Stereoselective dialkylation of the proximal hydroxy groups of calix- And thiacalix[4]arenes

Article abstract of DOI:10.1039/b315867e

Treatment of p-tert-butylcalix[4]arene (C1) and its sulfur-bridged analog T1 with 1,3-dichloro-1,1,3,3-tetraiso-propyldisiloxane in the presence of imidazole gives proximally O,O′-disiloxane-1,3-diyl-bridged calixarenes C2 and T2 in excellent yields, resp

Full text of DOI:10.1039/b315867e

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Stereoselective dialkylation of the proximal hydroxy groups of
calix- and thiacalix[4]arenes
Fumitaka Narumi,*a Tetsutaro Hattori,*b Naoya Morohashi,b Nobuji Matsumura,b
Waka Yamabuki,a Hiroshi Kameyamaa and Sotaro Miyanob
a Department of Basic Sciences, School of Science and Engineering,
Ishinomaki Senshu University, 1 Shinmito, Minamisakai, Ishinomaki 986-8580, Japan.
E-mail: fnarumi@isenshu-u.ac.jp
b Department of Environmental Studies, Graduate School of Environmental Studies,
Tohoku University, Aramaki-Aoba 07, Aoba-ku, Sendai 980-8579, Japan.
E-mail: hattori@orgsynth.che.tohoku.ac.jp
Received 9th December 2003, Accepted 27th January 2004
First published as an Advance Article on the web 18th February 2004
Treatment of p-tert-butylcalix[4]arene (C1) and its sulfur-bridged analog T1 with 1,3-dichloro-1,1,3,3-tetraiso-
propyldisiloxane in the presence of imidazole gives proximally O,OЈ-disiloxane-1,3-diyl-bridged calixarenes C2
and T2 in excellent yields, respectively. Subsequent base-catalyzed etherification of the remaining hydroxy groups
with alkyl halides gives syn- and anti-OЉ,Oٞ-dialkylated products, the stereoselectivity of which varies depending
on the nature of the macrocycle, as well as the metal cation of the base employed. Thus, conventional calixarene
C2 preferentially affords syn compounds of 1,2-alternate conformation (C3) with the aid of tert-BuOK and K2CO3
and anti counterparts of partial-cone conformation (C4) with Cs2CO3. On the other hand, thiacalixarene T2 affords
syn compounds of 1,2-alternate conformation (T3) with any of the bases. The disiloxanediyl bridge of the resulting
products can readily be removed by treatment with tetrabutylammonium fluoride. Thus, the net process provides
an efficient method for the regio- and stereoselective synthesis of proximally dialkylated calix[4]arenes.
(TIPDS) moiety is quite useful as a protective group for the
proximal dialkylation to give syn- and anti-OЉ,Oٞ-dialkylated
Introduction
The calix[4]arene skeleton is an extensively utilized scaffold for
the construction of synthetic receptors of metal ions and neu-
tral molecules, taking advantage of easy availability and feasi-
bility of various modifications at the phenolic hydroxy groups
products stereoselectively, depending on the reaction condi-
tions.12 Herein we report the net proximal dialkylation of calix-
and thiacalix[4]arenes C1 and T1 with high stereoselectivity via
TIPDS derivatives C2 and T2 in detail. Also reported is the
(lower rim), as well as at the para positions (upper rim), to
mechanism of the high syn/anti selectivity deduced from a
develop varying functions.1,2 It is well known in calixarene
chemistry that dialkylation of calix[4]arenes with alkyl halides
1
detailed study of stepwise alkylation monitored by H NMR
spectroscopy.
in the presence of a base occurs preferentially at the distal
hydroxy groups by virtue of a circular intramolecular hydrogen
bonding in the monoalkylated intermediate,3 which provides an
easy access to distally O,OЈ-dialkylated calix[4]arenes. On the
other hand, a general protocol for the regioselective O,OЈ-di-
alkylation at the proximal hydroxy groups, which is highly
desirable for the development of synthetic receptors,4–7 has yet
to be established despite efforts toward this end.5–10
Results and discussion
Synthesis of syn- and anti-O,OЈ-dialkylcalixarenes
Calixarenes C1 and T1 were treated with an excess of
1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane in DMF in the
presence of imidazole at room temperature to give, after one
crystallization from dichloromethane–methanol, proximally
O,OЈ-bridged derivatives C2 and T2 in 90 and 92% yields,
respectively (Scheme 1). It is of interest to note that the reaction
gave neither detectable amounts of O,OЉ-bridged isomer nor
intermolecularly bridged oligomers without relying on a high-
dilution technique (see Experimental section). It seems that the
short chain length of three atoms, with the aid of the steric bulk
of the four isopropyl substituents, prevented the dichloride
from such unwanted bridging.
The dialkylation of the TIPDS derivatives C2 and T2 was
performed by treatment with an alkyl halide in THF in the
presence of a base at appropriate temperatures (Scheme 2, Table
1). The reaction gave the corresponding syn- (C3 and T3) and
anti-OЉ,Oٞ-dialkylated products (C4 and T4) in good to excel-
lent yields except the cases of iodobutane with K2CO3 (entries 5
and 15). The product ratio varied depending on the substrate,
as well as the metal cation of the base employed. Thus, in the
dialkylation of conventional calixarene C2, tert-BuOK gave syn
compound C3 exclusively with no detectable amount of anti
counterpart C4 (entries 1–3). A weaker base bearing potassium
Among such endeavors, a promising approach may be to
block only one or two adjacent hydroxy groups of the starting
calixarenes with a proper protective group before alkylation.10
Shinkai et al. examined alkylation of mono-O-benzyl-protected
p-tert-butylcalix[4]arene with 1-bromopropane to obtain, after
debenzylation of the resulting triether, syn-O,OЈ-dipropyl
ether.6 On the other hand, Böhmer et al. proposed O,OЈ-bridg-
ing of calixarene C1 with phthaloyl dichloride to protect
two adjacent hydroxy groups.7 However, the derivatization
suffered from low yield and subsequent alkylation with ethyl
bromoacetate gave, after hydrolysis, a mixture of syn- and anti-
O,OЈ-diethers. Alternatively, Lattman et al. prepared O,OЈ-di-
methylsilylene-bridged p-tert-butylcalix[4]arene, attempted
proximal dimethylation of which with butyllithium and methyl
trifluoromethanesulfonate resulted in failure, giving not the
desired product but a doubly O,OЈ- and OЉ,Oٞ-silylene-bridged
compound, accompanied by the formation of tetramethyl
ether of calixarene C1.9 During the course of our studies on
the development of novel functions of thiacalixarene T1,11
we have found that the 1,1,3,3-tetraisopropyldisiloxane-1,3-diyl
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 8 9 0 – 8 9 8
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 4
890

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Table 1 Dialkylation of TIPDS derivatives C2 and T2 with RX in THF
Yield (%) [Product]
Entry
Starting material
RX (mol equiv.)
Base (mol equiv.)
Temp./ЊC
Time
C3 or T3
C4 or T4
1
2
C2
BrCH2Ph (6.0)
BuI (6.0)
BrCH2COOEt (6.0)
BrCH2Ph (20.0)
BuI (20.0)
BrCH2COOEt (6.0)
BrCH2Ph (8.0)
BuI (8.0)
BrCH2COOEt (6.0)
BrCH2COOEt (6.0)
tert-BuOK (3.0)
tert-BuOK (3.0)
tert-BuOK (3.0)
K2CO3 (20.0)
K2CO3 (20.0)
K2CO3 (6.0)
Cs2CO3 (6.0)
Cs2CO3 (6.0)
Cs2CO3 (6.0)
Cs2CO3 (6.0)
0
0
0
1 h
2 h
2 h
5 days
5 days
12 h
12 h
18 h
6 h
90 [C3a]
67 [C3b]
52 [C3c]
61 [C3a]
13 [C3b]
79 [C3c]
2 [C3a]
0 [C4a]
0 [C4b]
0 [C4c]
6 [C4a]
0 [C4b]
16 [C4c]
94 [C4a]
85 [C4b]
25 [C4c]
68 [C4c]
3
4a
5b
6
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
7
8
2 [C3b]
9
69 [C3c]
28 [C3c]
10c
4 h
11
12d
13
14
15e
16
17
18
19
T2
BrCH2Ph (6.0)
BuI (6.0)
BrCH2COOEt (6.0)
BrCH2Ph (20.0)
BuI (20.0)
BrCH2COOEt (6.0)
BrCH2Ph (6.0)
BuI (8.0)
tert-BuOK (3.0)
tert-BuOK (3.0)
tert-BuOK (3.0)
K2CO3 (20.0)
K2CO3 (20.0)
K2CO3 (6.0)
Cs2CO3 (6.0)
Cs2CO3 (6.0)
Cs2CO3 (6.0)
RT
RT
RT
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
2 days
4 days
4
24
63 [T3a]
58 [T3b]
67 [T3c]
81 [T3a]
26 [T3b]
88 [T3c]
74 [T3a]
88 [T3b]
88 [T3c]
0 [T4a]
0 [T4b]
0 [T4c]
8 [T4a]
5 days
0 [T4b]
9
4
9
4
0 [T4c]
9 [T4a]
0 [T4b]
BrCH2COOEt (6.0)
trace [T4c]
a Monoalkylated compound C8a was obtained in 21% yield. b Monoalkylated compound C7b and C8b were obtained in 64 and 13% yields,
respectively. c The reaction was carried out in THF–DMF (4:1). d Monoalkylated compound T7b was obtained in 24% yield. e Monoalkylated
compound T7b was obtained in 63% yield.
Scheme 1 Reagents: i, 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane, imidazole, DMF.
Scheme 2 Reagents: i, RX, base, THF; ii, tetrabutylammonium fluoride, THF.
cations, K2CO3, also gave syn compound C3 preferentially,
though it was less active than tert-BuOK (entries 4–6). Altern-
ation of the base to Cs2CO3, however, drastically shifted the
stereoselectivity toward the anti counterpart C4 (entries 7–10).
