Synthesis of all stereoisomers of sulfinylcalix[4]arenes

Article abstract of DOI:10.1021/jo026801x

All four stereoisomers of p-tert-butylsulfinylcalix[4]arene [4(rccc), 4(rcct), 4(rctt), and 4(rtct)], arising from the disposition of the four sulfinyl groups with respect to the mean plane of the four bridging sulfur atoms, have been prepared via oxidati

Full text of DOI:10.1021/jo026801x

Syn th esis of All Ster eoisom er s of Su lfin ylca lix[4]a r en es1
Naoya Morohashi,*,†,§ Hiroshi Katagiri,† Nobuhiko Iki,† Yusuke Yamane,† Chizuko Kabuto,‡
Tetsutaro Hattori,† and Sotaro Miyano*,†
Department of Biomolecular Engineering, Graduate School of Engineering, Tohoku University,
Aramaki-Aoba 07, Aoba-ku, Sendai 980-8579, J apan, and Instrumental Analysis Center for Chemistry,
Graduate School of Science, Tohoku University, Aoba, Aoba-ku, Sendai 980-8578, J apan
miyano@orgsynth.che.tohoku.ac.jp; n-moro@yz.yamagata-u.ac.jp
Received December 4, 2002
All four stereoisomers of p-tert-butylsulfinylcalix[4]arene [4(rccc), 4(rcct), 4(rctt), and 4(rtct)], arising
from the disposition of the four sulfinyl groups with respect to the mean plane of the four bridging
sulfur atoms, have been prepared via oxidation of p-tert-butylthiacalix[4]arene (2) or its tetra-O-
benzyl ethers 5 of defined conformations. Thus, treatment of 2 with 4.4 molar equiv of NaBO3‚
4H2O gave the rtct and rctt isomers in 27% and 17% yields, respectively, while oxidation of cone
5 (5C) and partial cone 5 (5PC) proceeded stereoselectively to give, after debenzylation of the resulting
tetrasulfoxides 12 and 15, the rccc and rcct isomers in 56% and 28% yields, respectively, based on
5. The sulfinylcalix[4]arenes 4 were treated with iodomethane in the presence of a base to give the
corresponding tetramethyl ethers 16, the structures of which in regard to the disposition of the
sulfinyl groups and the conformation of the phenol units were determined by X-ray crystallography.
Also reported is the synthesis of all four conformational isomers of tetra-O-benzyl ether of 2 (5C,
5
PC, 51,2-A, and 51,3-A).
In tr od u ction
Calix[4]arenes (e.g., 1) are an extensively utilized
molecular scaffold for synthetic receptors in supramo-
lecular and molecular recognition chemistry.2 This is
mainly due to the availability of the basic macrocycles
in substantial quantities from base-catalyzed condensa-
tion of p-alkylphenols with formaldehyde.3 The macro-
cycles are, in turn, amenable to various modifications at
the hydroxy groups (lower rim) and/or at the para
positions (upper rim) of the phenolic units to bring about
various functions.2 Although modification of the bridging
methylene groups or their replacement with heteroatoms
such as nitrogen, phosphorus, sulfur, and the like is a
highly intriguing method to alter the properties of the
calix class compounds, there have been only few such
attempts because of the synthetic difficulties.4
Replacement of any of the four bridging methylene
groups by epithio groups was first reported by Sone et
al. in 1993 via the stepwise joining of the component
phenol units by methylene or epithio bonds followed by
ultimate cyclization of the resulting acyclic tetramer.5
However, it was not until 1997 when we disclosed a facile
synthesis of 2,8,14,20-tetrathiacalix[4]arenes (e.g., 2), by
simply heating a p-alkylphenol with elemental sulfur in
the presence of NaOH,6 that these new members of the
calix family were proved to be not a simple substitute
for the parent calix[4]arenes but second-generation calix-
es bearing intrinsic advantages not attainable by the
* To whom correspondence should be addressed. Phone/Fax: +81-
22-217-7262.
† Department of Biomolecular Engineering.
‡ Instrumental Analysis Center for Chemistry.
§ Present address: Department of Chemistry and Chemical Engi-
neering, Faculty of Engineering, Yamagata University, Yonezawa 992-
8510, J apan.
(1) Preliminary communications: (a) Iki, N.; Kumagai, H.; Moro-
hashi, N.; Ejima, K.; Hasegawa, M.; Miyanari, S.; Miyano, S. Tetra-
hedoron Lett. 1998, 39, 7559. (b) Morohashi, N.; Iki, N.; Kabuto, C.;
Miyano, S. Tetrahedron Lett. 2000, 41, 2933.
(2) (a) Gutsche, C. D. Calixarenes; The Royal Society of Chemistry:
Cambridge, 1989. (b) Gutsche, C. D. Calixarenes Revisited; The Royal
Society of Chemistry: Cambridge, 1998. (c) Asfari, Z.; Bo¨hmer, V.;
Harrowfield, J . M.; Vicens, J . Calixarenes 2001; Kluwer Academic
Publishers: Dordrecht, 2001.
(3) (a) Gutsche, C. D.; Iqbal, M. Org. Synth. 1990, 68, 234. (b)
Gutsche, C. D.; Dhawan, B.; Lenois, M.; Stewart, D. R. Org. Synth.
1990, 68, 238. (c) Munch, J . H.; Gutsche, C. D. Org. Synth. 1990, 68,
243.
(4) (a) Biali, S. E.; Bo¨hmer, V.; Cohen, S.; Ferguson, G.; Gru¨ttner,
C.; Grynszpan, F.; Paulus, E. F.; Thondorf, I.; Vogt, W. J . Am. Chem.
Soc. 1996, 118, 12938. (b) Middel, O.; Greff, Z.; Taylor, N. J .; Verboom,
W.; Reinhoudt, D. N.; Snieckus, V. J . Org. Chem. 2000, 65, 667. (c)
Ko¨nig, B.; Fonseca, M. H. Eur. J . Inorg. Chem. 2000, 2303 and
references therein.
(5) (a) Sone, T.; Ohba, Y.; Moriya, K.; Kumada, H. Abstract Book of
Workshop on Calixarenes and Related Compounds; Fukuoka, J apan,
1993; p PS/B-36. (b) Sone, T.; Ohba, Y.; Moriya, K.; Ito, K. Tetrahedron
1997, 53, 10689.
(6) Kumagai, H.; Hasegawa, M.; Miyanari, S.; Sugawa, Y.; Sato, Y.;
Hori, T.; Ueda, S.; Kamiyama, H.; Miyano, S. Tetrahedoron Lett. 1997,
38, 3971.
10.1021/jo026801x CCC: $25.00 © 2003 American Chemical Society
Published on Web 02/27/2003
2324
J . Org. Chem. 2003, 68, 2324-2333

Stereoisomers of Sulfinylcalix[4]arenes
F IGURE 2. Schematic representation of all four conforma-
tional isomers of tertrabenzyl ether 5.
F IGURE 1. Schematic representation of four stereoisomers
of 4. Herein we use the term cis (c) or trans (t) to denote the
disposition of sulfoxide oxygen with respect to reference oxygen
from the mean plane containing four sulfur atoms, as sug-
gested by Dr. V. Bo¨hmer; see ref 7a. The isomer notation
proceeds around the system in a clockwise direction from
reference oxygen, which should be chosen to maximize the
number of cis, and cis is preferable to trans.
It is quite interesting to note that the sulfinylcalix[4]-
arenes of rtct configuration [e.g., 4(rtct)] can extract a
wide variety of metal ions ranging from soft to hard.8 It
was concluded that 4(rtct) can alternate the ligating atom
between the oxygen and sulfur of the sulfinyl function
depending on the hardness or softness of the metal ions
to be extracted. This hypothesis was actually substanti-
ated by X-ray crystallography of several complexes of
4(rtct) with Pd(II)14 and Ti(IV)15 ions, which in turn
brought about further interest in the complexation ability
of isomers of 4 other than 4(rtct) toward metal ions.
