, PhenCO) ppm. MS (FAB): m/z (%) = 815 (7) [M + Na]+,
792 (100) [M]+. C56H56O4 (793.04): calcd. C 84.81, H 7.12; found
C 84.41, H 7.13.
solid with m.p. 134–136 °C. IR (KBr): ν = 3046 (w), 2959 (s), 2930
˜
(m), 2872 (m), 2732 (w), 1590 (w), 1510 (w), 1454 (s), 1440 (s), 1413
(w), 1380 (w), 1335 (w), 1286 (w), 1248 (w), 1215 (m), 1200 (m),
1134 (w), 1101 (m), 1082 (w), 1064 (w), 1036 (w), 1003 (s), 967 (m),
881 (w), 838 (w), 805 (m), 762 (m), 744 (m) cm–1. UV/Vis (n-hex-
ane): λmax [log(ε/cm2 mmol–1)] = 258 [4.9], 307 [4.5, sh], 343 [3.3],
359 [3.2] nm. 1H NMR (400 MHz, CDCl3): δ = δ = 0.94 (t, J =
7.4 Hz, 3 H, CH3), 1.00 (t, J = 7.4 Hz, 3 H, CH3), 1.06 (t, J =
7.4 Hz, 3 H, CH3), 1.11 (t, J = 7.4 Hz, 3 H, CH3), 1.87–2.03 (m, 8
H, CH2), 3.04 (d, J = 13.9 Hz, 1 H, ArCH2Ar), 3.41 (d, J =
13.7 Hz, ArCH2Ar), 3.74–4.13 (m, 7 H, OCH2), 4.22–4.28 (m, 1 H,
OCH2), 4.38 (d, J = 13.8 Hz, 1 H, ArCH2Ar), 4.52 (d, J = 14.8 Hz,
1 H, ArCH2Ar), 4.66 (d, J = 15.5 Hz, ArCH2Ar), 4.73 (d, J =
13.6 Hz, 1 H, ArCH2Ar), 4.94 (d, J = 14.8 Hz, 1 H, ArCH2Ar),
5.31 (d, J = 15.5 Hz, 1 H, ArCH2Ar), 6.18 (t, J = 7.5 Hz, 1 H),
6.39 (br. s, 2 H), 6.52 (d, J = 6.9 Hz, 3 H), 6.88 (d, J = 8.5 Hz, 1
H), 7.19 (d, J = 8.7 Hz, 1 H), 7.38–7.44 (m, 4 H), 7.49 (br. s, 2 H),
7.61 and 7.62 (m, 1 H), 7.73 (br. “s”, 1 H), 8.73 (“d”, “J” = 7.4 Hz,
2 H, Phen-5-H) ppm. 13C{1H} NMR (100 Hz, CDCl3): δ = 10.3,
10.5, 10.75, 10.78 (all q, CH3), 23.0, 23.3, 23.5 (all t, CH2), 30.0,
30.7, 31.4, 31.5 (all t, ArCH2Ar), 76.2, 77.0, 77.4, 77.8 (all t,
OCH2), 120.9, 122.5, 123.9, 124.0, 124.8, 125.1, 125.4, 125.6, 127.5,
127.6, 127.75, 127.84, 128.1, 128.2, 128.3, 128.5, 128.7 (s), 128.76
(s), 128.83 (s), 129.2 (s), 129.8 (s), 130.4 (s), 130.5 (s), 130.6 (s),
132.8 (s), 133.2 (s), 133.8 (s), 134.5 (s), 134.87 (s), 134.89 (s), 136.2
(s), 156.4, 157.0 (both s, ArCO), 157.9 (s, PhenCO) ppm. MS
(FAB): m/z (%) = 792 (100) [M]+.