Almost perfect anti-selective dialkylation was achieved with
bromomethylbenzene and iodobutane (entries 7 and 8), com-
pensating well the syn selectivity achieved by the use of tert-
BuOK (entries 1 and 2). Thus, a practical synthesis of both the
stereoisomers is now available only by changing the base.
Although the dialkylation with ethyl bromoacetate still pre-
ferred the formation of syn isomer C3c even by using Cs2CO3,
an addition of DMF greatly improved the anti selectivity
(entries 9 and 10). On the other hand, the stereoselectivity in the
dialkylation of thiacalixarene T2 was not altered by the metal
cation, giving syn isomer T3 selectively (entries 11–19). Addi-
tion of DMF had no effect on the stereoselectivity in this case.
Desilylation of the dialkylated products was carried out
by a simple treatment with tetrabutylammonium fluoride in
THF to liberate the corresponding proximally O,OЈ-dialkylated
calix[4]arenes quantitatively (Scheme 2).
Structural analyses of compounds C2–6 and T2–6
The TIPDS derivative C2 showed the molecular ion peak at 891
(Mϩ) in the FAB mass spectrum, indicating that it is an
intramolecularly bridged compound. Its 1H NMR spectrum in
CDCl3 showed two singlets (18 H each) for the tert-butyl
protons and four doublets (2 H each) for the aryl protons to
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 8 9 0 – 8 9 8
891

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support O,OЈ- rather than O,OЉ-bridged structures, as the latter
should show only two singlets for the aryl protons. It is known
that the chemical shift difference (∆δ) between the geminal
protons of a bridging methylene group of conventional calix-
[4]arenes varies depending on the circumstances.1a Thus, the
methylene protons between two adjacent phenol units of syn
conformation have the ∆δ value of ca. 0.9 ppm in nonpolar
solvents, whereas those between the units of anti conformation
less than 0.5 ppm. Compound C2 showed ∆δ values of more
than 0.9 ppm for all the methylene groups, indicating that it
adopted a cone conformation in solution. The intramolecularly
proximally bridged structure of the thiacalixarene analog T2
was also deduced from the molecular ion peak at 963 (Mϩ) in
the FAB mass spectrum and the resonance patterns of the tert-
protons, the magnetic equivalences suggesting C2-symmetric
structure. On the other hand, only one methylene carbon
appeared around 32 ppm in the 13C NMR spectra, indicating
that only two aryl units adjacent to the methylene group
statically adopted syn conformation. These observations indi-
cate that anti-diethers C6 rapidly interconvert between two par-
tial-cone conformations in solution. Although sulfur-bridged
analogs T5 and T6 lack structural information from the bridg-
ing moieties in the NMR analysis, their conformations are
expected to be the same as those of the corresponding methyl-
ene-bridged ones, considering the similarities in their 1H NMR
spectra.
Mechanistic consideration of the dialkylation reaction
1
butyl and aryl protons in the H NMR spectrum as described
In order to gain insight into the origin of the high stereo-
selectivity in the dialkylation, a stepwise alkylation of the
TIPDS derivative C2 was examined (Scheme 3, Table 2). Mono-
alkylation of compound C2 could be achieved by decreasing
molar equivalences of the alkyl halide and the base to the sub-
strate and reducing the reaction time to give compounds C7
and C8. Both compounds (e.g. C7a and C8a) showed four sing-
lets (9 H each) for the tert-butyl protons and eight doublets (1 H
each) for the aryl protons in the 1H NMR spectra in accordance
with their unsymmetrical structures. All the ∆δ values of the
methylene protons of compound C8a were larger than 0.9 ppm,
indicating that the compound adopted cone conformation and
thus the benzyl group was introduced from the same side to the
TIPDS moiety in regard to the mean plane of the macrocycle.
On the other hand, the conformation of counterpart C7a could
not be deduced from its NMR spectra, though it is apparent
that the benzyl group was introduced from the opposite side to
the TIPDS moiety, considering the fact that benzylation of this
compound gave dibenzyl ether C3a with 1,2-alternate conform-
ation (vide infra). The stereoselectivity of the monoalkylation
was strongly affected by the base employed. Thus, K2CO3
preferentially gave compound C7 (entries 1 and 2), while
Cs2CO3 gave compound C8 except the alkylation with ethyl
bromoacetate (entries 3–5). Monobenzyl ethers C7a and C8a
were then treated with bromomethylbenzene (6 mol equiv.) in
the presence of Cs2CO3 (6 mol equiv.) in THF to give dibenzyl
ethers C3a and C4a in 92 and 88% yields, respectively, as single
stereoisomers (Scheme 3). These observations should indicate
that the second alkylation in the one-pot dialkylation occurs
from the opposite side to the TIPDS moiety regardless of the
stereochemistry of the monoalkylated intermediates and that
the net stereochemistry of the dialkylation is determined at the
first alkylation step.
for compound C2. Although compound T2 lacks methylene
bridges which have been a probe for assigning the conformation
of conventional calix[4]arenes, its conformation was rather
safely deduced to be cone by comparing the chemical shifts of
the methyl protons of the TIPDS moiety [four doublets (6 H
each) at δ 0.80–1.38] with those of compound C2 [four doublets
(6 H each) at δ 0.79–1.37]; if compound T2 adopted 1,2-alter-
nate conformation, these protons should appear at a higher
field (ca. 0.4 ppm) because of the anisotropic shielding effects
by the facing benzene rings (vide infra).
The stereochemistry of dialkylated compounds C3, T3, C4
and T4 was determined by 1H and 13C NMR analyses as
exemplified by the cases of dibenzyl ethers C3a and C4a given
1
below. The H NMR spectrum of dibenzyl ether C3a showed
two singlets (18 H each) for the tert-butyl protons and four
doublets (2 H each) for the aromatic protons, indicating that the
compound adopted either cone or 1,2-alternate conformation
with the syn arrangement of the two benzyl moieties. The
signals of the bridging methylene protons appeared as three
pairs of doublets with an intensity ratio of 1 : 2 : 1. The double
intensity signals, which are assigned to the methylenes between
the benzene ring bearing a siloxy moiety and that bearing a
benzyloxy moiety, had the ∆δ value (0.2 ppm) of less than 0.5
ppm, indicating that the compound adopted 1,2-alternate con-
formation. The methyl signals of the TIPDS moiety appeared
at a higher field [δ 0.31, 0.71, 0.95 and 0.99 (each 6 H)] than
those of compound C2 (δ 0.79, 1.10, 1.31 and 1.37), which was
attributed to the shielding effects by the facing benzene rings. It
has been reported that conformation of calix[4]arenes can be
deduced from the 13C NMR chemical shifts of the methylene
signals. Thus, methylene carbons between two adjacent phenol
units of syn conformation resonate at 30–32 ppm, whereas
those between the units of anti conformation at 37–39 ppm.13
Dibenzyl ether C3a showed three signals at δ 33.8, 34.0 and 39.2
for the bridging methylene carbons, which supported the
assignment based on the 1H NMR analysis. On the other hand,
the 1H NMR spectrum of compound C4a showed four singlets
(9 H each) for the tert-butyl protons and eight doublets (1 H
each) for the aromatic protons. The unsymmetrical spectral pat-
terns unambiguously assigned the compound to the anti isomer
of partial-cone conformation. The conformation of thiacalix-
arene derivatives T3 was determined to be 1,2-alternate simi-
larly to the case of the methylene-bridged analogs C3 based on
the splitting patterns of the tert-butyl and aromatic protons
combined with the upfield shifts of the methyl signals of the
TIPDS moiety in the 1H NMR spectra. The NOESY spectrum
of dibenzyl ether T3a revealed a correlation between the methyl
protons of the TIPDS moiety and the tert-butyl protons to
support the assignment.
1
The reaction mechanism was supported by H NMR analy-
ses of metal salts formed by treatment of the substrates with the
Desilylated syn-diethers C5 had ∆δ values of larger than 0.9
ppm for all four methylene protons, indicating that the com-
pounds adopted cone conformation in solution.5,14 The 1H
NMR spectrum of the anti counterparts C6 showed one singlet
(2 H) for the hydroxy protons, two singlets (18 H each) for the
tert-butyl protons and four doublets (2 H each) for the aryl
Scheme 3 Reagents: i, RX, base, THF; ii, bromomethylbenzene,
Cs2CO3, THF.
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 8 9 0 – 8 9 8
892

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Table 2 Monoalkylation of TIPDS derivative C2 with RX in THF at reflux
Yield (%) [Product]
Entry
RX (mol equiv.)
Base (mol equiv.)
Time/h
C7
C8
1
2
3
BrCH2Ph (6.0)
BuI (12.0)
BrCH2Ph (2.0)
BuI (4.0)
K2CO3 (6.0)
K2CO3 (12.0)
Cs2CO3 (2.0)
Cs2CO3 (2.0)
Cs2CO3 (1.0)
8
30
4
6
10
70 [C7a]
78 [C7b]
0 [C7a]
3 [C7b]
34 [C7c]
18 [C8a]
18 [C8b]
89 [C8a]
77 [C8b]
21 [C8c]
4
5a
BrCH2COOEt (1.1)
a Dialkylated compound C3c was obtained in 28% yield.
Fig. 1 1H NMR spectra (300 MHz) of 10.0 mM solution of TIPDS derivatives C2 (a–c) and T2 (d–f) in THF-d8 in the presence or absence of a base
at 20 ЊC: (a and d) no base; (b and e) tert-BuOK (1.0 mol equiv.); (c and f) Cs2CO3 (saturated).
bases. Fig. 1 shows the 1H NMR spectra of compounds C2 and
T2 measured in the presence or absence of a base in THF-d8.
The signals of the free calixarene decreased or even disappeared
by addition of 1.0 mol equiv. of tert-BuOK or an excess of
Cs2CO3 with the appearance of new signals, indicating the
formation of a salt between the phenoxide and the metal cation.