Herein, as the first endeavor in this line, we report the
preparation of all four stereoisomers of 4 in detail. In the
course of this investigation, we needed specific confor-
mational isomers of tetra-O-benzylthiacalix[4]arenes 5
as the intermediates for stereoselective synthesis of 4 of
particular configurations, and the synthesis of all ster-
eoisomers of 5 is also reported.
methylene-bridged counterparts.7 In particular, the ready
oxidizability of the thio function to the sulfinyl and
sulfonyl groups should be mentioned first, significantly
widening the versatility of the thia-macrocycles. Thus,
treatment of 2 with 8 molar equiv of NaBO3‚4H2O gave
sulfonylcalix[4]arene 3 in excellent yield.1a,8,9 In the
preparation of sulfinylcalix[4]arene 4, the situation be-
comes somewhat complicated because of the possible
stereoisomers due to the disposition of the four sulfinyl
functions to give the rccc, rcct, rctt, and rtct isomers
(Figure 1). Previously, we reported that isomer 4(rtct)
was obtained in 31% yield by direct oxidation of 2 with 4
molar equiv of NaBO3‚4H2O.8,10
Another noticeable feature of the sulfur-bridged calix-
[4]arenes is their unique metal binding ability.11 It has
been found that 2 extracts very well the so-called “soft”
metal ions from an aqueous phase into an organic phase,
by coordination of the bridging sulfur to the metal center
with cooperative ligation of the two neighboring phenox-
ides to form two sets of five-membered chelates as
Resu lts a n d Discu ssion
Syn th esis of All F ou r Con for m a tion a l Isom er s of
Tetr a -O-ben zyl Eth er 5. Calixarene O-benzyl ethers of
defined conformation have commonly been used as
intermediates for the preparation of calixarenes of the
desired conformation.16 Therefore, it is highly desirable
to have a set of all four conformational isomers of p-tert-
butylthiacalix[4]arene tetra-O-benzyl ethers, that is, cone
(5C), partial cone (5PC), 1,2-alternate (51,2-A), and 1,3-
alternate (51,3-A) (Figure 2).17 First of all, a one-step
procedure for the tetra-O-benzylation of 2 with bromo-
methylbenzene was examined, varying a base, and Table
1 lists the isolated yields of the four conformational
isomers of 5. Treatment of 2 with a large excess of the
bromide in THF-DMF using NaH as a base afforded a
mixture containing 5C as the major product accompanied
with small amounts of 5PC and 51,3-A (entry 1). It can be
seen that the alkali metal carbonates used significantly
affected the conformational outcome of the reaction.
Thus, Na2CO3 required the addition of NaI for the
1
exemplified by H NMR spectroscopy11 and X-ray crystal-
lography of 2-metal complexes.12 On the other hand, the
sulfonyl counterpart 3 prefers “hard” metal ions by
coordination of the hard sulfonyl oxygen ligand.8,13
(7) (a) Iki, N.; Miyano, S. J . Incl. Phenom. Macrocycl. Chem. 2001,
41, 99. (b) Iki, N.; Miyano, S. Nippon Kagaku Kaishi 2001, 609; Chem.
Abstr. 2002, 136, 216664. (c) Morohashi, N.; Iki, N.; Miyano, S. Yuki
Gosei Kagaku Kyokaishi, 2002, 60, 550; Chem. Abstr. 2002, 136,
452024.
(8) Morohashi, N.; Iki, N.; Sugawara, A.; Miyano, S. Tetrahedron
2001, 57, 5557.
(9) Mislin, G.; Graf. E.; Hosseini, M. W.; De Cian, A.; Fischer, J . J .
Chem. Soc., Chem. Commun. 1998, 1345.
(10) Hosseini and co-workers reported the use of H2O2 as the
oxidizing reagent: Mislin, G.; Graf, E.; Hosseini, M. W.; Cian, A. D.;
Fisher, J . Tetrahedron Lett. 1999, 40, 1129.
(11) Iki, N.; Morohashi, N.; Narumi, F.; Miyano, S. Bull. Chem. Soc.
J pn. 1998, 71, 1597.
(12) (a) Iki, N.; Morohashi, N.; Kabuto, C.; Miyano, S. Chem. Lett.
1999. 219. (b) Mislin, G.; Graf, E.; Hosseini, M. W.; Bilyk, A.; Hall, A.
K.; Harrowfield, J . M.; Skelton, B. W.; White, A. H. Chem. Commun.
1999, 373. (c) Bilyk, A.; Hall, A. K.; Harrowfield, J . M.; Hosseini, M.
W.; Skelton, B. W.; White, A. H. Inorg. Chem. 2001, 40, 672.
(13) (a) Kajiwara, T.; Yokozawa, S.; Ito, T.; Iki, N.; Morohashi, N.;
Miyano, S. Chem. Lett. 2001, 6. (b) Kajiwara, T.; Yokozawa, S.; Ito,
T.; Iki, N.; Morohashi, N.; Miyano, S. Angew. Chem., Int. Ed. 2002,
41, 2076.
(14) Morohashi, N.; Iki, N.; Miyano, S.; Kajiwara, T.; Ito, T. Chem.
Lett. 2001, 66.
(15) Morohashi, N. PhD Thesis, Tohoku University, 2001.
(16) See, for example: (a) Casnati, A.; Arduini, A.; Ghidini, E.;
Pochini, A.; Ungaro, R. Tetrahedron 1991, 47, 2221. (b) Iwamoto, K.;
Araki, K.; Shinkai, S. Tetrahedron 1991, 25, 4325.
(17) The conformational preferences in the alkylation of thiacalix-
[4]arenes have been reported very recently: Lhota´k, P.; Himl, M.;
Stibor, I.; Petrˇ´ıcˇkova´, H. Tetrahedron Lett. 2002, 43, 9621.
J . Org. Chem, Vol. 68, No. 6, 2003 2325

Morohashi et al.
TABLE 1. Con for m er Distr ibu tion for Rea ction of 2
w ith Br om om eth ylben zen e
yield (%)a
entry base
NaH
solvent
time (h) 5C 5PC 51,2-A 51,3-A
1
THF-DMF (9:1)
2b 68
9
c
1
1
1
2
6
2
2d Na2CO3 acetone
144b 50 12
3
4
5
K2CO3
Cs2CO3
K2CO3 DMF
48b
2b
7
c
c
12
3
3
50
70
63
24e
a
d
Isolated yield. b At reflux. c Not detected. NaI (4 molar equiv)
F IGURE 3. X-ray structure of 5C. H atoms are omitted for
clarity.
was added. e At 60 °C.
SCHEME 1
bromide to react with 2 at a practical rate, giving
preferentially the cone conformer in acetone, whereas K2-
CO3 and Cs2CO3 did not need the addition of NaI and
preferred the formation of the 1,3-alternate isomer in the
same solvent (entries 2-4). On the other hand, the
solvent seems not to affect so much the isomer distribu-
tion as can be seen from the reaction with K2CO3 in DMF,
which also gave the 1,3-alternate isomer selectively
(entry 5). These results are in contrast to those reported
by Gutsche et al., in which the one-step tetra-O-benzy-
lation of methylene-bridged calix[4]arene 1 with NaH
gave the cone isomer but the reaction with K2CO3 gave
the partial cone conformer selectively.18 Unfortunately,
we could find suitable conditions for a one-step synthesis
of neither 5PC nor 51,2-A, and thus these conformers were
prepared by multistep procedures (vide infra).
1
the basis of the H NMR spectrum. Thus, two singlets
for the tert-butyl protons [δ 0.79 and 1.34 (each 18H)]
and two singlets for the aryl protons [δ 6.96 and 7.68
(each 4H)] ruled out the possibility of 6 to be a 1,2-
regioisomer or an anti-1,3-isomer. Then, syn-1,3-6 was
further treated with the bromide (1 molar equiv) in DMF
employing 1 molar equiv of NaH to afford a tribenzyl
ether 7 in 70% yield, the stereochemistry of which was
deducible from that of the product of the subsequent
reaction. We have learned previously that in the O-
alkylation of a mono-O-alkylated thiacalix[4]arene using
Cs2CO3 as the base, the alkyl group coming in tends to
replace the remaining phenolic hydroxy protons from the
opposite side of the already residing alkyl groups with
respect to the mean plane defined by the four S atoms.19
By relying on this experimental generalization, tribenzyl
ether 7 should most probably be converted to 5PC by
treatment with an additional bromomethylbenzene in
acetone using Cs2CO3 as the base. The fourth benzylation
gave two tetrabenzyl ethers in 82% and 12% yields,
respectively, the minor product of which was proved to
be 5C. Therefore, the major product should be the partial
cone conformer 5PC. Thus, 5PC was obtained in 49% yield
via the three-step sequential benzylation of 2.