(1-Phenylethyl)triphenylphosphonium Bromide (20): 1-Bromoethyl-
benzene (19; 2.71 g, 14.6 mmol) and triphenylphosphane (4.00 g,
15.3 mmol) were dissolved in toluene (15 mL) and stirred at 110–
120 °C for 3 d in a screw-capped flask. The colourless precipitate
was filtered off, washed with toluene and dried in vacuo (0.76–
2.5 mbar, 100 °C, 3 h) to give 5.77 g (88%) of 20 as a solid with
m.p. 229–231 °C (ref.[15] m.p. 231–234 °C). 1H NMR (200 MHz,
CDCl3): δ = 1.82 (dd, J = 19.1, J = 7.2 Hz, 3 H, CH3), 6.82 (dq, J
= 14.2, J = 7.3 Hz, 1 H, CH), 7.15–7.26 (m, 5 H, ArH), 7.58–7.88
(m, 15 H, ArH) ppm. MS (FAB): m/z (%) = 367 (100) [M]+. The
NMR spectroscopic data are in accord with the literature.[14,15]
Second Fraction: 31 mg (7%) of 17b were isolated as a colourless
solid with m.p. 129–131 °C. IR (KBr): ν = 3046 (w), 2959 (s), 2930
˜
(m), 2872 (m), 1592 (w), 1510 (w), 1454 (s), 1441 (s), 1413 (w), 1380
(w), 1332 (w), 1288 (w), 1249 (w), 1214 (m), 1201 (m), 1177 (w),
cone-5,17-Bis(2-methyl-2-phenylethenyl)-25,26,27,28-tetra-n-prop-
1134 (w), 1101 (m), 1082 (w), 1064 (w), 1037 (w), 1004 (s), 967 (m), oxycalix[4]arene (21): nBuLi (1.5 mL, 15% in hexane, 2.39 mmol)
882 (w), 838 (w), 804 (m), 758 (m), 744 (m), 700 (w) cm–1. UV/Vis was added to a cooled (–78 °C) suspension of phosphonium bro-
1
(n-hexane): λmax [log(ε/cm2 mmol–1)] = 269 [5.0], 310 [4.3] nm. H
mide 20 (854 mg, 1.92 mmol) in dry THF (20 mL). The reaction
NMR (400 MHz, CDCl3): δ = 1.02 (t, J = 7.4 Hz, 6 H, CH3), 1.08 mixture was stirred for 45 min at –78 °C and for 30 min at room
(t, J = 7.4 Hz, 6 H, CH3), 1.88–1.96 (m, 4 H, CH2), 1.98–2.11 (m,
4 H, CH2), 2.90 (d, J = 14.3 Hz, 1 H, ArCH2Ar), 3.46 (d, J =
temperature. A solution of diformylcalixarene 3 (475 mg,
733 μmol) in dry THF (10 mL) was added at –78 °C. The reaction
14.2 Hz, 1 H, ArCH2Ar), 3.79–3.92 (m, 4 H, OCH2), 4.03–4.09 (m, mixture was warmed to room temperature overnight. The suspen-
Eur. J. Org. Chem. 2010, 6786–6797
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6795

W. Hüggenberg, A. Seper, I. M. Oppel, G. Dyker
FULL PAPER
sion was hydrolysed with water (25 mL) and the aqueous layer was
extracted with dichloromethane (3ϫ20 mL). The combined or-
ganic layers were washed twice with water (20 mL) and once with
brine (30 mL) and then dried with MgSO4. The solvent was evapo-
rated and the residue (1.37 g) purified by flash chromatography (sil-
ica, PE/EtOAc, 30:1 to 20:1) and dried in vacuo (0.61 mbar, 75 °C,
2 h) to yield 418 mg (69%) of calixarene 21 [Rf (PE/EtOAc, 20:1)
= 0.46] in as a colourless solid. Recrystallization from CH2Cl2/
MeOH and CH2Cl2/iPrOH gave 252 mg (42%) of 21 as crystals
ArH 22a), 5.94 (t, J = 7.6 Hz, 2 H, p-ArH 22a), 6.03 (d, J = 6.7 Hz,
2 H, m-ArH 22a), 7.52–7.62 (m, 8 H, Phen-H), 8.05 (“t”, J = 7.5,
J = 7.8 Hz, 2 H, Phen-H), 8.60 (d, J = 7.9 Hz, 2 H, Phen-5-H) ppm.