As mentioned above, TIPDS derivatives of 1,2-alternate con-
formation can be distinguished from those of the other con-
the TIPDS moiety.15 On the other hand, the cesium salt of
compound C2 showed two singlets for the tert-butyl protons
and four doublets for the aryl protons with no methyl signals of
the TIPDS moiety around 0.4 ppm (c), indicating that the salt
adopted a cone conformation. It has been reported that the
monocesium salt of p-tert-butylcalix[4]arene adopts a cone con-
formation in the solid state and chloroform solution, the metal
ion being included within the calixarene cavity through inter-
actions with the π electrons of the aromatic rings.16 Therefore, it
seems likely that in the cone conformation of the monoanion of
compound C2, the Csϩ ion is also located within the cavity and
the resulting cation-π interactions stabilize the cone conform-
ation. The stereochemical course of the dialkylation can be
rationalized by the conformations of these salts which should
mediate the reaction (Scheme 4). Thus, the first alkylation of the
potassium salt of 1,2-alternate conformation should occur
from the opposite side to the TIPDS moiety to give monoalkyl-
1
formations by H NMR spectrum, where some of the methyl
protons of the TIPDS moiety are strongly shielded by the
facing benzene ring, appearing around 0.4 ppm. Based on this
criteria, the conformation of the salt between the monoanion
of compound C2 and Kϩ was assigned as 1,2-alternate (b). The
monoanion seems to bind to a Kϩ ion in this conformation to
avoid steric repulsion imposed by the bulky TIPDS moiety, with
the aid of coordination of the adjacent phenolic hydroxy group
and cation-π interactions with the two benzene rings bridged by
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 8 9 0 – 8 9 8
893

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Scheme 4
ated intermediate C7, while a similar reaction of the cesium salt
of cone conformation will occur from the same side to give
intermediate C8. The second alkylation seems to be allowed
only from the opposite side to the TIPDS moiety in both cases
because of the steric congestion, yielding the dialkylated prod-
ucts of syn (C3) and anti (C4) conformations for Kϩ and Csϩ
ions, respectively.7 On the contrary, because the metal salts of
thiacalix[4]arene tend to form five-membered bischelate com-
plexes by coordination of the adjacent hydroxy group and a
bridging sulfur atom,17 the cesium salt, as well as the potassium
salt, adopts 1,2-alternate conformation like the potassium salt
internal standard and CDCl3 as a solvent, unless otherwise
noted. J-values are given in Hz. Mass spectra were measured on
a JEOL JMS-DX602 spectrometer. Silica gel columns were
prepared by use of Merck silica gel 60 (63–200 µm). THF was
distilled from sodium diphenylketyl just before use. Compound
C1 was prepared according to the Gutsche’s procedure.18 Com-
pound T1 was prepared as described previously.11a Other
materials were used as purchased.
General procedure for the preparation of TIPDS derivatives
C2 and T2
1
of conventional calixarene C2, as is clearly shown by the H
To a suspension of calix[4]arene C1 or T1 (5.00 mmol) in dry
DMF (50 cm3) was added imidazole (1.02 g, 15.0 mmol) and
the mixture was stirred at room temperature for 30 min. To the
mixture was added dropwise a solution of TIPDSCl (1.90 g,
6.02 mmol) in DMF (25 cm3) over 1 h and the resulting mixture
was stirred for 11 h. The mixture was cooled to 0 ЊC and
quenched by addition of 2 M HCl (100 cm3) to liberate a pre-
cipitate, which was collected by filtration, washed with water
and then purified by recrystallization from dichloromethane–
methanol.
NMR analysis [Fig. 1, (e) and (f)]. Thus the first alkylation
should occur from the opposite side to the TIPDS moiety,
giving syn diether T3.
Conclusion
We have shown here that the 1,1,3,3-tetraisopropyldisiloxane-
1,3-diyl unit is very useful in protecting two adjacent hydroxy
groups of calix[4]arenes; the O,OЈ-capping reaction, subsequent
alkylation of the remaining hydroxy groups and final desilyl-
ation proceed quite smoothly with excellent yields to provide an
efficient method for the net proximal dialkylation of calix-
[4]arenes. The syn/anti selectivity in the alkylation was very high
and could be altered by the entity of the macrocycle and the
metal cation of the base employed, the origin of which was
ascribed to the conformation of the metal salt generated in situ
from the macrocycle and the base.
Compound C2. As a colorless powder (90%), mp 238–240 ЊC
(Found: C, 75.2; H, 9.3. Calc. for C56H82O5Si2: C, 75.5; H,
9.3%); δH(500 MHz) 0.79 (6 H, d, J 7.4, CHCH3 × 2), 1.10 (6 H,
d, J 7.4, CHCH3 × 2), 1.17 [18 H, s, C(CH3)3 × 2], 1.17–1.21
[2 H, m, CH(CH3)2 × 2], 1.23 [18 H, s, C(CH3)3 × 2], 1.31 (6 H,
d, J 7.4, CHCH3 × 2), 1.37 (6 H, d, J 7.4, CHCH3 × 2), 1.47–
1.53 [2 H, m, CH(CH3)2 × 2], 3.33–3.42 (4 H, m, ArCHAr × 4),
4.20 (1 H, d, J 13.6, ArCHAr), 4.55 (1 H, d, J 13.3, ArCHAr),
4.60 (2 H, d, J 13.1, ArCHAr × 2), 6.95 (2 H, d, J 2.5, ArH × 2),
6.98 (2 H, d, J 2.3, ArH × 2), 7.02 (2 H, d, J 2.5, ArH × 2), 7.06
(2 H, d, J 2.3, ArH × 2) and 8.66 (2 H, s, OH × 2); m/z (FAB)
891 (Mϩ).
Experimental
Mps were taken using a Mitamura Riken MP-P or Yamato
IA-9000 apparatus. Samples for the mp measurement were
routinely recrystallized from dichloromethane–methanol, unless
otherwise noted. Microanalyses were carried out in the Micro-
analytical Laboratory of the Institute of Multidisciplinary
Research for Advanced Materials, Tohoku University. IR
spectra were recorded on a JEOL JIR-3510 spectrophotometer.
1H and 13C NMR spectra were recorded on a Bruker DPX-400,
DRX-500 or JEOL JNM-ECA300 spectrometer using tetra-
methylsilane (1H NMR) or chloroform (13C NMR) as an
Compound T2. As a colorless powder (92%), mp 308–310 ЊC
(Found: C, 64.7; H, 7.7; S, 13.3. Calc. for C52H74O5S4Si2: C, C,
64.8; H, 7.7; S, 13.3%); δH(500 MHz) 0.80 (6 H, d, J 7.6,
CHCH3 × 2), 1.14–1.20 [14 H, m, CHCH3 × 4 and CH(CH3)2
× 2], 1.16 [18 H, s, C(CH3)3 × 2], 1.24 [18 H, s, C(CH3)3 × 2],
1.32–1.39 [2 H, m, CH(CH3)2 × 2], 1.38 (6 H, d, J 2.1, CHCH3
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 8 9 0 – 8 9 8
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× 2), 7.49 (2 H, d, J 2.5, ArH × 2), 7.51 (2 H, d, J 2.5, ArH × 2),
7.54–7.56 (4 H, m, ArH × 4) and 8.12 (2 H, s, OH × 2); m/z
(FAB) 963 [(M ϩ 1)ϩ].
31.57, 31.71, 33.81, 34.02, 39.25, 59.93, 69.60, 125.59, 125.73,
125.85, 126.62, 129.46, 129.81, 131.83, 134.25, 142.01, 144.25,
149.61, 153.25 and 170.02; m/z (FAB) 1086 [(MϩNa)ϩ].
General procedure for the alkylation of TIPDS derivatives C2
and T2 (Tables 1 and 2)
Compound T3a. Dichloromethane–hexane (1 : 2) as the
eluent; crystals, mp 287–288 ЊC (Found: C, 69.1; H, 7.5; S, 11.0.
Calc. for C66H86O5S4Si2: C, 69.3; H, 7.6; S, 11.2%); δH(500
MHz) 0.38 (6 H, d, J 7.5, CHCH3 × 2), 0.74 (6 H, d, J 7.6,
CHCH3 × 2), 0.82–0.88 [2 H, m, CH(CH3)2 × 2], 1.02 (6 H, d,
J 7.6, CHCH3 × 2), 1.12 (6 H, d, J 7.5, CHCH3 × 2), 1.13–1.20
[2 H, m, CH(CH3)2 × 2], 1.13 [18 H, s, C(CH3)3 × 2], 1.27 [18 H,
s, C(CH3)3 × 2], 4.45 (2 H, d, J 12.2, OCHPh × 2), 4.14 (2 H, d,
J 12.2, OCHPh × 2), 6.37 (4 H, d, J 7.4, OCH2Ph × 2), 6.94
(4 H, t, J 7.6, OCH2Ph × 2), 7.04 (2 H, t, J 7.3, OCH2Ph × 2),
7.35 (2 H, d, J 2.5, ArH × 2), 7.45 (2 H, d, J 2.6, ArH × 2), 7.50
(2 H, d, J 2.6, ArH × 2) and 7.72 (2 H, d, J 2.5, ArH × 2);
m/z (FAB): 1143 [(M ϩ 1)ϩ].
To a 50.0 mM solution of compound C2 or T2 in dry THF were
added a base and an alkyl halide at 0 ЊC (Table 1, entries 1–3) or
room temperature (the other entries) and the mixture was
stirred at an appropriate temperature for 1 h to 5 days, after
which it was cooled to 0 ЊC and quenched with 2 M HCl. The
mixture was extracted with chloroform and the extract was
washed successively with 2 M HCl and water, dried (MgSO4)
and evaporated. The residue was chromatographed on silica gel
by using the indicated eluent. See Tables 1 and 2 for the reaction
conditions and the product yields.