Finally, another stepwise procedure was devised for
the synthesis of 51,2-A. It is conceivable that the possible
intermediary di-O-benzyl ethers 6 to 51,2-A should be
limited to syn- or anti-1,2-6, or anti-1,3-6. However, it
has been a common understanding in calixarene chem-
istry that O-dialkylation of a native calix[4]arene usually
affords the 1,3- rather than the 1,2-isomer of syn confor-
mation as the main product.20 The preferential formation
of a syn-1,3-conformer also stands for a disubstitution
reaction of thiacalix[4]arenes as exemplified by the
dibenzylation of 2 as stated above. Therefore, it should
Although it has been well-known that the conformation
of conventional calix[4]arene derivatives can conveniently
be assigned by relying on the 1H NMR resonance pattern
of the methylene groups between the phenol nuclei,2 it
is rather difficult to assign the conformation of thiacalix-
[4]arene derivatives because of the lack of the probing
methylene moiety. However, the conformation of thiacalix-
[4]arenes of partial cone and 1,2-alternative can be
1
deduced from their H NMR resonances of the tert-butyl
and aromatic protons. Thus, the isomer that showed
three singlets for the tert-butyl protones [δ 0.75 (9H), 0.85
(18H), and 1.21 (9H)] and two singlets [δ 7.38 and 7.61
(each 2H)] and two doublets [δ 6.92 and 7.38 (each 2H)]
for the aryl protons was safely assigned to 5PC, and the
other that showed one singlet for the tert-butyl protones
[δ 1.13 (36H)] and two doublets for the aryl protons [δ
7.31 and 7.67 (each 4H)] was assigned to 51,2-A (see
Experimental Section). The distinction between the cone
and 1,3-alternate conformers is very difficult, because 1H
NMR spectra of these conformers show quite similar
resonance patterns, in which both the tert-butyl and aryl
signals appear as singlet absorption. Eventually, the
structural assignment of 5C and 51,3-A relied on the X-ray
analysis of 5C (Figure 3). It can be seen that, in the solid
state, 5C takes a typical pinched cone structure with a
C
2v symmetry. Therefore, the other isomer of the similar
1H NMR spectrum was unambiguously assigned to be
51,3-A
.
In the next step, we tried the synthesis of 5PC by a
multistep procedure (Scheme 1). Treatment of 2 with
bromomethylbenzene in acetone using Na2CO3 as the
base without the addition of NaI afforded a dibenzylated
product 6, the stereo- and regiochemistry of which was
assigned to be syn-1,3-di-O-benzyl ether (syn-1,3-6) on
(19) Iki, N.; Narumi, F.; Fujimoto, T.; Morohashi, N.; Miyano, S. J .
Chem. Soc., Perkin Trans. 2 1998, 2745.
(18) Gutsche, C. D.; Reddy P. A. J . Org. Chem. 1991, 56, 4783.
2326 J . Org. Chem., Vol. 68, No. 6, 2003
(20) Chaper 5 of ref 2a,b.

Stereoisomers of Sulfinylcalix[4]arenes
SCHEME 2
SCHEME 4
SCHEME 3
be noted that the preparation of a tetra-O-substituted
calix[4]arene of 1,2-alternate conformation is a rather
challenging task. In a previous paper,21 we have reported
a facile method for the synthesis of syn-1,2-di-O-alkylated
thiacalix[4]arenes via 1,2-O-disiloxane-capping by treat-
ment of 2 with 1,3-dichloro-1,1,3,3-tetraisopropyldisilox-
ane in the presence of imidazole, followed by dialkylation
of the two remaining phenolic hydroxy groups with an
alkyl halide using Cs2CO3 as a base, and subsequent
deprotection of the disiloxane moiety with tetrabutylam-
monium fluoride, which was conveniently adopted to the
preparation of syn-1,2-6. The diether thus obtained in
69% yield based on the starting 2 was treated with an
additional bromomethylbenzene in acetone using Cs2CO3
to give 51,2-A (40%) with concomitant formation of 5PC
(35%) and 5C (10%) (Scheme 2); thus, the four-step route
gave 51,2-A in a net 28% yield based on 2.
Although several attempts to increase the selectivity
of the production of the 1,2-alternate isomer of 5 were
not fruitful, we could now have all the stereoisomers of
tetra-O-benzyl ether 5 in hand in substantial amounts.
Syn th esis of 4(r tct) a n d 4(r ctt) Isom er s by Oxid a -
tion of 2. Although we1a and others10 have previously
obtained the rtct isomer of 4 from oxidation of native 2
with NaBO3 or H2O2, we were aware of the fact that the
reaction of 2 with NaBO3‚4H2O (4.4 molar equiv) gave a
mixture containing several oxidation products. These
were hardly separable by chromatography because of the
decomposition of the phenolic entities on silica gel seem-
ingly by oxidation. We revisited the reaction to improve
the product yield and found that 4(rtct) could be obtained
as an insoluble part of the reaction mixture boiled in
methanol (Scheme 3). Concentration of the methanol
solution gave 4(rctt) as a precipitate. Finally, spectro-
metrically pure samples of 4(rtct) (27%) and 4(rctt) (17%)
were obtained by recrystallization of the solids from a
dichloromethane-methanol and a chloroform-hexane
solution, respectively. These results indicate that the
configurations of the sulfinyl groups of 4 significantly
affect the solubility of the molecules; 4(rctt) is highly
soluble in methanol, whereas 4(rtct) is essentially in-
soluble in hot methanol. The absolute dispositions of the
four sulfinyl groups of 4(rtct) were confirmed by X-ray
crystallography,8 and those of 4(rctt) were determined
after conversion into tetramethyl ether 16 (vide infra).
It was shown by 1H NMR assay that the NaBO3 oxidation
of 2 produced a small amount of 4(rcct), besides 4(rtct)
and 4(rctt), while the presence of 4(rccc) isomer was not
detectable.
Syn th esis of 4(r ccc) a n d 4(r cct) Isom er s via Ste-
r eocon tr olled Oxid a tion of Tetr a -O-ben zyl Eth er s
5C a n d 5P C, Resp ectively, F ollow ed by Deben zyla -
tion . As the direct oxidation of 2 did not seem promising
to obtain the rccc and rcct isomers of 4, we then tackled
a strategy to control the direction of the approach of the
oxidant by introducing bulky substituents at the phenolic
hydroxy groups, which are also able to freeze the flip-
flop motion of the calix phenol units. We chose a benzyl
moiety as the candidate because it possesses not only
sufficient steric bulk to fulfill the requirements but also
easiness of introduction (vide supra) and removal.1b
Initially, the oxidation of 5C was examined in detail
(Scheme 4).22 Oxidation of 5C with varying amounts of
NaBO3‚4H2O (1.1-4.4 molar equiv) produced mono- to
tetrasulfinyl derivatives 8-12, which were readily sepa-
rated by chromatography on silica gel. It can be seen that
the distribution of the products was mainly determined
by the amounts of the oxidant (Table 2). The identities
of the sulfinylcalix[4]arenes 8-12 were established by
1H NMR and MS spectra except for the absolute stereo-
chemistry of the sulfinyl groups, which was finally
determined by X-ray crystallography on tetrasulfinlycalix-
[4]arene 12 (Figure 4). It can be seen that all four sulfinyl
groups direct toward equatorial orientation in a down-
(22) Recently Lhota´k reported the oxidation of thiacalix[4]arene
tetraacetate having cone conformation to the sulfinyl derivative, the
absolute stereochemistry of which was not determined: Lhota´k, P.
Tetrahedron 2001, 57, 4775.
(21) Narumi, F.; Morohashi, N.; Matsumura, N.; Iki, N.; Kameyama,
H.; Miyano, S. Tetrahedron Lett. 2002, 43, 621.
J . Org. Chem, Vol. 68, No. 6, 2003 2327

Morohashi et al.
TABLE 2. Oxid a tion of 5C w ith Na BO3‚4H2O
yield (%)a
NaBO3‚4H2O
(molar equiv)
entry
8
9
10
11
12
1
2
3
4
1.1
2.2
3.3
4.4
56
18
b
21
32
23
b
15
30
2
b
11
57
b
b
b
11
94
b
b
a
b
Isolated yield. Not detected.
F IGURE 5. X-ray structure of 14. H atoms and included
solvents are not shown for clarity.
F IGURE 4. X-ray structure of 12. H atoms and included
solvents are not shown for clarity.
F IGURE 6. Schematic representation of syn- and anti-4(rccc).
SCHEME 6
SCHEME 5
the opposite side of the three anti benzyl groups with
respect to the mean plane containing four sulfur atoms
to avoid steric hindrance. Although the stereochemistry
of the third oxidation step was not elucidated, the fourth
oxidation seemed to avoid dipole repulsion toward the
third sulfinyl, resulting in the up-and-down relationship
between the third and fourth sulfinyl groups to form 15.
Oxidation of 51,2-A and 51,3-A was found to give complex,
hardly isolable mixtures, showing that stereocontrol of
the oxidation was difficult by relying on the arrangement
of the benzyl moieties in these conformational isomers.
Although iodotrimethylsilane is a conventional re-
source used for the deprotection of O-benzylated calix-
arenes,14 attempted debenzylation of 12 and 15 with the
iodide accompanied partial reduction of the sulfinyl
groups of the resulting 4(rccc) and 4(rcct) to sulfide bonds.
It was found, however, that sodium octane-1-thiolate was
acceptable as the deprotection agent for 12 and 15, giving
4(rccc) (60%) and 4(rcct) (60%), respectively (Scheme 6).
Thus, synthetic methods for all four stereoisomers of
p-tert-butylsulfinylcalix[4]arene 4 have now been pro-
vided.