1
Isomer 22b: H NMR (400 MHz, CDCl3): δ = 0.95 (t, J = 7.5 Hz,
6 H, CH2CH3), 1.16 (t, J = 7.4 Hz, 3 H, CH2CH3), 1.32 (t, J =
7.4 Hz, 3 H, CH2CH3), 1.89–2.16 (m, 8 H, CH2), 2.73 (s, 6 H,
CH3), 3.35 and 3.39 (2 d, superimposed, J = 14.9, J = 13.8 Hz, 2
H, ArCH2Ar), 3.74 (t, J = 6.7 Hz, 2 H, OCH2), 3.87 (t, J = 6.5 Hz,
2 H, OCH2), 4.15–4.26 (m, 2 H, OCH2), 4.32–4.44 (m, 2 H, OCH2),
4.60 (d, J = 13.4 Hz, 1 H, ArCH2Ar), 4.62 (d, J = 13.2 Hz, 1 H,
with m.p. 229–231 °C. IR (KBr): ν = 3057 (w), 3023 (w), 2958 (m),
˜
2929 (m), 2871 (m), 1592 (w), 1492 (m), 1459 (s), 1383 (m), 1308 ArCH2Ar), 4.66 (d, J = 14.9 Hz, 1 H, ArCH2Ar), 4.72 (d, J =
(m), 1287 (w), 1247 (m), 1219 (s), 1196 (m), 1169 (w), 1136 (m), 14.6 Hz, 1 H, ArCH2Ar), 4.87 (d, J = 14.7 Hz, 2 H, ArCH2Ar),
1106 (w), 1082 (m), 1037 (m), 1005 (s), 965 (m), 889 (w), 858 (w), 5.12 (d, J = 7.5 Hz, 2 H, m-ArH 22b), 5.64 (t, J = 7.6 Hz, 1 H, p-
837 (w), 801 (w), 757 (s) cm–1. UV/Vis (n-hexane): λmax [log (ε/ ArH 22b), 6.23–6.31 (m, 3 H, p-ArH, m-ArH 22b), 7.52–7.62 (m,
cm2 mmol–1)] = 280 [4.2], 228 [4.3, sh] nm. 1H NMR (400 MHz, 8 H, Phen-H), 8.05 (“t”, J = 7.5, J = 7.8 Hz, 2 H, Phen-H), 8.57
CD2Cl2, diagnostic signals of the minor isomer are marked with
an asterisk): δ = 0.89*, 0.95*, 0.99*, 1.03, 1.05 (all t, J = 7.4 Hz,
(d, J = 8.0 Hz, 2 H, Phen-5-H) ppm. 13C{1H} NMR (100 Hz,
CDCl3): δ = 10.1, 11.0, 11.2, 11.3 (all q, all CH2CH3), 19.8 (q,
12 H, CH2CH3), 1.89 and 2.12* (both br. s, 6 H, CH3), 1.93–2.08 CH3), 23.3, 23.4, 23.8, 23.9, 24.0 (all t, all CH2), 30.2, 31.2 (both
(m, 8 H, CH2), 2.88*, 3.16*, 3.19 (all d, J = 13.2, J = 13.1 Hz, 4 t, both ArCH2Ar), 76.5, 76.7, 77.0, 77.8, 78.0 (all t, all OCH2),
H, ArCH2Ar), 3.78*, 3.87, 3.94 (all t, J = 7.3, J = 7.4, J = 7.6 Hz, 122.7, 122.8, 122.9 (all d, all p-ArCH), 124.3, 124.4 (both d, both
8 H, OCH2), 4.32*, 4.46*, 4.50 (all d, J = 13.1, J = 13.1 Hz, 4 H, Phen-8-C), 124.5 (d, Phen-6-C), 125.8 (d, Phen-7-C), 126.3, 126.8,
ArCH2Ar), 6.23–6.84 (m, 12 H, ArH and alkene-H), 7.10–7.50 (m,
10 H, ArЈH) ppm. 13C{1H} NMR (100 Hz, CD2Cl2): δ = 10.7, 10.8
(both q, CH2CH3), 17.6 (q, CH3), 23.8, 24.0 (both t, CH2), 31.6 (t,
ArCH2Ar), 77.4, 77.7 (both t, OCH2), 122.6 (d, ArCH), 126.3 (d,
ArЈCH), 127.1, 128.1 (d, alkene-CH), 128.7 (d, ArЈCH), 128.8 (d,
127.1 (all d, all m-ArCH), 127.2 (d, Phen-1-C), 127.4 (d, Phen-C),
127.6 (d, m-ArCH), 127.7, 128.4 (both s, both Phen-C), 128.5,
128.6 (both d, both Phen-5-C), 130.3 (s), 130.6 (s), 131.0, 131.1
(both s, both Phen-C), 132.2, 132.7 (both s, ArCCH2Phen), 133.27
(s), 133.33 (s), 134.6, 134.9 (both s, both ArCCH2Phen), 136.91,
ArCH, ArЈCH), 129.03* (d, ArЈCH), 129.68* (d, ArCH), 129.81 136.96 (both s), 154.6, 154.9, 155.3 (all s, all ArCO), 159.6, 159.7
(d, m-ArCH), 132.4, 135.0, 135.97, 136.00, 144.7 (all s), 155.8 (s,
ArCO), 157.2 (s, styryl-CO) ppm. MS (FAB): m/z (%) = 824 (100)
[M]+, 751 (8). C58H64O4·1͞8CH2Cl2 (835.74): calcd. C 83.53, H 7.75;
found C 83.41, H 7.34.