Compound C3a. Dichloromethane–hexane (1 : 3) as the
eluent; crystals, mp 238–239 ЊC (Found: C, 78.4; H, 8.8. Calc.
for C70H94O5Si2: C, 78.5; H, 8.8%); δH(500 MHz) 0.31 (6 H, d,
J 7.5, CHCH3 × 2), 0.71 (6 H, d, J 7.0, CHCH3 × 2), 0.74–0.82
[2 H, m, CH(CH3)2 × 2], 0.95 (6 H, d, J 7.0 Hz, CHCH3 × 2),
0.99 (6 H, d, J 7.5, CHCH3 × 2), 0.97–1.06 [2 H, m, CH(CH3)2
× 2], 1.14 [18 H, s, C(CH3)3 × 2], 1.26 [18 H, s, C(CH3)3 × 2],
2.30 (1 H, d, J 12.3, ArCHAr), 3.32 (1 H, d, J 12.3, ArCHAr),
3.36 (1 H, d, J 13.3, ArCHAr), 3.75 (2 H, d, J 16.5, ArCHAr
× 2), 3.96 (2 H, d, J 12.2, OCHPh × 2), 3.97 (2 H, d, J 16.5,
ArCHAr × 2), 4.14 (2 H, d, J 12.2, OCHPh × 2), 4.43 (1 H, d,
J 13.3, ArCHAr), 6.19 (4 H, d, J 7.3, OCH2Ph × 2), 6.91 (2 H,
d, J 2.4, ArH × 2), 6.94–6.97 (6 H, m, ArH × 2, OCH2Ph × 2),
7.03–7.06 (4 H, m, ArH × 2, OCH2Ph × 2) and 7.25 (2 H, d,
J 2.4, ArH × 2); δC(125 MHz) 13.71, 14.02, 16.67, 16.87, 17.21,
17.68, 29.29, 31.29, 31.52, 33.72, 34.01, 34.17, 39.60, 73.59,
125.00, 125.05, 125.44, 125.56, 126.18, 127.35, 127.87, 129.36,
130.65, 132.10, 135.13, 137.82, 142.30, 144.28, 149.82 and
152.75; m/z (FAB) 1071 (Mϩ).
Compound T3b. Dichloromethane–hexane (1 : 6) as the
eluent; crystals, mp 322–323 ЊC (Found: C, 66.9; H, 8.4; S,12.2.
Calc. for C60H90O5S4Si2: C, 67.0; H, 8.4; S,11.9%); δH(300 MHz)
0.40 (6 H, d, J 7.5, CHCH3 × 2), 0.77 (6 H, d, J 7.6, CHCH3
× 2), 0.78 (6 H, t, J 7.2, CH2CH3 × 2), 0.79–0.89 [2 H, m,
CH(CH3)2 × 2], 1.01 (6 H, d, J 7.5, CHCH3 × 2), 1.07 (6 H, d,
J 7.2, CHCH3 × 2), 1.04–1.21 [6 H, m, CH(CH3)2 × 2 and
CH2CH3 × 2], 1.27 [18 H, s, C(CH3)3 × 2], 1.32 [18 H, s, C(CH3)3
× 2], 1.24–1.35 (4 H, m, OCH2CH2 × 2), 3.53–3.67 (4 H, m,
OCH2CH2 × 2), 7.31 (2 H, d, J 2.4, ArH × 2), 7.52 (2 H, d,
J 2.4, ArH × 2), 7.56 (2 H, d, J 2.4, ArH × 2) and 7.71 (2 H, d,
J 2.8, ArH × 2).
Compound T3c. Dichloromethane as the eluent; crystals, mp
284–285 ЊC (Found: C, 63.2; H, 7.5; S, 11.3. Calc. for C60H86-
O9S4Si2: C, 63.5; H, 7.6; S, 11.3%); νmax/cmϪ1 1765 (CO); δH(500
MHz) 0.47 (6 H, d, J 7.4, CHCH3 × 2), 0.80 (6 H, d, J 7.6,
CHCH3 × 2), 0.85–0.95 [2 H, m, CH(CH3)2 × 2], 1.03 (6 H, d,
J 7.4, CHCH3 × 2), 1.09 (6 H, d, J 7.6, CHCH3 × 2), 1.14 (6 H,
t, J 7.2, OCH2CH3 × 2), 1.14–1.22 [2 H, m, CH(CH3)2 × 2], 1.27
[18 H, s, C(CH3)3 × 2], 1.30 [18 H, s, C(CH3)3 × 2], 3.62 (2 H, d,
J 16.3, OCHCO × 2), 4.03 (4 H, q, J 7.2, OCH2CH3 × 2), 4.96
(2 H, d, J 16.3, OCHCO × 2), 7.33 (2 H, d, J 2.5, ArH × 2), 7.48
(2 H, d, J 2.5, ArH × 2), 7.58 (2 H, d, J 2.6, ArH × 2) and 7.75
(2 H, d, J 2.6, ArH × 2); m/z (FD) 1134 (Mϩ).
Compound C3b. Dichloromethane–hexane (1 : 3) as the
eluent; crystals, mp 243–244 ЊC (Found: C, 76.6; H, 9.9. Calc.
for C64H98O5Si2: C, 76.6; H, 9.8%); δH(300 MHz) 0.36 (6 H, d,
J 7.2, CHCH3 × 2), 0.56–0.72 (2 H, m, OCH2CH × 2), 0.72–
0.85 [14 H, m, CHCH3 × 2, CH(CH3)2 × 2 and CH2CH3 × 2],
0.91–0.96 (12 H, m, CHCH3 × 4), 0.92–1.18 [8 H, m, CH(CH3)2
× 2, OCH2CH × 2 and CH2CH2CH3 × 2], 1.27 [18 H, s,
C(CH3)3 × 2], 1.30 [18 H, s, C(CH3)3 × 2], 3.07 (1 H, d, J 12.4,
ArCHAr), 3.16–3.29 (5 H, m, OCH2CH2 × 2 and ArCHAr),
3.78 (2 H, d, J 16.1, ArCHAr × 2), 3.94 (2 H, d, J 16.5,
ArCHAr × 2), 4.14 (1 H, d, J 12.0, ArCHAr), 4.31 (1 H, d,
J 13.1, ArCHAr), 6.94 (2 H, d, J 2.1, ArH × 2), 6.98 (2 H, d,
J 2.4, ArH × 2), 7.09 (2 H, d, J 2.4, ArH × 2) and 7.18 (2 H, d,
J 2.8, ArH × 2); δC(75 MHz) 13.66, 13.90, 13.98, 14.23, 14.51,
16.96, 17.04, 17.36, 17.69, 19.06, 29.79, 30.04, 60.18, 61.60,
61.79, 31.91, 33.83, 34.07, 39.38, 73.50, 125.34, 125.40, 125.54,
125.66, 126.27,129.97, 132.17, 134.51, 141.84, 143.85, 149.96
and 154.24.
Compound C4a. Dichloromethane–hexane (1 : 4) as the
eluent; crystals, mp 236–237 ЊC (Found: C, 78.7; H, 9.0. Calc.
for C70H94O5Si2: C, 78.5; H, 8.8%); δH(500 MHz) 0.61 (3 H, d,
J 7.3, CHCH3), 0.70 [9 H, s, C(CH3)3], 0.75 [9 H, s, C(CH3)3],
0.78 (3 H, d, J 7.6, CHCH3), 0.83–0.89 [1 H, m, CH(CH3)2],
0.85 (3 H, d, J 7.3, CHCH3), 0.90 (3 H, d, J 7.3, CHCH3), 1.01–
1.06 (9 H, m, CHCH3 × 3), 1.13–1.22 [2 H, m, CH(CH3)2 × 2],
1.30–1.36 [1 H, m, CH(CH3)2], 1.31 (3 H, d, J 7.1, CHCH3),
1.34 [9 H, s, C(CH3)3], 1.40 [9 H, s, C(CH3)3], 2.88 (1 H, d,
J 12.2, ArCHAr), 2.89 (1 H, d, J 13.4, CHPh), 3.09 (1 H,
d, J 13.4, CHPh), 3.22 (1 H, d, J 13.2, ArCHAr), 3.47 (1 H, d,
J 15.7, ArCHAr), 3.56 (1 H, d, J 15.7, ArCHAr), 3.68 (1 H, d,
J 15.4, ArCHAr), 3.92 (1 H, d, J 15.4, ArCHAr), 4.25 (1 H,
d, J 12.2, ArCHAr), 4.39 (1 H, d, J 12.2, ArCHAr), 4.66 (1 H,
d, J 11.5, CHPh), 4.71 (1 H, d, J 11.5, CHPh), 5.93 (2 H, d,
J 7.1, CH2Ph), 6.47 (1 H, d, J 2.4, ArH), 6.62 (1 H, d, J 2.4,
ArH), 6.77 (2 H, t, J 7.4, CH2Ph), 6.78 (1 H, d, J 2.4, ArH), 6.85
(1 H, t, J 7.3, CH2Ph), 6.88 (1 H, d, J 2.5, ArH), 7.00–7.03 (2 H,
m, CH2Ph), 7.05 (1 H, d, J 2.5, ArH), 7.10 (1 H, d, J 2.4, ArH),
7.12 (1 H, d, J 2.5, ArH), 7.14 (1 H, d, J 2.4, ArH), 7.21–7.25
(2 H, m, CH2Ph) and 7.26–7.30 (1 H, m, CH2Ph); m/z (FD)
1071 (Mϩ).