Com p a r ison of Sp ectr a l P r op er ties of Ster eoiso-
m er s of 4. It is interesting to compare the IR absorption
of 2 with that of stereoisomers of 4. The OH stretching
absorption (νOH) of 4(rccc) substantially shifted to a lower
frequency (KBr disk, 3128 cm-1) as compared to that of
2 (3324 cm-1) and other stereoisomers of 4 (3188-3423
cm-1), strongly indicating an increased intramolecular
hydrogen bonding in 4(rccc) compared to that in the
others. The X-ray analyses have shown the presence of
hydrogen bonding between the hydroxy and sulfinyl
down-down-down manner seemingly to avoid the benzyl
moieties. Considering the fact that the oxidation of 5C
with NaBO3‚4H2O eventually ends up in the formation
of 12, it is concluded that the disposition of the sulfinyl
units of the intermediary 8, 9, 10, and 11 should also be
equatorial, showing that the stereochemistry of the
oxidation was completely controlled by the benzyl groups.
In the next step, the oxidation of 5PC was studied in
detail (Scheme 5). Oxidation of 5PC with 1.1 and 2.2 molar
equiv of NaBO3‚4H2O gave mono- and disulfinyl deriva-
tive 13 and 14 as the main products, respectively,
although concomitant formation of small amounts of
unidentified products was also suggested by 1H NMR
assay of the reaction mixtures. X-ray crystallography of
14 revealed that Sa and Sb of 5PC had been converted to
sulfinyl groups with the oxygens disposed anti to the
three proximal benzyl groups (Figure 5). Treatment of
5PC with NaBO3‚4H2O (4.4 molar equiv) eventually gave
15, which should come to 4(rcct) after deprotection as
evidenced hereinafter. These results show that the
oxidizing agent attacks at first at Sa and then Sb from
2328 J . Org. Chem., Vol. 68, No. 6, 2003

Stereoisomers of Sulfinylcalix[4]arenes
F IGURE 7. X-ray structures of 16(rccc), 16(rcct), 16(rctt), and 16(rtct). H atoms and included solvents are not shown for clarity.
groups in 4(rtct),7b,10 whereas circular intramolecular
hydrogen bonding exists among the four hydroxy groups
in 2.23 On the other hand, the SdO stretching absorption
(νSdO) of 4(rccc) appears at 1028 cm-1, falling between
the dipole repulsion between the sulfinyl and methoxy
groups, the parent 4(rtct) also adopting 1,3-alternate
conformation as reported before.7b,10 Furthermore, 16(rcct)
and 16(rctt) have partial cone conformation, in which
methoxy groups between two syn sulfinyl groups direct
oppositely to them to minimize the steric hindrance and
dipole repulsion between the sulfinyl and methoxy groups.
From these results it seems that the configuration of the
four sulfinyl groups would significantly influence the
conformational arrangement of the phenol units of
sulfinylcalix[4]arene derivatives.
the absorptions of 12 (1049 cm-1) and 4(rtct) (1001 cm-1
)
to indicate the presence of some hydrogen bonding
between the hydroxy and sulfinyl groups in 4(rccc).
Therefore, the hydroxy groups of 4(rccc) seem to form
hydrogen bonding not only with adjacent hydroxy but
also sulfinyl groups. Furthermore, the 1H NMR spectrum
of 4(rccc) in CDCl3-DMSO-d6 showed a sharp singlet at
7.69 ppm for the aryl ring protons, indicating that they
were equivalent on the NMR time scale. On the other
hand, the ring protons of 4(rtct) are nonequivalent,
showing two broad peaks at 7.37 and 7.76 ppm due to
the two adjacent sulfinyl groups in a trans relationship.
From these discussions, the conformation of 4(rccc) may
tentatively be assigned as a cone structure in the solution
with sulfinyl groups in a syn relationship to the phenolic
hydroxy groups rather than an anti structure as depicted
in Figure 6. Furthermore, 4(rctt) and 4(rcct) showed two
νSdO peaks at 1053 and 1005 cm-1 and 1028 and 1003
cm-1, respectively, indicating that 4(rctt) and 4(rcct) had
more than two sulfinyl groups under different circum-
stances in the solid state because of the differences in
the form of hydrogen bonding.
Con clu sion
We have provided here the routes for the synthesis of
all four stereoisomers of p-tert-butylsulfinylcalix[4]arene
4. Direct oxidation of native 2 gave the rtct and rctt
isomers. On the other hand, the rcct and rccc isomers
were obtained by stereocontrolled oxidation of tetrabenzyl
ether 5 of defined conformations followed by debenzyla-
tion by treatment with a thiolate. The configurations of
four sulfinyl groups of all four stereoisomers of 4 were
confirmed after being converted into tetramethyl ether
derivatives 16. Furthermore, synthetic procedures for all
four conformational isomers of tetra-O-benzylthiacalix-
[4]arene 5 were presented.
X-r a y Cr ysta llogr a p h y of Tetr a m eth yl Eth er s 16.
As it was very difficult to obtain single crystals of
sulfinylcalix[4]arenes 4 except 4(rtct),7b,10 the configura-
tions of the sulfinyl groups of all four isomers of 4 were
determined after conversion into tetramethyl ether de-
rivatives 16. Treatment of 4 with iodomethane in THF
using K2CO3 or Cs2CO3 as the base afforded tetramethyl
ethers 16 in high yields (∼80%). Single crystals of all
stereoisomers 16 were obtained as usual, and their X-ray
structural analyses were carried out (Figure 7). In the
solid state, 16(rccc) adopts a cone conformation, in which
all four sulfinyl groups direct in opposite direction toward
all four methoxy groups. On the other hand, 16(rtct)
adopts 1,3-alternate conformation seemingly to minimize
Exp er im en ta l Section
Gen er a l Meth od s. Melting points were taken using a micro
melting point apparatus and are uncorrected. 1H NMR and
13C NMR spectra were measured using tetramethylsilane as
an internal standard and CDCl3 as a solvent, unless otherwise
noted. Microanalyses were carried out in the Microanalytical
Laboratory of the Institute of Multidisciplinary Research for
Advanced Materials, Tohoku University. Silica gel 60GF254 was
used for TLC. Silica gel columns were prepared by use of silica
gel 60 (63-200 µm). Water- and air-sensitive reactions were
routinely carried out under nitrogen. THF was distilled from
sodium diphenyl ketyl just before use. Acetone and DMF were
distilled from CaSO4 and stored under nitrogen. 5,11,17,-
23-Tetra-tert-butyl-2,8,14,20-tetrathiapentacyclo[19.3.1.13,7.-
19,13.115,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),-
21,23-dodecaene-25,26,27,28-tetrol (2)6 and 27,28-dibenzyl-
oxyl-5,11,17,23-tetra-tert-butyl-2,8,14,20-tetrathiapentacy-
clo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,-
19(26),21,23-dodecaene-25,26-diol (syn-1,2-6)21 were synthe-
(23) (a) Akdas, H.; Bringel, L.; Graf, E.; Hosseini, M. W.; Mislin,
G.; Pansanel, J .; De Cian, A.; Fischer, J . Tetrahedron Lett. 1998, 39,
2311. (b) Iki, N.; Kabuto, C.; Fukushima, T.; Kumagai, H.; Takeya,
H.; Miyanari, S.; Miyashi, T.; Miyano, S. Tetrahedron 2000, 56, 1437.
J . Org. Chem, Vol. 68, No. 6, 2003 2329

Morohashi et al.
sized as described in the literatures. Densities (d) are given
in units of g mL-1
filtered. After the filtrate was evaporated, the residue was
.
crystallized from dichloromethane-ethanol to give syn-1,3-6
1
(3.18 g, 85%) as colorless crystals: mp 257-259 °C; H NMR
Gen er a l P r oced u r e for th e Ben zyla tion of 2 to Con -
for m a tion a l Isom er s of 25,26,27,28-Tetr a ben zyloxyl-5,-
11,17,23-t et r a -ter t-b u t yl-2,8,14,20-t et r a t h ia p en t a cyclo-
[19.3.1.13,7.19,13.115,19]oct a cosa -1(25),3,5,7(28),9,11,13(27),-
15,17,19(26),21,23-d od eca en e (5) (Ta ble 1). Thiacalix[4]-
arene 2 was suspended in a dry solvent (ca. 50 mM solution)
containing 16 molar equiv of an anhydrous alkali metal
carbonate and bromomethylbenzene. To the suspension was
added 4 molar equiv of NaI, if necessary (entry 2). The mixture
was heated at reflux (entries 2-4) or 60 °C (entry 5) for 2-144
h. After cooling, precipitates were removed by filtration. The
filtrate was poured into water and extracted with chloroform.
The extract was washed with water, and the solvent was
evaporated. The residual oil was triturated with methanol to
give a solid, which was chromatographed on silica gel with
hexane-chloroform (5:1) as the eluent. See Table 1 for the
reaction conditions and the product distribution. In entry 1,
the reaction was conducted as follows. A mixture of 2 (1.00 g,
1.39 mmol), NaH (534 mg, 22.3 mmol), DMF (1.5 mL), and
THF (13.5 mL) was stirred at room temperature for 30 min.