(both s, both PhenCO) ppm. MS (FAB): m/z (%) = 820 (100)
[M]+. C58H60O4 (821.09): calcd. C 84.84, H 7.37; found C 84.62, H
7.12.
cone-5,11,17,23-Tetrakis(2-methyl-2-phenylethenyl)-25,26,27,28-
cone-25,26,27,28-Tetra-n-propoxycalix[4]bis(9-methylphenanthrene) tetra-n-propoxycalix[4]arene (24): nBuLi (8.55 mL, 15% in hexane,
(22a and 22b): In three parallel reactions, a suspension of calixarene
21 (84 mg, 102 μmol and twice 100 mg, 121 μmol), iodine (57 mg,
0.22 mmol; 68 mg, 0.27 mmol) and potassium carbonate (759 mg,
5.49 mmol; 903 mg, 6.51 mmol) in benzene (200 mL) was degassed
with argon (30 min) and irradiated for 17 h (125 W medium-pres-
sure lamp, quartz filter) while a permanent stream of argon was
bubbled through the solution. Benzene was removed in vacuo, the
combined residues were suspended in dichloromethane (20 mL)
and insoluble material was filtered off. The solvent was evaporated
and the resulting brown solid (307 mg) was purified by flash
chromatography [silica, hexane/toluene, 5:1 to 2:1, Rf (5:1) = 0.21;
silica, PE/EtOAc, 100:1, Rf = 0.17] to yield 129 mg (46%) of cycli-
zation products. By HPLC (PE/EtOAc, 200:1, p = 1.1 MPa) and
subsequent drying in vacuo (0.47 mbar, 75–80 °C, 1.5 h) 57 mg
(20%) of a mixture of isomers 22a and 22b were obtained as a
colourless solid with m.p. 161–163 °C. Single crystals were obtained
13.6 mmol) was added to a cooled (–78 °C) suspension of phospho-
nium bromide 20 (5.09 g, 11.4 mmol) in dry THF (70 mL). The
reaction mixture was stirred for 1 h at –78 °C and for 30 min at
room temperature. A solution of tetraformylcalixarene 23 (802 mg,
1.13 mmol) in dry THF (15 mL) was added at –78 °C. The reaction
mixture was warmed to room temperature overnight. The suspen-
sion was hydrolysed with water (80 mL), the aqueous layer was
extracted with ethyl acetate (2ϫ40 mL) and the organic layers were
washed with water (50 mL) and brine (50 mL) and dried with
MgSO4. The solvent was evaporated and the residue (3.04 g) puri-
fied by flash chromatography (silica, PE/EtOAc, 20:1) and dried in
vacuo (1.6–2.1 mbar, 75 °C, 1.5 h) to yield 773 mg (64%) of calixar-
ene 24 [Rf (PE/EtOAc, 10:1) = 0.54] as a colourless solid with m.p.