Compound C3c. Dichloromethane–hexane (1 : 1) as the
eluent; crystals, mp 213–214 ЊC (Found: C, 72.05; H, 8.8. Calc.
for C64H94O9Si2: C, 72.3; H, 8.9%); νmax(KBr)/cmϪ1 1761 (CO);
δH(500 MHz) 0.42 (6 H, d, J 7.4, CHCH3 × 2), 0.80 (6 H, d,
J 7.1, CHCH3 × 2), 0.93 (6 H, d, J 7.4, CHCH3 × 2), 0.96 (6 H,
d, J 7.1, CHCH3 × 2), 0.97–1.06 [4 H, m, CH(CH3)2 × 4], 1.11
(6 H, t, J 7.0, OCH2CH3 × 2), 1.26 [18 H, s, C(CH3)3 × 2], 1.28
[18 H, s, C(CH3)3 × 2], 3.14 (1 H, d, J 12.8, ArCHAr), 3.30 (1 H,
d, J 13.2, ArCHAr), 3.55 (2 H, d, J 16.3, OCHCO × 2), 3.93
(2 H, d, J 16.3, OCHCO × 2), 3.89–4.00 (8 H, m, ArCHAr × 4
and OCH2CH3 × 2), 4.33 (1 H, d, J 13.2, ArCHAr), 4.83 (1 H,
d, J 12.8, ArCHAr), 6.94 (2 H, d, J 2.2, ArH × 2), 7.05–7.06
(4 H, m, ArH × 4) and 7.23 (2 H, d, J 2.5, ArH × 2); δC(125
MHz) 14.07, 14.15, 15.11, 17.05, 17.38, 17.60, 31.36, 31.48,
Compound C4b. Dichloromethane–hexane (1 : 4) as the
eluent; crystals, mp 217–219 ЊC (Found: C, 76.8; H, 10.0. Calc.
for C64H98O5Si2: C, 76.6; H, 9.8%); δH(500 MHz) 0.56–0.66
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 8 9 0 – 8 9 8
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(7 H, m, CH2CH2CH3), 0.66 (3 H, d, J 7.0, CHCH3), 0.81 (3 H,
d, J 7.5, CHCH3), 0.87–1.07 [17 H, m, CHCH3 × 4, CH(CH3)2
× 2 and CH2CH3], 1.09–1.21 [1 H, m, CH(CH3)2], 1.11 [3 H, d,
J 7.5, CH(CH3)2], 1.14 [18 H, s, C(CH3)3 × 2], 1.22–1.31 [6 H,
m, CHCH3, CH(CH3)2 and CH2CH2CH3], 1.26 [9 H, s,
C(CH3)3], 1.34 [9 H, s, C(CH3)3], 1.55–1.61 (2 H, m, OCH2-
CH2), 2.45–2.51 (1 H, m, OCHCH2), 2.60–2.66 (1 H, m,
OCHCH2), 3.11 (1 H, d, J 12.2, ArCHAr), 3.20 (1 H, d, J 13.2,
ArCHAr), 3.55–3.67 (2 H, m, OCH2CH2), 3.72 (1 H, d, J 15.3,
ArCHAr), 3.74 (1 H, d, J 15.7, ArCHAr), 3.83 (1 H, d, J 15.7,
ArCHAr), 3.91 (1 H, d, J 15.3, ArCHAr), 4.35 (1 H, d, J 13.2,
ArCHAr), 4.46 (1 H, d, J 12.2, ArCHAr), 6.83 (1 H, d, J 2.3,
ArH), 6.85 (1 H, d, J 2.4, ArH), 6.88 (1 H, d, J 2.4, ArH), 6.97
(1 H, d, J 2.4, ArH), 7.00 (1 H, d, J 2.3, ArH), 7.06 (1 H, d,
J 2.1, ArH), 7.07 (1 H, d, J 2.4, ArH) and 7.10 (1 H, d, J 2.1,
ArH); m/z (FD) 1004 [(M ϩ 1)ϩ].
4.63 (1 H, d, J 12.1, CHPh), 6.27 (1 H, s, OH), 6.33 (2 H, d,
J 7.4, CH2Ph), 6.86–6.88 (2 H, m, ArH × 2), 6.92 (1 H, d, J 2.4,
ArH), 6.95 (2 H, t, J 7.3, CH2Ph), 6.98 (1 H, d, J 2.3, ArH), 7.02
(1 H, t, J 7.3, CH2Ph), 7.08 (1 H, d, J 2.2, ArH), 7.14 (1 H, d,
J 2.3, ArH) and 7.26–7.28 (2 H, m, ArH × 2); δC(125 MHz)
13.63, 13.67, 14.28, 14.48, 16.29, 16.79, 17.02, 17.12, 17.22,
17.27, 17.42, 18.16, 31.27, 31.40, 31.51, 31.65, 31.87, 32.74,
33.71, 33.77, 34.05, 34.07, 34.25, 38.68, 39.84, 74.59, 124.24,
124.45, 125.24, 125.62, 125.91, 125.96, 126.00, 126.24, 126.33,
126.98, 127.64, 128.06, 129.34, 129.71, 129.96, 131.51, 132.61,
134.11, 136.29, 143.05, 143.11, 146.39, 149.52, 149.60, 150.69
and 151.60; m/z (FD) 981 (Mϩ).
Compound C7b. Dichloromethane–hexane (1 : 3) as the
eluent; crystals, mp 191–193 ЊC (Found: C, 76.1; H, 9.7. Calc.
for C60H90O5Si2: C, 76.1; H, 9.6%); δH(300 MHz) Ϫ0.13 (3 H, d,
J 7.2, CHCH3), 0.36–0.54 [2 H, m, CH(CH3)2 and OCH2CH],
0.69 (3 H, d, J 7.6, CHCH3), 0.69 (3 H, t, J 7.2, CH2CH3), 0.73–
0.82 [6 H, m, CHCH3, CH(CH3)2 and CH2CH3], 0.86 (3 H, d,
J 7.6, CHCH3), 0.88–1.04 [8 H, m, CHCH3 × 2, CH(CH3)2 and
OCH2CH], 1.01 (3 H, d, J 7.2, CHCH3), 1.06–1.19 [1 H, m,
CH(CH3)2], 1.10 (3 H, d, J 7.6, CHCH3), 1.25 [9 H, s, C(CH3)3],
1.27 [9 H, s, C(CH3)3], 1.30 [9 H, s, C(CH3)3], 1.33 [9 H, s,
C(CH3)3], 3.21–3.35 (2 H, m, OCH2CH2), 3.29 (1 H, d, J 13.1,
ArCHAr), 3.34 (1 H, d, J 12.7, ArCHAr), 3.84 (1 H, d, J 16.8,
ArCHAr), 3.85 (1 H, d, J 12.7, ArCHAr), 3.86 (1 H, d, J 17.5,
ArCHAr), 4.04 (1 H, d, J 17.5, ArCHAr), 4.06 (1 H, d, J 15.8,
ArCHAr), 4.36 (1 H, d, J 13.1, ArCH2Ar), 6.42 (1 H, s, OH),
6.91–6.98 (3 H, m, ArH × 3), 6.99 (1 H, d, J 2.4, ArH), 7.04
(1 H, d, J 2.4, ArH), 7.17 (2 H, d, J 2.4, ArH × 2) and 7.32 (1 H,
d, J 2.4, ArH); δC(75 MHz) 13.29, 13.50, 13.78, 14.46, 14.62,
15.90, 16.67, 17.03, 17.20, 17.26, 17.39, 17.51, 18.02, 18.68,
29.42, 31.47, 31.63, 31.78, 32.46, 33.51, 33.90, 34.18, 39.52,
39.84, 74.19, 124.15, 124.75, 124.83, 125.53, 125.57, 126.21,
126.26, 126.45, 127.54, 128.16, 128.69, 129.06, 131.24, 131.69,
131.73, 134.46, 141.74, 142.64, 142.82, 146.43, 148.80, 150.10,
150.44 and 151.62; m/z (FD) 946 (Mϩ).
Compound C4c. Dichloromethane–hexane (2 : 1) as the
eluent; crystals, mp 195–197 ЊC (Found: C, 72.2; H, 9.1. Calc.
for C64H94O9Si2: C, 72.3; H, 8.9%); νmax/cmϪ1 1760 (CO); δH(400
MHz) 0.65 (3 H, d, J 7.3, CHCH3), 0.77 (3 H, d, J 7.3, CHCH3),
0.84 (3 H, d, J 7.6, CHCH3), 0.78–0.84 [1 H, m, CH(CH3)2],
0.91 (3 H, d, J 7.5, CHCH3), 1.02 (3 H, d, J 7.5, CHCH3), 1.06
(3 H, d, J 7.6, CHCH3), 1.08 [9 H, s, C(CH3)3], 1.09 [9 H, s,
C(CH3)3], 1.15 (3 H, t, J 7.2, OCH2CH3), 1.13–1.16 [2 H, m,
CH(CH3)2], 1.18–1.24 [1 H, m, CH(CH3)2], 1.27 (3 H, t, J 7.2,
OCH2CH3), 1.27 (3 H, d, J 8.7, CH(CH3)2), 1.30 [9 H, s,
C(CH3)3], 1.32 [9 H, s, C(CH3)3], 1.38–1.40 [3 H, br, CH(CH3)2],
2.75 (1 H, d, J 15.7, OCHCO), 3.07 (1 H, d, J 15.7, OCHCO),
3.15 (1 H, d, J 12.6, ArCHAr), 3.20 (1 H, d, J 13.2, ArCHAr),
3.85 (1 H, d, J 14.9, ArCHAr), 3.92 (1 H, d, J 14.9, ArCHAr),
3.91–4.03 (4 H, m, OCH2CH3 and ArCHAr × 2), 4.16 (2 H, q,
J 7.2, OCH2CH3), 4.31 (1 H, d, J 13.2, ArCH2Ar), 4.32 (1 H, d,
J 15.8, OCH2CO), 4.45 (1 H, d, J 15.8, OCH2CO), 4.61 (1 H, d,
J 12.6, ArCH2Ar), 6.85 (1 H, d, J 2.5, ArH), 6.92 (1 H, d, J 2.4,
ArH), 6.97 (2 H, d, J 2.5, ArH × 2), 7.01 (1 H, d, J 2.5, ArH),
7.08 (1 H, d, J 2.5, ArH), 7.10 (1 H, d, J 2.4, ArH) and 7.24
(1 H, d, J 2.4, ArH); m/z (FD) 1062 (Mϩ).