To the mixture was added bromomethylbenzene (3.93 g, 23.0
mmol), and the mixture was refluxed for 2 h. The reaction was
quenched by addition of several drops of methanol. After most
of the THF was evaporated, the residue was poured into water
(50 mL) and worked up as above. Chromatographic purification
of the resulting oil gave 5C (1.02 g, 68%), 5PC (134 mg, 9%),
and 51,3-A (87 mg, 6%).
Da ta for 5C: mp 208-209.5 °C; 1H NMR (500 MHz) δ 1.06
(36H, s), 5.24 (8H, s), 7.15-7.19 (12H, m), 7.22 (8H, s), 7.47-
7.48 (8H, m); 13C NMR (125 MHz) δ 31.2, 34.1, 76.7, 127.6,
127.7, 129.9, 133.9, 136.4, 137.4, 145.8, 158.1; FAB-MS m/z
1081 [(M + 1)+]. Anal. Calcd for C68H72O4S4: C, 75.51; H, 6.71;
S, 11.86. Found: C, 75.73; H, 6.67; S, 11.65.
Da ta for 5P C: mp 222.5-224 °C; 1H NMR (500 MHz) δ 0.75
(9H, s), 0.85 (18H, s), 1.21 (9H, s), 4.87 (2H, s), 4.92 (2H, d, J
) 10.1 Hz), 5.08 (2H, s), 5.11 (2H, d, J ) 10.1 Hz), 6,92 (2H,
d, J ) 2.51 Hz), 7.02-7.08 (3H, m), 7.30-7.36 (9H, m), 7.38
(2H, d, J ) 2.51 Hz), 7.38 (2H, s), 7.39-7.43 (2H, m), 7.61
(2H, s), 7.65-7.68 (4H, m), 7.76-7.77 (2H, m); 13C NMR (125
MHz) δ 30.8, 31.0, 31.3, 33.8, 33.9, 34.1, 71.1, 75.9, 77.6, 126.8,
126.9, 128.0, 128.2, 128.3, 128.4, 128.6, 128.9, 129.8, 129.9,
130.0, 133.5, 133.6, 134.2, 136.1, 137.2, 137.3, 137.6, 144.7,
145.6, 146.1, 156.3, 158.8, 160.2; FAB-MS m/z 1081 [(M + 1)+].
Anal. Calcd for C68H72O4S4: C, 75.51; H, 6.71; S, 11.86.
Found: C, 75.62; H, 6.79; S, 11.84.
Da ta for 51,2-A: mp 280-282 °C; 1H NMR (500 MHz) δ 1.13
(36H, s), 4.50 (4H, d, J ) 12.0 Hz), 4.70 (4H, d, J ) 12.0 Hz),
6.58 (8H, d, J ) 7.44 Hz), 6.94 (8H, t, J ) 7.44 Hz), 7.05 (4H,
t, J ) 7.44 Hz), 7.31 (4H, d, J ) 2.51 Hz), 7.67 (4H, d, J )
2.51 Hz); 13C NMR (125 MHz) δ 31.1, 34.2, 73.4, 126.6, 127.5,
127.6, 128.8, 129.7, 129.9, 134.2, 137.4, 146.4, 157.3; FAB-MS
m/z 1081 [(M + 1)+]. Anal. Calcd for C68H72O4S4: C, 75.51; H,
6.71; S, 11.86. Found: C, 75.49; H, 6.76; S, 11.63.
Da ta for 51,3-A: mp 278-280 °C; 1H NMR (500 MHz) δ 0.84
(36H, s), 5.07 (8H, s), 7.00-7.16 (20H, m), 7.14 (8H, s); 13C
NMR (125 MHz) δ 30.8, 33.8, 71.1, 126.8, 127.3, 128.0, 128.6,
129.4, 137.7, 146.0, 156.9; FAB-MS m/z 1081 [(M + 1)+]. Anal.
Calcd for C68H72O4S4: C, 75.51; H, 6.71; S, 11.86. Found: C,
75.26; H, 6.70; S, 12.06.
26,28-Diben zyloxyl-5,11,17,23-tetr a -ter t-bu tyl-2,8,14,20-
t e t r a t h ia p e n t a c y c lo [19.3.1.13 ,7 .19 ,1 3 .11 5 ,1 9 ]o c t a c o s a -
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en e-
25,27-d iol (syn -1,3-6). A mixture of thiacalix[4]arene 2 (3.00
g, 4.16 mmol), Na2CO3 (3.53 g, 33.3 mmol), bromomethylben-
zene (5.70 g, 33.3 mmol), and dry acetone (100 mL) was
refluxed for 2 d. After cooling, precipitates were removed by
filtration. The filtrate was poured into water (200 mL) and
extracted with chloroform. The organic layer was washed with
water and evaporated to leave an oil, which was suspended
in hot dichloromethane-ethanol, and the insoluble part was
(500 MHz) δ 0.79 (18H, s), 1.34 (18H, s), 5.49 (4H, s), 6.96
(4H, s), 7.23-7.27 (2H, m), 7.30-7.34 (4H, m), 7.60-7.64 (4H,
m), 7.68 (4H, s), 7.97 (2H, s); 13C NMR (125 MHz) δ 30.8, 30.9,
34.0, 34.2, 76.4, 122.2, 128.3, 128.5, 129.0, 129.3, 132.7, 134.4,
136.7, 142.7, 148.1, 155.6, 155.8; FAB-MS m/z 901 [(M + 1)+].
Anal. Calcd for C54H60O4S4: C, 71.96; H, 6.71; S, 14.23.
Found: C, 72.03; H, 6.70; S, 14.09.
26,27,28-Tr iben zyloxyl-5,11,17,23-tetr a -ter t-bu tyl-2,8,-
14,20-t et r a t h ia p en t a cyclo[19.3.1.13,7.19,13.115,19]oct a cosa -
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en -25-
ol (7). NaH (60% dispersion in mineral oil; 1.4 mg, 35 µmol)
was washed with dry hexane (2.0 mL) and suspended in dry
DMF (3 mL). To it was added syn-1,3-6 (27.7 mg, 30.7 µmol),
and the mixture was stirred at room temperature for 30 min
and then cooled to 0 °C. To the mixture was added bromo-
methylbenzene (d ) 1.438; 3.7 µL, 31 µmol), and the resulting
mixture was stirred at this temperature for 4 h. The mixture
was quenched by addition of several drops of methanol, and
the DMF was removed under reduced pressure at 60 °C. To
the residue was added 2 M HCl (50 mL), and the mixture was
extracted with chloroform. The organic layer was washed with
water and evaporated to dryness. The residual oil was
triturated with methanol to give a solid, which was purified
by TLC with hexane-ethyl acetate (15:1) as the eluent to give
1
7 as a colorless powder (21.2 mg, 70%): mp 200-202 °C; H
NMR (500 MHz) δ 0.85 (18H, s), 1.25 (9H, s), 1.27 (9H, s), 5.14
(2H, d, J ) 11.1 Hz), 5.14 (2H, d, J ) 11.1 Hz), 5.37 (2H, s),
6.96 (2H, d, J ) 2.5 Hz), 6.97 (2H, d, J ) 2.5 Hz), 7.14-7.16
(3H, m), 7.28-7.30 (6H, m), 7.34-7.35 (2H, m), 7.49-7.50 (4H,
m), 7.55 (2H, s), 7.60 (2H, s), 7.74 (1H, s); 13C NMR (125 MHz)
δ 30.9, 31.4, 31.4, 34.0, 34.1, 34.2, 74.7, 78.3, 121.9, 127.3,
127.4, 128.1, 128.3, 128.9, 129.2, 129.5, 129.8, 131.1, 132.4,
133.6; FAB-MS m/z 991[(M + 1)+]. Anal. Calcd for C61H66
-
O4S4: C, 73.90; H, 6.71; S, 12.94. Found: C, 73.82; H, 6.85; S,
13.19.
Ben zyla tion of 7 to 5P C a n d 5C. Tri-O-benzyl ether 7 (21.2
mg, 21.4 µmol) was suspended in dry acetone (4.0 mL),
containing Cs2CO3 (34.7 mg, 107 µmol) and bromomethylben-
zene (d ) 1.438; 12 µL, 100 µmol), and the mixture was heated
at reflux for 2 h. After cooling, precipitates were removed by
filtration, and the filtrate was poured into water (50 mL). The
mixture was extracted with chloroform, and the extract was
washed with water. After the solvent was evaporated, the
residual oil was triturated with methanol (20 mL) to give
a solid, which was purified by TLC with hexane-chloroform
(5:1) as the eluent to give 5PC (18.9 mg, 82%) and 5C (2.8 mg,
12%).