167–168 °C. IR (KBr): ν = 3079 (w), 3053 (w), 3020 (w), 2959 (m),
˜
2931 (m), 2873 (m), 1597 (w), 1576 (w), 1542 (w), 1493 (m), 1465
(s), 1444 (m), 1383 (w), 1310 (w), 1288 (w), 1219 (m), 1145 (w),
1126 (w), 1106 (w), 1067 (w), 1036 (w), 1006 (m), 964 (w), 941 (w),
from trifluorotoluene/methanol. IR (KBr): ν = 3066 (w), 3020 (w),
˜
2959 (s), 2931 (s), 2872 (s), 2729 (w), 1621 (w), 1589 (w), 1518 (w), 894 (w), 853 (w), 756 (m), 695 (m) cm–1. UV/Vis (n-hexane): λmax
1478 (m), 1452 (s), 1416 (m), 1382 (m), 1338 (m), 1290 (w), 1243 [log(ε/cm2 mmol–1)] = 278 [4.5], 228 [4.4] nm. H NMR (400 MHz,
1
(s), 1196 (m), 1179 (s), 1142 (w), 1128 (w), 1083 (m), 1065 (w), 1036 CDCl3, diagnostic signals of the minor isomer are marked with an
(m), 1002 (s), 966 (s), 888 (w), 839 (w), 818 (w), 799 (w), 755 (s),
720 (w) cm–1. UV/Vis (n-hexane): λmax [log(ε/cm2 mmol–1)] = 366 7.4, J = 7.5 Hz, 12 H, CH2CH3), 1.83*, 1.96, 2.16* (all s, CH3),
[3.3], 348 [3.4], 315 [4.4], 266 [5.1], 218 [4.9] nm. Isomer 22a: 1H
1.88–2.08 (m, 20 H), 2.90*, 3.19*, 3.22 (all d, J = 13.0, J = 12.7, J
asterisk): δ = 0.96*, 1.00*, 1.02*, 1.05 (all t, J = 7.4, J = 7.3, J =
NMR (400 MHz, CDCl3): δ = 0.94 (t, J = 7.5 Hz, 6 H, CH2CH3), = 13.0 Hz, 4 H, ArCH2Ar), 3.79* (t, J = 7.3 Hz) and 3.88–4.01*
1.24 (t, J = 7.4 Hz, 6 H, CH2CH3), 1.89–2.16 (m, 8 H, CH2), 2.74 (m with 3.94, t, J = 7.6 Hz, 8 H, OCH2), 4.34*, 4.49*, 4.53 (all d,
(s, 6 H, CH3), 3.35 and 3.39 (2 d, superimposed, J = 14.9, J =
J = 12.9, 14.0, 13.0 Hz, 4 H, ArCH2Ar), 6.22–6.90 (m, 12 H,
13.8 Hz, 2 H, ArCH2Ar), 3.76–3.86 (m, 4 H, OCH2), 4.15–4.26 (m, C=CH, m-ArH), 7.12–7.49 (m, 20 H, ArЈH) ppm. 13C{1H} NMR
2 H, OCH2), 4.32–4.44 (m, 2 H, OCH2), 4.60 (d, J = 13.4 Hz, 1 H, (100 Hz, CDCl3): δ = 10.35* , 10.52, 10.64* (all q, CH2CH3),
ArCH2Ar), 4.62 (d, J = 13.2 Hz, 1 H, ArCH2Ar), 4.66 (d, J =
14.9 Hz, 1 H, ArCH2Ar), 4.72 (d, J = 14.6 Hz, 1 H, ArCH2Ar), 31.30 (all t, ArCH2Ar), 76.96, 77.21 (all t, OCH2), 125.9, 126.0,
4.87 (d, J = 14.7 Hz, 2 H, ArCH2Ar), 5.33 (d, J = 6.4 Hz, 2 H, m- 126.1*, 126.7*, 126.8 (all d, m-ArCH, ArЈCH), 127.8, 127.9* (both
17.15*, 17.29, 17.68 (all q, CH3), 23.47, 23.50* (all t, CH2), 31.22*,
6796
www.eurjoc.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 6786–6797

Multifold Photocyclization Reactions of Styrylcalixarenes
Compounds, Kluwer, Dordrecht, 1991; c) V. Böhmer, Angew.
Chem. 1995, 107, 785–818; d) S. Shinkai, Tetrahedron 1993, 49,
8933–8968; e) A. Ikeda, S. Shinkai, Chem. Rev. 1997, 97, 1713–
1734; f) C. D. Gutsche, Calixarenes Revisited, The Royal Soci-
ety of Chemistry, Cambridge, 1998; g) Z. Asfari, V. Böhmer, J.
Harrowfield, J. Vicens (Eds.), Calixarenes, Kluwer, Dordrecht,
2001.
For examples of binding cations, anions and neutral molecules,
see: a) G. D. Andreetti, J. Chem. Soc., Chem. Commun. 1979,
1005–1007; b) L. J. Bauer, C. D. Gutsche, J. Am. Chem. Soc.
1985, 107, 6063–6069; c) P. Lhoták, S. Shinkai, J. Phys. Org.
Chem. 1997, 10, 273–285; d) A. Casnati, L. Pirondini, N. Pel-
izzi, R. Ungaro, Supramol. Chem. 2000, 12, 53–65; e) A. Ardu-
ini, G. Giorgi, A. Pochini, A. Secchi, F. Ugozzoli, J. Org. Chem.
2001, 66, 8302–8308; f) P. D. Beer, P. A. Gale, Angew. Chem.