Compound C7c. Dichloromethane–hexane (1 : 2) as the
eluent; crystals, mp 228–230 ЊC (decomp.) (Found: C, 73.5; H,
9.2. Calc. for C60H88O7Si2: C, 73.7; H, 9.1%); νmax/cmϪ1 1745
(CO); δH(300 MHz) 0.29 (3 H, d, J 7.2, CHCH3), 0.42 (3 H, d,
J 7.2, CHCH3), 0.69–0.84 [3 H, m, CH(CH3)2 × 3], 0.77 (3 H, d,
J 7.2, CHCH3), 0.81 (3 H, d, J 6.5, CHCH3), 0.91–1.02 (12 H,
m, CHCH3 × 3 and OCH2CH3), 1.02–1.13 [1 H, m, CH(CH3)2],
1.05 (3 H, d, J 7.6, CHCH3), 1.27 [18 H, s, C(CH3)3 × 2], 1.28 [9
H, s, C(CH3)3], 1.29 [9 H, s, C(CH3)3], 3.32 (2 H, d, J 14.1,
ArCHAr × 2), 3.56 (1 H, d, J 15.6, OCHCO), 3.79–4.11 (8 H,
m, ArCHAr × 5, OCHCO and OCH2CH3), 4.37 (1 H, d, J 13.1,
ArCHAr), 6.18 (1 H, s, OH), 6.93 (1 H, d, J 2.1, ArH), 6.97–
7.03 (4 H, m, ArH × 4), 7.16 (1 H, d, J 2.1, ArH), 7.18 (1 H, d,
J 2.8, ArH) and 7.26 (1 H, d, J 3.1, ArH); δC(75 MHz) 13.72,
13.82, 14.06, 14.13, 14.18, 16.47, 16.91, 17.03, 17.28, 17.40,
17.46, 17.90, 31.44, 31.61, 31.68, 31.86, 33.64, 33.85, 33.91,
34.22, 39.11, 39.59, 60.85, 69.92, 76.68, 124.48, 124.90, 125.14,
125.74, 126.10, 126.19, 126.37, 127.19, 128.95, 129.05, 130.25,
131.04, 132.19, 133.95, 140.99, 142.72, 142.80, 146.54, 149.16,
149.53, 150.68, 151.46 and 168.43; m/z (FD) 978 [(M ϩ 1)ϩ].
Compound T4a. Dichloromethane–hexane (1 : 2) as the
eluent; crystals, mp 266–267 ЊC (Found: C, 69.4; H, 7.6; S, 11.4.
Calc. for C66H86O5S4Si2: C, 69.3; H, 7.6; S, 11.2%); δH(300
MHz) 0.61 (3 H, d, J 6.9, CHCH3), 0.74 (3 H, d, J 7.6, CHCH3),
0.76–0.80 (3 H, m, CHCH3), 0.78 [9 H, s, C(CH3)3], 0.80 [9 H, s,
C(CH3)3], 0.84 (3 H, d, J 7.2, CHCH3), 0.99 (3 H, d, J 5.5,
CHCH3), 1.02–1.11 [1 H, m, CH(CH3)2], 1.06 (3 H, d, J 7.5,
CHCH3), 1.10 (3 H, d, J 7.2, CHCH3), 1.15–1.40 [3 H, m,
CH(CH3)2 × 3], 1.28 (3 H, d, J 6.9, CHCH3), 1.32 [9 H, s,
C(CH3)3], 1.36 [9 H, s, C(CH3)3], 4.73 (2 H, s, OCH2Ph), 4.92
(1 H, d, J 11.0, OCHPh), 5.13 (1 H, d, J 11.0, OCHPh), 6.22
(2 H, d, J 7.2, OCH2Ph), 6.71 (2 H, t, J 7.5, OCH2Ph), 6.89
(1 H, t, J 7.2, OCH2Ph), 7.02 (1 H, d, J 2.4, ArH), 7.16 (1 H, d,
J 2.4, ArH), 7.26–7.32 (5 H, m, ArH × 2 and OCH2Ph), 7.35–
7.40 (4 H, m, ArH × 2 and OCH2Ph), 7.71 (1 H, d, J 2.7, ArH)
and 7.78 (1 H, d, J 2.7, ArH).
Compound C7a. Dichloromethane–hexane (1 : 3) as the
eluent; crystals, mp 193–194 ЊC (Found: C, 76.9; H, 9.2. Calc.
for C63H88O5Si2: C, 77.1; H, 9.0%); δH(500 MHz) 0.23 (3 H, d,
J 7.4, CHCH3), 0.56 (3 H, d, J 7.5, CHCH3), 0.68–0.75 [1 H, m,
CH(CH3)2], 0.76 (3 H, d, J 7.5, CHCH3), 0.80 (3 H, d, J 7.0,
CHCH3), 0.85 (3 H, d, J 7.4, CHCH3), 0.79–0.89 [1 H, m,
CH(CH3)2], 0.92–1.05 [7 H, m, CHCH3 × 2 and CH(CH3)2],
1.01 [9 H, s, C(CH3)3], 1.14 (3 H, d, J 7.5, CHCH3), 1.08–1.15
[1 H, m, CH(CH3)2], 1.21 [9 H, s, C(CH3)3], 1.30 [9 H, s,
C(CH3)3], 1.38 [9 H, s, C(CH3)3], 3.23 (1 H, d, J 13.9, ArCHAr),
3.39 (1 H, d, J 13.2, ArCHAr), 3.54 (1 H, d, J 13.9, ArCHAr),
3.76 (1 H, d, J 16.4, ArCHAr), 3.91 (1 H, d, J 16.5, ArCHAr),
4.01 (1 H, d, J 16.4, ArCHAr), 4.07 (1 H, d, J 12.1, CHPh),
4.14 (1 H, d, J 16.5, ArCHAr), 4.46 (1 H, d, J 13.2, ArCHAr),
Compound T7b. Dichloromethane–hexane (1 : 6) as the
eluent; crystals, mp 284–286 ЊC (Found: C, 65.6; H, 8.1; S,12.5.
Calc. for C56H82O5S4Si2: C, 66.0; H, 8.1; S,12.6%); δH(300 MHz)
0.12 (3 H, d, J 7.2, CHCH3), 0.52 (3 H, d, J 7.5, CHCH3), 0.56–
0.67 (2 H, m, CHCH3 and OCH2CH ), 0.69 (3 H, t, J 7.6,
CH2CH3), 0.77 (3 H, d, J 7.2, CHCH3), 0.71–0.82 [1 H, m,
CH(CH3)2], 0.85 (3 H, d, J 7.6, CHCH3), 0.97 (3 H, d, J 7.6,
CHCH3), 1.01 (3 H, d, J 7.2, CHCH3), 1.05 (3 H, d, J 7.9,
CHCH3), 1.14 (3 H, d, J 7.6, CHCH3), 0.93–1.17 [4 H, m,
CH(CH3)2, OCH2CH and CH2CH3], 1.22–1.33 [1 H, m,
CH(CH3)2], 1.25 [9 H, s, C(CH3)3], 1.29 [9 H, s, C(CH3)3], 1.30
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 8 9 0 – 8 9 8
896

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[9 H, s, C(CH3)3], 1.34 [9 H, s, C(CH3)3], 3.40–3.48 (1 H, m,
OCHCH2), 3.77–3.85 (1 H, m, OCHCH2), 7.25 (1 H, s, OH),
7.28 (1 H, d, J 2.4, ArH), 7.35 (1 H, d, J 2.7, ArH), 7.40 (1 H, d,
J 2.4, ArH), 7.50 (1 H, d, J 2.7, ArH), 7.60 (1 H, d, J 2.4, ArH),
7.61 (1 H, d, J 2.4, ArH), 7.66 (1 H, d, J 2.4, ArH) and 7.82
(1 H, d, J 2.4, ArH).
J 13.4, ArCHAr), 4.41 (1 H, d, J 13.1, ArCHAr), 4.48 (1 H,
d, J 15.8, OCHCO), 4.55 (1 H, d, J 15.8, OCHCO), 4.77 (1 H,
d, J 12.7, ArCHAr), 6.40 (1 H, d, J 2.4, ArH), 6.50 (1 H, d,
J 2.4, ArH), 6.56 (1 H, s, OH), 6.66 (1 H, d, J 2.7, ArH), 6.79
(1 H, d, J 2.4, ArH), 7.00 (1 H, d, J 2.4, ArH), 7.04 (1 H, d,
J 2.4, ArH), 7.08 (1 H, d, J 2.1, ArH) and 7.10 (1 H, d, J 2.4,
ArH); δC(75 MHz) 13.31, 14.21, 14.36, 14.95, 16.29, 17.35,
17.51, 17.66, 17.80, 17.92, 18.20, 30.38, 30.99, 31.07, 31.70,
31.76, 32.14, 33.62, 33.80, 33.85, 34.64, 60.77, 72.12, 124.47,
124.67, 124.76, 125.10, 125.28, 125.48, 125.65, 125.72, 127.06,
128.30, 129.25, 131.32, 131.69, 131.90, 133.50, 140.83, 143.46,
143.75, 144.71, 145.55, 148.70, 151.06, 152.71 and 170.02; m/z
(FD) 977 (Mϩ).