Diben zyla tion of syn -1,2-6 to 51,2-A, 5P C, a n d 5C. syn-1,2-
Di-O-benzyl ether 6 (40.8 mg, 45.3 µmol) was suspended in
dry acetone (4.0 mL), containing Cs2CO3 (127 mg, 390 µmol)
and bromomethylbenzene (d ) 1.438; 47 µL, 400 µmol). The
mixture was heated at reflux for 2 h. After cooling, precipitates
were removed by filtration. The filtrate was poured into water
(50 mL) and extracted with chloroform. The organic layer was
washed with water and evaporated to dryness. The residual
oil was triturated with methanol (20 mL) to give a solid, which
was chromatographed on silica gel with hexane-chloroform
(5:1) as the eluent to give 51,2-A (19.5 mg, 40%), 5PC (17.3 mg,
35%), and 5C (4.9 mg, 10%).
Oxid a tion of 2 to 4(r ctt) a n d 4(r tct). To a solution of 2
(3.00 g, 4.16 mmol) in chloroform (60 mL) were added acetic
acid (90 mL) and NaBO3‚4H2O (2.82 g, 18.3 mmol), and the
mixture was heated at 50 °C for 4 h. The cooled mixture was
poured into 2 M HCl (200 mL), and the aqueous layer was
extracted with chloroform. The combined organic layer was
washed with 6 M HCl and evaporated to leave an oil.
Trituration with hexane (100 mL) gave a solid, which was
suspended in boiled methanol (200 mL). The insoluble part
was collected by filtration and crystallized from dichlo-
2330 J . Org. Chem., Vol. 68, No. 6, 2003

Stereoisomers of Sulfinylcalix[4]arenes
romethane-methanol to give 5,11,17,23-tetra-tert-butyl-
25,26,27,28-t et r a h ydr oxy-2,8,14,20-t et r a t h ia pen t a cyclo-
[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9,11,13(27),-
15,17,19(26),21,23-dodecaene-r-2,t-8,c-14,t-20-tetraone [4(rtct)]
as colorless crystals (890 mg, 27%): mp 295 °C (decomp); IR
+ 1)+]. Anal. Calcd for C68H72O6S4: C, 73.34; H, 6.52; S, 11.52.
Found: C, 73.48; H, 6.71; S, 11.38.
25,26,27,28-Tetr a ben zyloxyl-5,11,17,23-tetr a -ter t-bu tyl-
2,8,14,20-tetr ath iapen tacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en e-r -
1
(KBr) 3188, 1001 cm-1; H NMR (500 MHz) δ 1.29 (36H, s),
2,c-8,c-14-tr ion e (11): mp 311-312.5 °C; IR (KBr) 1047 cm-1
;
1
1H NMR (500 MHz) δ 1.07 (18H, s), 1.14 (18H, s), 5.18 (2H, d,
J ) 11.2 Hz), 5.19 (4H, s), 5.56 (2H, d, J ) 11.2 Hz), 7.22-
7.32 (16H, m), 7.38 (2H, d, J ) 2.31 Hz), 7.39 (2H, d, J ) 2.31
Hz), 7.43-7.45 (4H, m), 7.62 (2H, d, J ) 2.39 Hz), 7.66 (2H, d,
J ) 2.39 Hz); 13C NMR (125 MHz) δ 31.0, 31.1, 77.7, 78.4,
122.8, 124.6, 124.8, 128.3, 128.5, 128.5, 128.8, 129.0, 130.0,
130.0, 135.1, 135.9, 136.9, 139.0, 139.3, 139.5, 148.0, 148.9,
149.2, 153.2; FAB-MS m/z 1129 [(M + 1)+]. Anal. Calcd for
7.65 (8H, s), 9.30 (4H, s); H NMR (500 MHz, CDCl3/DMSO-
d6 1:1) δ 1.23 (36H, s), 7.37 (4H, s), 7.76 (4H, s); 13C NMR (125
MHz) δ 31.3, 34.7, 124.2 (br), 130.2 (br), 142.1, 152.8; FAB-
MS m/z 785 [(M + 1)+]. Anal. Calcd for C40H48O8S4: C, 61.20;
H, 6.16; S, 16.34. Found: C, 60.88; H, 6.12; S, 16.06. On the
other hand, the filtrate was evaporated, and the residue was
crystallized from chloroform-hexane to give 5,11,17,23-tetra-
tert-butyl-25,26,27,28-tetrahydroxy-2,8,14,20-tetrathiapenta-
cyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9,11,13(27),-
15,17,19(26),21,23-dodecaene-r-2,c-8,t-14,t-20-tetraone [4(rctt)]
as colorless crystals (550 mg, 17%): mp 225-228 °C (decomp);
C
68H72O7S4: C, 72.30; H, 6.42; S, 11.36. Found: C, 72.24; H,
6.67; S, 11.30.
25,26,27,28-Tetr a ben zyloxyl-5,11,17,23-tetr a -ter t-bu tyl-
2,8,14,20-tetr ath iapen tacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en e-r -
2,c-8,c-14,c-20-tetr a on e (12): mp 318-319 °C; IR (KBr) 1049
1
IR (KBr) 3423, 1053, 1005 cm-1; H NMR (500 MHz) δ 1.19
(18H, s), 1.24 (18H, s), 7.47 (4H, br),7.58 (4H, s); 13C NMR
(125 MHz, CDCl2CDCl2, 360 K) δ 31.0, 31.1, 34.5, 34.6, 125.3,
126.6 (br), 128.5, 129.0, 143.7, 143.7, 152.3, 153.3; FAB-MS
m/z 785 [(M + 1)+]. Anal. Calcd for C40H48O8S4: C, 61.20; H,
6.16; S, 16.34. Found: C, 61.17; H, 6.34; S, 16.50.
1
cm-1; H NMR (500 MHz) δ 1.12 (36H, s), 5.22 (8H, s), 7.30-
7.37 (20H, m), 7.63 (8H, s); 13C NMR (125 MHz) δ 31.0, 35.2,
78.8, 124.9, 128.6, 129.3, 130.1, 134.8, 139.2, 148.9, 149.4; FAB-
MS m/z 1145 [(M + 1)+]. Anal. Calcd for C68H72O8S4: C, 71.30;
H, 6.34; S, 11.20. Found: C, 71.50; H, 6.35; S, 11.26.
Gen er a l P r oced u r e for th e Oxid a tion of 5C to 8-12
(Ta ble 2). To a solution of 5C (50.0 mg, 46.2 µmol) in
chloroform (2.0 mL) were added acetic acid (3.0 mL) and
NaBO3‚4H2O (1.1-4.4 molar equiv), and the mixture was
heated at 50 °C for 1 d. The cooled mixture was poured into
water and extracted with chloroform. The extract was washed
with water, and the solvent was evaporated to dryness. The
residue was purified by column chromatography on silica gel
with hexane-ethyl acetate (4:1 or 2:1) as the eluent to give
8-12. See Table 2 for the reaction conditions and the product
distribution.
Gen er a l P r oced u r e for th e Oxid a tion of 5P C to 13-15
(Sch em e 5). Oxidation of 5PC was performed by the same
procedure as used for the oxidation of 5C. See Scheme 5 for
the reaction conditions and the product distribution.
25,26,27,28-Tetr a ben zyloxyl-5,11,17,23-tetr a -ter t-bu tyl-
2,8,14,20-tetr ath iapen tacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en -2-
on e (13): mp 259.5-261 °C; IR (KBr) 1045 cm-1; 1H NMR (500
MHz) δ 0.75 (9H, s), 0.82 (9H, s), 0.93 (9H, s), 1.26 (9H, s),
4.05 (1H, d, J ) 14.8 Hz), 4.81 (1H, d, J ) 9.9 Hz), 5.08 (2H,
s), 5.15 (1H, d, J ) 9.9 Hz), 5.19 (1H, d, J ) 10.4 Hz), 5.38
(1H, d, J ) 10.4 Hz), 5.98 (1H, d, J ) 12.8 Hz), 6.78 (1H, d, J
) 2.51 Hz), 7.09-7.16 (5H, m), 7.13 (1H, d, J ) 2.51 Hz), 7.25-
7.30 (3H, m), 7.33 (1H, d, J ) 2.51 Hz), 7.34-7.41 (6H, m),
7.51 (1H, d, J ) 2.51 Hz), 7.52 (1H, d, J ) 2.48 Hz), 7.64 (1H,
d, J ) 2.50 Hz), 7.67 (1H, d, J ) 2.50 Hz), 7.55-7.57 (2H, m),
7.67-7.73 (4H, m), 7.72 (1H, d, J ) 2.48 Hz); 13C NMR (125
MHz) δ 30.9, 30.9, 31.3, 33.8, 33.9, 34.5, 34.7, 70.9, 75.9, 77.5,
77.9, 121.6, 123.4, 127.6, 127.7, 127.8, 128.1, 128.3, 128.4,
128.5, 128.5, 128.6, 128.9, 129.3, 129.8, 129.8, 135.5, 135.8,
136.6, 136.9, 137.3, 139.0, 146.0, 146.6, 147.4, 150.6, 155.9,
157.5, 160.0; FAB-MS m/z 1097[(M + 1)+]. Anal. Calcd for
25,26,27,28-Tetr a ben zyloxyl-5,11,17,23-tetr a -ter t-bu tyl-
2,8,14,20-tetr ath iapen tacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en -2-
1
on e (8): mp 262-264 °C; IR (KBr) 1045 cm-1; H NMR (500
MHz) δ 1.04 (18H, s), 1.11 (18H, s), 5.11 (2H, d, J ) 11.5 Hz),
5.21 (2H, d, J ) 11.0 Hz), 5.27 (2H, d, J ) 11.0 Hz), 5.54 (2H,
d, J ) 11.5 Hz), 7.17-7.25 (16H, m), 7.31 (2H, d, J ) 1.55
Hz), 7.32 (2H, d, J ) 1.55 Hz), 7.39 (2H, d, J ) 2.36 Hz), 7.41
(2H, d, J ) 2.36 Hz), 7.53-7.55 (4H, m); 13C NMR (125 MHz)
δ 31.1, 31.2, 34.1, 34.6, 76.5, 77.5, 122.3, 128.0, 128.1, 128.1,
129.6, 129.8, 129.9, 130.2, 133.7, 134.2, 136.5, 136.9, 137.0,
139.5, 146.4, 146.8, 153.5, 158.0; FAB-MS m/z 1097 [(M + 1)+].