Int. Ed. 2001, 40, 486–516; g) A. Arduini, D. Demuru, A. Poch-
ini, A. Secchi, Chem. Commun. 2005, 645–647; h) G. Dyker,
M. Mastalerz, I. M. Müller, Eur. J. Org. Chem. 2005, 3801–
3812; i) O. Danylyuk, K. Suwinska, Chem. Commun. 2009,
5799–5813.
a) M. Mastalerz, W. Hüggenberg, G. Dyker, Eur. J. Org. Chem.
2006, 3977–3987; b) M. Mastalerz, Ph. D. Thesis, Ruhr-Uni-
versität Bochum, 2005.
M. Larsen, F. C. Krebs, M. Jorgensen, N. Harrit, J. Org. Chem.
1998, 63, 4420–4424.
H. Hopf, H. Greiving, C. Beck, I. Dix, P. G. Jones, J.-P.
Desvergne, H. Bouas-Laurent, Eur. J. Org. Chem. 2005, 567–
581.
C. Jaime, J. de Mendoza, P. Prados, P. M. Nieto, C. Sanchez,
J. Org. Chem. 1991, 56, 3372–3376.
d, m-ArCH, C=CH), 128.2*, 128.27, 128.33*, 128.6* (all d,
ArЈCH), 129.2*, 129.5 (both d, m-ArCH), 132.1*, 132.3, 132.4 (all
s), 134.63 (s, ArCCH2Ar), 135.6*, 135.7 (both s), 144.2 (s), 154.8*,
155.2 (both s, ArCO) ppm. MS (FAB): m/z (%) = 1056 (79) [M]+,
940 (17). C76H80O4 (1057.45): calcd. C 86.32, H 7.63; found C
86.33, H 7.46.
[2]
X-ray Crystallography: The intensity data were collected with an
Oxford Diffraction Xcalibur2 diffractometer with a Sapphire2
CCD. The crystal structures were solved by direct methods using
SHELXS-97[19] and refined with SHELXL-97.[19] For refinement
details see the following section.
Crystal Structure of 6: Colourless prisms, 0.42ϫ0.22ϫ0.17 mm3,
monoclinic, P21/c, a = 20.5290(7), b = 17.7566(6), c = 24.2824(8) Å,
β = 92.535(3)°, V = 8842.9(5) Å3, Z = 8, ρcalcd. = 1.197 g/cm3, θmax
= 25.0°, λ(Mo-Kα) = 0.71073 Å, T = 110(2) K, 61209 measured
reflections, 15535 independent reflections (Rint = 0.0963), 6248 re-
flections [IϾ2σ(I)], 1089 parameters, R = 0.0438, wR = 0.1085 (for
all data).
[3]
Crystal Structure of 17a: Colourless prisms, 0.22ϫ0.20ϫ
0.10 mm3, orthorhombic, P2(1)2(1)2(1), a = 11.0221(6), b =
[4]
[5]
13.3367(8), c = 29.644(2) Å, V = 4357.6(4) Å3, Z = 4, ρcalcd.
=
1.209 g/cm3, θmax = 26.0°, λ(Mo-Kα) = 0.71073 Å, T = 113(2) K,
28159 measured reflections, 4774 [8555] independent reflections
(Rint = 0.0420), 3657 [6093] reflections [IϾ2σ(I)], 545 parameters,
R = 0.0367 [0.0359], wR = 0.0567 [0.0555] (for all data) [data before
merging, Flack: –0.6(7)]. As we were unable to obtain a satisfying
dataset using Cu radiation we decided to merge the Mo data as the
absolute structure could not be determined exactly. Nevertheless
the Flack parameter for the unmerged data set suggests that the
enantiomer shown is predominates within the crystal.
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Crystal Structure of 22a: Colourless prisms, 0.32ϫ0.27ϫ
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3
¯
0.22 mm , triclinic, P1, a = 11.1909(4), b = 14.9553(6), c =
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Compound 11 was isolated by dry column chromatography
starting with PE/toluene (1:1) and increasing the ratio of tolu-
ene in 10% steps until pure toluene finally eluted the product.
G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112.
Received: August 6, 2010
We gratefully acknowledge financial support from the Deutsche
Forschungsgemeinschaft (DFG) (project Dy 12/9-2).
[1] For reviews and monographs on calixarenes including supra-
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Royal Society of Chemistry, Cambridge, 1989; b) J. Vicens, V.
Böhmer (Eds.), Calixarenes, a Versatile Class of Macrocyclic
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Published Online: November 2, 2010
Eur. J. Org. Chem. 2010, 6786–6797
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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