Compound C8a. Dichloromethane–hexane (1 : 4) as the
eluent; crystals, mp 232–233 ЊC (Found: C, 76.9; H, 9.15. Calc.
for C63H88O5Si2: C, 77.1; H, 9.0%); δH(300 MHz) 0.62 (3 H, d,
J 6.8, CHCH3), 0.78 [9 H, s, C(CH3)3], 0.88 (3 H, d, J 7.5,
CHCH3), 0.90–1.01 [10 H, m, CHCH3 × 3 and CH(CH3)2], 0.96
[9 H, s, C(CH3)3], 1.10 (3 H, d, J 7.6, CHCH3), 1.22–1.43 [9 H,
m, CHCH3 × 2 and CH(CH3)2 × 3], 1.30 [9 H, s, C(CH3)3], 1.31
[9 H, s, C(CH3)3], 3.14 (1 H, d, J 12.9, ArCHAr), 3.16 (1 H, d,
J 12.4, ArCHAr), 3.25 (2 H, d, J 13.4, ArCHAr × 2), 4.33 (1 H,
d, J 13.6, ArCHAr), 4.38 (1 H, d, J 13.2, ArCHAr), 4.42
(1 H, d, J 12.9, ArCHAr), 4.71 (1 H, d, J 12.4, ArCHAr), 4.79
(1 H, d, J 11.8, CHPh), 4.90 (1 H, d, J 11.8, CHPh), 6.47 (1 H,
d, J 2.3, ArH), 6.61 (1 H, d, J 2.4, ArH), 6.66 (1 H, d, J 2.4,
ArH), 6.69 (1 H, s, OH), 6.78 (1 H, d, J 2.5, ArH), 7.01 (1 H, d,
J 2.4, ArH), 7.02 (1 H, d, J 2.6, ArH), 7.06 (1 H, d, J 2.3, ArH),
7.11 (1 H, d, J 2.4, ArH), 7.30–7.37 (3 H, m, CH2Ph) and 7.59
(2 H, d, J 7.8, CH2Ph); δC(125 MHz) 13.85, 13.90, 14.42, 14.78,
16.55, 17.24, 17.46, 17.47, 17.59, 17.87, 17.94, 17.99, 29.68,
31.12, 31.70, 31.76, 31.83, 32.17, 33.68, 33.72, 33.87, 33.91,
34.79, 77.60, 124.51, 124.76, 124.83, 125.16, 125.21, 125.40,
125.54, 125.64, 127.33, 127.54, 128.02, 128.15, 128.60, 129.36,
129.46, 131.71, 131.98, 132.46, 133.36, 138.27, 141.00, 143.44,
143.75, 144.83, 145.67, 148.70, 151.23 and 152.22; m/z (FD)
981 (Mϩ).
General procedure for the desilylation of dialkylated compounds
C3,4 and T3,4
To a 50.0 M solution of dialkylated compound C3,4 or T3,4
in THF was added 1.0 mol equiv. of tetrabutylammonium
fluoride (1.0 M in THF) and the mixture was stirred at room
temperature for 1 h, after which it was cooled to 0 ЊC and
quenched with 2 M HCl. The mixture was extracted with
chloroform and the extract was washed with water, dried
(MgSO4) and evaporated. The residue was purified by
column chromatography on silica gel by using the indicated
eluent.
Compound C5b. Dichloromethane–hexane (1 : 3) as the
eluent; crystals (98%), mp 79–81 ЊC (Found: C, 82.1; H, 9.6.
Calc. for C52H72O4: C, 82.1; H, 9.5%); δH(300 MHz) 1.05 (6 H, t,
J 7.2, CH2CH3 × 2), 1.11 [18 H, s, C(CH3)3 × 2], 1.21 [18 H, s,
C(CH3)3 × 2], 1.51–1.64 (4 H, m, CH2CH3 × 2), 2.02–2.13 (4 H,
m, OCH2CH2 × 2), 3.28–3.38 (4 H, m, ArCHAr × 4), 3.85–3.94
(2 H, m, OCHCH2 × 2), 4.03–4.11 (2 H, m, OCHCH2 × 2),
4.28–4.37 (3 H, m, ArCHAr × 3), 4.48 (1 H, d, J 12.4,
ArCHAr), 6.91 (2 H, d, J 2.1, ArH × 2), 6.97 (2 H, d, J 2.4,
ArH × 2), 6.99 (2 H, d, J 2.4, ArH × 2), 7.01 (2 H, d, J 2.4, ArH
× 2) and 8.95 (2 H, s, OH × 2).
Compound C8b. Dichloromethane–hexane (1 : 6) as the
eluent; crystals, mp 118–121 ЊC (Found: C, 75.7; H, 9.5. Calc.
for C60H90O5Si2: C, 76.1; H, 9.6%); δH(300 MHz) 0.68 (3 H, d,
J 7.0, CHCH3), 0.77 [9 H, s, C(CH3)3], 0.89 (3 H, d, J 7.5,
CHCH3), 0.96 [9 H, s, C(CH3)3], 0.96 (3 H, t, J 7.4, CH2CH3),
0.99–1.05 [4 H, m, CHCH3 and CH(CH3)2], 1.11 (3 H, d, J 7.6,
CHCH3), 1.25–1.35 [10 H, m, CHCH3 × 3 and CH(CH3)2], 1.30
[9 H, s, C(CH3)3], 1.32 [9 H, s, C(CH3)3], 1.42 (3 H, d, J 7.4,
CHCH3), 1.41–1.46 [2 H, m, CH(CH3)2 and CHCH3], 1.49–1.58
(1 H, m, CHCH3), 1.58–1.65 [1 H, m, CH(CH3)2], 1.69–1.78
(1 H, m, OCH2CH ), 1.82–1.91 (1 H, m, OCH2CH ), 3.17–3.27
(4 H, m, ArCHAr × 4), 3.71 (1 H, dt, J 9.8 and 7.5, OCHCH2),
3.90 (1 H, ddd, J 5.1, 8.2 and 9.8, OCHCH2), 4.32 (1 H, d,
J 13.1, ArCHAr), 4.38 (1 H, d, J 13.3, ArCHAr), 4.39 (1 H, d,
J 13.2, ArCHAr), 4.66 (1 H, d, J 12.4, ArCHAr) 6.45 (1 H,
d, J 2.4, ArH), 6.59 (1 H, d, J 2.4, ArH), 6.64 (1 H, d, J 2.5,
ArH), 6.69 (1 H, s, OH), 6.75 (1 H, d, J 2.5, ArH), 7.01 (1 H, d,
J 2.4, ArH), 7.02 (1 H, d, J 2.6, ArH), 7.05 (1 H, d, J 2.4, ArH)
and 7.09 (1 H, d, J 2.6, ArH); δC(125 MHz) 13.64, 14.11, 14.73,
14.83, 16.41, 17.29, 17.41, 17.49, 17.60, 17.80, 18.12, 18.30,
19.50, 29.60, 31.09, 31.69, 31.77, 31.99, 33.59, 33.64,
33.80, 33.84, 34.83, 75.88, 124.53, 124.77, 124.87, 125.12,
125.35, 125.53, 127.74, 128.26, 128.82, 129.51, 131.87, 132.14,
133.14, 140.76, 143.29, 144.55, 145.97, 148.60, 151.18 and
152.29.
Compound T5a. Dichloromethane–hexane (1 : 2) as the
eluent; crystals (93%), mp 114–116 ЊC (Found: C, 71.7; H, 6.7;
S, 14.5. Calc. for C54H60O4S4: C, 72.0; H, 6.7; S, 14.2%); δH(500
MHz) 0.90 [18 H, s, C(CH3)3 × 2], 1.21 [18 H, s, C(CH3)3 × 2],
5.19 (2 H, d, J 10.9, CHPh × 2), 5.54 (2 H, d, J 10.9, CHPh
× 2), 7.07 (2 H, d, J 2.5, ArH × 2), 7.15 (2 H, d, J 2.5, ArH × 2),
7.40–7.32 (6 H, m, CH2Ph × 2), 7.48 (2 H, d, J 2.5, ArH × 2),
7.51 (2 H, d, J 2.5, ArH × 2), 7.64–7.61 (4 H, m, CH2Ph × 2)
and 8.35 (2 H, s, OH × 2); m/z (FAB) 901 [(M ϩ 1)ϩ].
Compound T5b. Dichloromethane–hexane (1 : 3) as the
eluent; crystals (95%), mp 96–98 ЊC (Found: C, 69.3; H, 7.8;
S, 15.7. Calc. for C48H64O4S4: C, 69.2; H, 7.7; S, 15.4%); δH(500
MHz) 0.89 [18 H, s, C(CH3)3 × 2], 1.03 (6 H, t, J 7.6, CH2-
CH3 × 2), 1.24 [18 H, s, C(CH3)3 × 2], 1.50–1.62 (4 H, m,
CH2CH3 × 2), 1.84–2.12 (4 H, m, OCH2CH2 × 2), 4.18 (2 H, dt,
J 5.9 and 8.9, OCHCH2 × 2), 4.39 (2 H, dt, J 6.2 and 8.9,
OCHCH2 × 2), 7.03 (2 H, d, J 2.4, ArH × 2), 7.14 (2 H, d, J 2.8,
ArH × 2), 7.54 (2 H, d, J 2.4, ArH × 2), 7.56 (2 H, d, J 2.4,
ArH × 2) and 8.91 (2 H, s, OH × 2).
Compound C8c. Dichloromethane–hexane (1 : 2) as the
eluent; crystals, mp 151–153 ЊC (Found: C, 73.7; H, 9.0. Calc.
for C60H88O7Si2: C, 73.7; H, 9.1%); νmax/cmϪ1 1758 (CO); δH(300
MHz) 0.69–0.73 (3 H, m, CHCH3), 0.71 [9 H, s, C(CH3)3],
0.90 (3 H, d, J 7.6, CHCH3), 0.96 [9 H, s, C(CH3)3], 0.93–1.03
[4 H, m, CHCH3 and CH(CH3)2], 1.12 (3 H, d, J 7.6, CHCH3),
1.25–1.34 [13 H, m, CHCH3 × 3, CH(CH3)2 and OCH2CH3],
1.31 [9 H, s, C(CH3)3], 1.32 [9 H, s, C(CH3)3], 1.35–1.50 [1 H, m,
CH(CH3)2], 1.41 (3 H, d, J 7.2, CHCH3), 1.52–1.65 [1 H, m,
CH(CH3)2], 3.23 (1 H, d, J 12.7, ArCHAr), 3.25 (2 H, d, J 13.4,
ArCHAr × 2), 3.26 (1 H, d, J 13.1, ArCHAr), 4.14–4.28 (2 H,
m, OCH2CH3), 4.33 (1 H, d, J 13.7, ArCHAr), 4.38 (1 H, d,
Compound T5c. Dichloromethane–hexane (1 : 1) as the
eluent; crystals (93%), mp 194–195 ЊC (Found: C, 64.5; H, 6.8;
S, 14.1. Calc. for C48H60O8S4: C, 64.5; H, 6.8; S, 14.4%); νmax
/
cmϪ1 1745 (CO); δH(500 MHz) 0.88 [18 H, s, C(CH3)3 × 2], 1.23
[18 H, s, C(CH3)3 × 2], 1.35 (6 H, t, J 7.2, OCH2CH3 × 2), 4.35–
4.30 (4 H, m, OCH2CH3 × 2), 4.81 (2 H, d, J 16.5, OCHCO ×
2), 5.31 (2 H, d, J 16.5, OCHCO × 2), 7.03 (2 H, d, J 2.5, ArH ×
2), 7.12 (2 H, d, J 2.5, ArH × 2), 7.52 (2 H, d, J 2.5, ArH × 2),
7.54 (2 H, d, J 2.5, ArH × 2) and 9.14 (2 H, s, OH × 2); m/z
(FAB) 893 [(M ϩ 1)ϩ].