Anal. Calcd for C68H72O5S4: C, 74.41; H, 6.61; S, 11.69.
Found: C, 74.43; H, 6.59; S, 11.59.
C
68H72O5S4: C, 74.41; H, 6.61; S, 11.69. Found: C, 74.15; H,
6.94; S, 11.50.
25,26,27,28-Tetr a ben zyloxyl-5,11,17,23-tetr a -ter t-bu tyl-
2,8,14,20-tetr ath iapen tacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en e-r -
25,26,27,28-Tetr a ben zyloxyl-5,11,17,23-tetr a -ter t-bu tyl-
2,8,14,20-tetr ath iapen tacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en e-r -
1
2,c-14-d ion e (9): mp 300-301.5 °C; IR (KBr) 1043 cm-1; H
1
2,c-8-d ion e (14): mp 267.5-269 °C; IR (KBr) 1053 cm-1; H
NMR (500 MHz) δ 1.09 (36H, s), 5.18 (2H, d, J ) 11.2 Hz),
5.55 (2H, d, J ) 11.2 Hz), 7.22-7.30 (12H, m), 7.38 (2H, d, J
) 2.44 Hz), 7.39 (2H, d, J ) 2.44 Hz), 7.40-7.42 (8H, m); 13C
NMR (125 MHz) δ 31.1, 34.6, 77.3, 122.5, 128.1, 128.3, 128.5,
129.9, 136.1, 136.6, 139.7, 147.5, 153.3; FAB-MS m/z 1113 [(M
+ 1)+]. Anal. Calcd for C68H72O6S4: C, 73.34; H, 6.52; S, 11.52.
Found: C, 73.20; H, 6.60; S, 11.34.
NMR (500 MHz) δ 0.83 (18H, s), 0.97 (9H, s), 1.32 (9H, s), 4.60
(2H, s), 5.06 (2H, s), 5.15 (2H, d, J ) 10.5 Hz), 5.37 (2H, d, J
) 10.5 Hz), 7.00-7.52 (20H, m), 7.05 (2H, d, J ) 2.42 Hz),
7.45 (2H, d, J ) 2.42 Hz), 7.68 (2H, s), 7.95 (2H, s); 13C NMR
(125 MHz) δ 30.8, 31.0, 31.4, 34.1, 34.4, 35.4, 73.6, 74.6, 77.4,
122.2, 123.5, 127.9, 128.1, 128.2, 128.3, 128.4, 128.5, 128.7,
128.7, 128.9, 129.3, 129.7, 134.7, 135.2, 135.8, 136.2, 137.2,
138.4, 138.8, 145.4, 146.3, 147.7, 148.0, 154.8, 159.4; FAB-MS
m/z 1113[(M + 1)+]. Anal. Calcd for C68H72O6S4: C, 73.34; H,
6.52; S, 11.52. Found: C, 73.27; H, 6.54; S, 11.41.
25,26,27,28-Tetr a ben zyloxyl-5,11,17,23-tetr a -ter t-bu tyl-
2,8,14,20-tetr ath iapen tacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en e-r -
2,c-8-d ion e (10): mp 294-296 °C; IR(KBr) 1045 cm-1 1H
;
25,26,27,28-Tetr a ben zyloxyl-5,11,17,23-tetr a -ter t-bu tyl-
2,8,14,20-tetr ath iapen tacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en e-r -
2,c-8,c-14,t-20-tetr a on e (15): mp 303-305 °C; IR (KBr) 1053
NMR (500 MHz) δ 0.82 (9H, s), 1.01 (9H, s), 1.26 (18H, s), 5.09
(2H, s), 5.20 (2H, d, J ) 11.7 Hz), 5.20 (2H, s), 5.82 (2H, d, J
) 11.7 Hz), 6.88 (2H, s), 7.15-7.36 (20H, m), 7.37 (2H, s), 7.62
(2H, d, J ) 2.46 Hz), 7.72 (2H, d, J ) 2.46 Hz); 13C NMR (125
MHz) δ 30.8, 30.9, 31.3, 34.0, 34.8, 35.0, 75.4, 79.2, 79.5, 121.9,
125.9, 128.1, 128.3, 128.3, 128.5, 128.5, 128.9, 129.0, 129.7,
129.9, 130.0, 132.6, 135.3, 136.4, 136.6, 137.5, 139.4, 139.7,
147.0, 147.2, 148.6, 151.2, 152.8, 157.1; FAB-MS m/z 1113 [(M
cm-1 1H NMR (500 MHz) δ 0.83 (9H, s), 0.86 (9H, s), 0.88
;
(9H, s), 1.34 (9H, s), 4.40 (1H, d, J ) 13.2 Hz), 4.66 (1H, d, J
) 13.2 Hz), 4.93 (1H, d, J ) 7.3 Hz), 5.13 (1H, d, J ) 10.1 Hz),
5.17 (1H, d, J ) 8.2 Hz), 5.29 (1H, d, J ) 10.1 Hz), 5.54 (1H,
d, J ) 8.2 Hz), 5.56 (1H, d, J ) 7.3 Hz), 7.05-7.07 (2H, m),
J . Org. Chem, Vol. 68, No. 6, 2003 2331

Morohashi et al.
7.12 (1H, d, J ) 2.40 Hz), 7.17 (1H, d, J ) 2.34 Hz), 7.19-
7.22 (3H, m), 7.34-7.42 (9H, m), 7.52 (1H, d, J ) 2.34 Hz),
7.57-7.59 (2H, m), 7.66 (1H, d, J ) 2.51 Hz), 7.70-7.81 (4H,
m), 7.94 (1H, d, J ) 2.40 Hz), 7.97 (1H, d, J ) 2.33 Hz), 8.03
(1H, d, J ) 2.33 Hz), 8.25 (1H, d, J ) 2.51 Hz); 13C NMR (100
MHz) δ 30.7, 30.7, 30.8, 31.3, 34.6, 34.6, 34.9, 35.5, 73.2, 80.4,
80.9, 83.0, 122.5, 122.6, 126.0, 126.1, 127.8, 127.9, 128.3, 128.8,
128.8, 128.8, 129.0, 129.1, 129.5, 130.0, 130.8, 130.9, 131.2,
131.8, 134.5, 135.1, 135.6, 135.8, 136.1, 136.2, 137.4, 137.6,
137.8, 138.1, 140.2, 144.6, 146.9, 148.1, 148.6, 149.0, 150.0,
152.6, 153.6; FAB-MS m/z 1145[(M + 1)+]. Anal. Calcd for
2,c-8,c-14,t-20-tetr a on e [16(r cct)]: yield 78%; mp 324.5-
327.5 °C; IR (KBr) 1055 cm-1; 1H NMR (500 MHz) δ 1.02 (9H,
s), 1.07 (9H, s), 1.39 (9H, s), 1.39 (9H, s), 3.43 (3H, s), 3.88
(3H, s), 4.03 (6H, s), 7.06 (1H, br), 7.29 (1H, br), 7.81 (1H, d,
J ) 2.1 Hz), 7.86 (1H, d, J ) 2.2 Hz), 7.97 (1H, d, J ) 2.2 Hz),
8.00 (1H, d, J ) 2.3 Hz), 8.06 (1H, br), 8.20 (1H, br); 13C NMR
(125 MHz) δ 30.8, 30.8, 31.3, 31.4, 34.7, 34.9, 34.9, 35.7, 61.6,
63.7, 64.0, 66.2, 122.5, 122.9, 125.4, 126.4, 127.6, 127.7, 130.5,
131.2, 135.3, 136.5, 136.5, 137.3, 137.6, 138.7, 138.8, 140.2,
144.4, 146.5, 148.3, 148.4, 150.1, 151.2, 152.7, 154.7; FAB-MS
m/z 841[(M + 1)+]. Anal. Calcd for C44H56O8S4: C, 62.83; H,
6.71; S, 15.25. Found: C, 62.48; H, 6.76; S, 15.56.