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 8 9 0 – 8 9 8
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Compound C6a. Dichloromethane–hexane (1 : 2) as the
eluent; crystals (96%), mp 239–241 ЊC (decomp.) (Found: C,
84.0; H, 8.5. Calc. for C58H68O4: C, 84.0; H, 8.3%); δH(500
MHz) 1.01 [36 H, s, C(CH3)3 × 4], 3.68 (2 H, s, ArCH2Ar), 3.81
(2 H, d, J 15.4, ArCHAr × 2), 3.85 (2 H, d, J 15.4, ArCHAr ×
2), 4.07 (2 H, s, ArCH2Ar), 4.40 (2 H, d, J 11.6, OCHPh × 2),
4.71 (2 H, d, J 11.6, OCHPh × 2), 6.22 (4 H, d, J 7.6, OCH2-
Ph × 2), 6.78 (4 H, t, J 7.6, OCH2Ph × 2), 6.84 (2 H, d, J 2.4,
ArH × 2), 6.87 (2 H, d, J 2.3, ArH × 2), 6.94 (2 H, t, J 7.6,
OCH2Ph × 2), 6.94 (2 H, d, J 2.3, ArH × 2), 7.13 (2 H, d, J 2.4,
ArH × 2) and 8.29 (2 H, s, OH × 2); δC(125 MHz) 31.16, 31.26,
32.40, 33.61, 33.89, 35.94, 39.47, 72.11, 124.36, 125.08, 125.33,
125.61, 126.16, 126.60, 127.29, 127.80, 128.5, 132.07, 133.65,
136.32, 142.65, 147.05, 149.08 and 151.50; m/z (FD) 828 (Mϩ).
ultrasound (38 kHz, 80 W) for 30 min and subsequent filtration
of the resulting suspension. These samples, together with the
solutions of compounds C2 and T2 in THF-d8, were analyzed
by 1H NMR spectroscopy (300 MHz) at 20 ЊC.
Acknowledgements
We are grateful to one of the referees for a useful suggestion
concerning the conformations of the metal salts of calixarenes.
This work was supported by Industrial Technology Research
Grant Program in 2003 from the New Energy and Industrial
Technology Development Organization (NEDO) and a Grant-
in-Aid for Scientific Research on Priority Areas (No. 14044009)
from the Ministry of Education and Technology, Japan.
Compound C6b. Dichloromethane–hexane (1 : 2) as the elu-
ent; crystals (98%), mp 108–110 ЊC (Found: C, 81.9; H, 9.65.
Calc. for C52H72O4: C, 82.1; H, 9.5%); δH(500 MHz) 0.49 (6 H, t,
J 7.3, CH2CH3 × 2), 0.57–0.65 (4 H, m, CH2CH3 × 2), 0.81–0.90
(2 H, m, OCH2CH × 2), 0.92–1.01 (2 H, m, OCH2CH × 2), 1.23
[18 H, s, C(CH3)3 × 2], 1.34 [18 H, s, C(CH3)3 × 2], 3.07 (2 H, dt,
J 5.8 and 8.7, OCHCH2 × 2), 3.28 (2 H, dt, J 5.8 and 8.7,
OCHCH2 × 2), 3.74 (2 H, d, J 14.7, ArCHAr × 2), 3.77 (2 H, s,
ArCH2Ar), 3.90 (2 H, d, J 14.7, ArCHAr × 2), 3.98 (2 H, s,
ArCH2Ar), 6.97 (2 H, d, J 2.4, ArH × 2), 7.03 (2 H, d, J 2.4,
ArH × 2), 7.05 (2 H, d, J 2.5, ArH × 2), 7.20 (2 H, d, J 2.5,
ArH × 2) and 8.18 (2 H, s, OH × 2); δC(125 MHz) 13.84, 18.37,
30.89, 31.56, 31.60, 33.90, 34.16, 35.66, 72.44, 124.63, 125.10,
125.86, 126.76, 127.81, 129.10, 132.53, 134.09, 142.84, 146.23,
149.19 and 152.28.
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S. Harkema, W. Vogt, V. Böhmer and D. N. Reinhoudt, J. Org.
Chem., 1990, 55, 5176–5179.
9 M. Fan, H. Zhang and M. Lattman, Organometallics, 1996, 15,
5216–5219.
10 A spirodienone prepared by the oxidation of calixarene C1 has also
been used as an intermediate for the derivatization of the proximal
hydroxy groups: O. Aleksiuk, F. Grynszpan and S. E. Biali, J. Chem.
Soc., Chem. Commun., 1993, 11–12.
Compound C6c. Dichloromethane–hexane (1 : 1) as the elu-
ent; crystals (92%), mp 154–155 ЊC (from MeOH) (Found: C,
75.95; H, 8.5. Calc. for C52H68O8: C, 76.1; H, 8.4%); νmax/cmϪ1
1745 (CO); δH(500 MHz) 1.01 (6 H, t, J 7.1, OCH2CH3 × 2),
1.21 (18 H, s, C(CH3)3 × 2), 1.25 [18 H, s, C(CH3)3 × 2], 3.38
(2 H, d, J 15.7, OCHCO × 2), 3.70 (2 H, d, J 14.7, ArCHAr ×
2), 3.75 (2 H, s, ArCH2Ar), 3.89 (2 H, d, J 15.7, OCHCO × 2),
3.92 (4 H, q, J 7.1, OCH2CH3 × 2), 4.00 (2 H, s, ArCH2Ar), 4.02
(2 H, d, J 14.7, ArCHAr × 2), 6.98 (2 H, d, J 2.4, ArH × 2), 7.00
(2 H, d, J 2.4, ArH × 2), 7.12 (2 H, d, J 2.5, ArH × 2), 7.21 (2 H,
d, J 2.5, ArH × 2) and 7.66 (2 H, s, OH × 2); δC(125 MHz)
13.98, 31.43, 31.60, 32.43, 33.91, 34.17, 35.03, 38.56, 60.90,
68.73, 124.99, 125.35, 126.20, 127.28, 127.77, 129.04, 133.10,
134.17, 142.93, 157.05, 149.03, 151.59 and 168.88; m/z (FD) 820
(Mϩ).
11 (a) H. Kumagai, M. Hasegawa, S. Miyanari, Y. Sugawa, Y. Sato,
T. Hori, S. Ueda, H. Kamiyama and S. Miyano, Tetrahedron Lett.,
1997, 38, 3971–3972; (b) N. Iki, F. Narumi, T. Fujimoto,
N. Morohashi and S. Miyano, J. Chem. Soc., Perkin Trans. 2, 1998,
2745–2750; (c) F. Narumi, N. Iki, T. Suzuki, T. Onodera and
S. Miyano, Enantiomer, 2000, 5, 83–93.
12 Preliminary communications: (a) F. Narumi, N. Morohashi,
N. Matsumura, N. Iki, H. Kameyama and S. Miyano, Tetrahedron
Lett., 2002, 43, 621–625; (b) F. Narumi, W. Yamabuki, T. Hattori,
H. Kameyama and S. Miyano, Chem. Lett., 2003, 32, 320–321.
13 C. Jaime, J. de Mendoza, P. Parados, P. M. Nieto and C. Sanchez,
J. Org. Chem., 1991, 56, 3372–3376.
14 I. Bitter, A. Grün, G. Tóth, B. Balázs, G. Horváth and L. Tõke,
Tetrahedron, 1998, 54, 3857–3870.
15 A. Ikeda and S. Shinkai, J. Am. Chem. Soc., 1994, 116, 3102–3110.
16 J. M. Harrowfield, M. I. Ogden, W. R. Richmond and A. H. White,
J. Chem. Soc., Chem. Commun., 1991, 1159–1161.
Compound T6a. Dichloromethane–hexane (1 : 3) as the
eluent; crystals (96%), mp 239–240 ЊC (Found: C, 71.95; H, 6.8;
S, 14.1. Calc. for C54H60O4S4: C, 71.9; H, 6.7; S, 14.2%); δH(300
MHz) 0.99 [18 H, s, C(CH3)3 × 2], 1.05 [18 H, s, C(CH3)3 × 2],
4.83 (2 H, d, J 11.3, OCHPh × 2), 5.29 (2 H, d, J 11.7, OCHPh
× 2), 6.38 (4 H, d, J 7.5, OCH2Ph × 2), 6.71 (4 H, t, J 7.6,
OCH2Ph × 2), 6.91 (2 H, t, J 7.5, OCH2Ph × 2), 7.14 (2 H, d,
J 2.4, ArH × 2), 7.38 (2 H, d, J 2.4, ArH × 2), 7.44 (2 H, d, J 2.4,
ArH × 2), 7.46 (2 H, d, J 2.4, ArH × 2) and 8.53 (2 H, s,
OH × 2).
1H NMR analyses of metal salts of compounds C2 and T2
Samples containing tert-BuOK were prepared from a 10.0 mM
solution of compound C2 or T2 in THF-d8 by simple addition
of 1.0 mol equiv. of the base, while Cs2CO3-saturated samples
were prepared by addition of 6.0 mol equiv. of the base to the
THF-d8 solution, followed by irradiation of the mixture with
17 A. Bilyk, A. K. Hall, J. M. Harrowfield, M. W. Hosseini, B. W.
Skelton and A. H. White, Inorg. Chem., 2001, 40, 672–686.
18 C. D. Gutsche, B. Dhawan, K. H. No and R. Muthukrishnan, J. Am.
Chem. Soc., 1981, 103, 3782–3792.
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 8 9 0 – 8 9 8
898