C
68H72O8S4: C, 71.30; H, 6.34; S, 11.20. Found: C, 71.03; H,
6.39; S, 11.34.
5,11,17,23-Tet r a -ter t-b u t yl-25,26,27,28-t et r a m et h oxy-
2,8,14,20-tetr ath iapen tacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en e-r -
2,c-8,t-14,t-20-tetr a on e [16(r ctt)]: yield 86%; mp 332.5-334
5,11,17,23-Tet r a -ter t-b u t yl-25,26,27,28-t et r a h yd r oxy-
2,8,14,20-tetr ath iapen tacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en e-r -
2,c-8,c-14,c-20-tetr a on e [4(r ccc)]. To a suspension of NaH
(8.1 mg, 340 µmol) in dry THF (5 mL) was added octane-1-
thiol (51.5 mg, 352 µmol), and the mixture was stirred at room
temperature for 30 min. To the mixture was added 12 (49.8
mg, 43.5 µmol), and the resulting mixture was refluxed for 2
h. After cooling, the mixture was poured into ice-cold methanol
(10 mL). To it was added 6 M HCl (10 mL), and the mixture
was extracted with chloroform. The organic layer was evapo-
rated to leave an oil, which was triturated with methanol.
Crystallization of the resulting solid from dichloromethane-
methanol gave 4(rccc) as a colorless powder (20.5 mg, 60%):
mp 316 °C (decomp); IR (KBr) 3128, 2959, 1028 cm-1; 1H NMR
(500 MHz, CDCl3/DMSO-d6 1:1) δ 1.14 (36H, s), 7.69 (8H, s);
13C NMR (125 MHz, CDCl3/DMSO-d6 1:1) δ 31.1, 34.6, 122.2,
133.0, 143.0, 150.4; FAB-MS m/z 785 [(M + 1)+]. Anal. Calcd
for C40H48O8S4: C, 61.20; H, 6.16; S, 16.34. Found: C, 60.98;
H, 6.11; S, 16.09.
1
°C; IR (KBr) 1053 cm-1; H NMR (400 MHz) δ 1.03 (18H, s),
1.38 (9H, s), 1.46 (9H, s), 3.47 (3H, s), 3.80 (3H, s), 4.07 (6H,
s), 7.21 (2H, s), 7.82 (2H, s), 7.97 (2H, s), 8.12 (2H, s); 13C NMR
(100 MHz) δ 30.8, 31.4, 34.6, 35.3, 35.7, 61.2, 61.7, 66.3, 119.6,
122.7 (br), 125.7, 127.4, 130.9, 135.2, 136.6, 138.8, 140.2 (br),
146.8, 148.1, 148.4, 150.1, 155.0; FAB-MS m/z 841 [(M + 1)+].
Anal. Calcd for C44H56O8S4: C, 62.83; H, 6.71; S, 15.25.
Found: C, 62.55; H, 6.65; S, 15.41.
5,11,17,23-Tet r a -ter t-b u t yl-25,26,27,28-t et r a m et h oxy-
2,8,14,20-tetr ath iapen tacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en e-r -
2,t-8,c-14,t-20-tetr a on e [16(r tct)]: yield 87%; mp 308.5-309
1
°C; IR (KBr) 1055 cm-1; H NMR (500 MHz) δ 1.32 (36H, s),
3.92 (12H, s), 7.68 (4H, d, J ) 2.4 Hz), 8.13 (4H, d, J ) 2.4
Hz); 13C NMR (125 MHz) δ 31.1, 34.8, 64.0, 127.4, 130.2, 136.5,
137.5, 146.7, 152.2; FAB-MS m/z 840 (M+). Anal. Calcd for
C44H56O8S4: C, 62.83; H, 6.71; S, 15.25. Found: C, 62.64; H,
6.68; S, 15.50.
5,11,17,23-Tet r a -ter t-b u t yl-25,26,27,28-t et r a h yd r oxy-
2,8,14,20-tetr ath iapen tacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en e-r -
2,c-8,c-14,t-20-tetr aon e [4(r cct)]. This compound was prepared
by the same procedure as used for the preparation of 4(rccc).
From 15 (2.00 g, 1.75 mmol) was obtained 4(rcct) as a colorless
powder (821 mg, 60%): mp 247-250 °C (decomp); IR (KBr)
X-r a y Cr ysta llogr a p h y. Data were collected on a Rigaku/
MSC mercury CCD diffractometer using Mo KR radiation (λ
) 0.71069 Å). The structures were solved by the direct methods
and refined by the full-matrix least-squares method. All
calculations were performed using the software package
teXsan (v 1.10).
1
3206, 1028, 1003 cm-1; H NMR (500 MHz) δ 1.21 (18H, s),
1.24 (18H, s), 7.49-7.87 (4H, m); 13C NMR (125 MHz, CDCl3/
DMSO-d6 1:1) δ 31.4, 31.5, 35.1, 35.5, 124.4 (br), 126.8 (br),
128.2 (br), 132.8 (br), 143.9, 153.4 (br); FAB-MS m/z 785 [(M
+ 1)+]. Anal. Calcd for C40H48O8S4: C, 61.20; H, 6.16; S, 16.34.
Found: C, 60.97; H, 6.41; S, 16.35.
Da ta for 5C: C68H72O4S4‚CH2ClCH2Cl, M ) 1180.51, mono-
clinic, a ) 21.617(1) Å, b ) 15.6187(9) Å, c ) 20.908(2) Å, â )
100.269°, V ) 6946.4(8) Å3, T ) 223 K, space group C2/c (No.
15), Z ) 4, Dcalc ) 1.129 g/cm3, µ(Mo KR) ) 2.57 cm-1, data
collection 900 images at 30.0 s, number of measured reflections
) 32460 (2θ < 54.9°), independent reflections ) 7795 (Rint
)
Gen er a l P r oced u r e for th e Meth yla tion of Ster eoiso-
m er s of 4 to 16. A stereoisomer of 4 was suspended in dry
THF (ca. 10 mM solution), containing 8.0 molar equiv of an
anhydrous alkali metal carbonate [K2CO3 for 4(rtct), Cs2CO3
for the other isomers of 4] and 20 molar equiv of iodomethane,
and the mixture was refluxed for 1 d. After cooling, precipitates
were removed by filtration, and the filtrate was poured into
water (50 mL). The mixture was extracted with chloroform,
and the extract was washed with water. After the solvent was
evaporated, the residue was chromatographed on silica gel
with chloroform-ethyl acetate as the eluent to give the
corresponding stereoisomer of 16, the yield and the spectral
and physical data of which are given below. Crystals suitable
for X-ray analyses were grown in chloroform-methanol.
0.022), final R ) 0.059, Rw ) 0.071 for 3635 observed
reflections [I0 > 3.0σ(I0)], GOF ) 1.90.
Da ta for 12: C68H72O8S4‚H2O‚CH3CN, M ) 1204.62, tet-
ragonal, a ) b ) 15.8724(6) Å, c ) 12.5804(9) Å, V ) 3169.4-
(3) Å3, T ) 150 K, space group P4/n (No. 85), Z ) 2, Dcalc
)
1.262 g/cm3, µ(Mo KR) ) 2.08 cm-1, data collection 480 images
at 30.0 s, number of measured reflections ) 21745 (2θ < 54.2°),
independent reflections ) 3444 (Rint ) 0.086), a symmetry-
related absorption correction, final R ) 0.062, Rw ) 0.073 for
1568 observed reflections [I0 > 3.5σ(I0)], GOF ) 1.56.
Da ta for 14: C68H72O6S4‚CHCl3, M ) 1232.93, triclinic, a
) 13.6278(7) Å, b ) 14.325(1) Å, c ) 18.048(1) Å, R ) 84.004-
(3)°, â ) 78.644(3)°, γ ) 68.0693(9)°, V ) 3202.7(4) Å3, T )
223 K, space group P1h(No. 2), Z ) 2, Dcalc ) 1.278 g/cm3, µ(Mo
KR) ) 3.24 cm-1, data collection 480 images at 30.0 s, number
of measured reflections ) 26431 (2θ < 52.0°), independent
reflections ) 11863 (Rint ) 0.025), a symmetry-related absorp-
tion correction, final R ) 0.063, Rw ) 0.067 for 6854 observed
reflections [I0 > 4.0σ(I0)], GOF ) 2.21.
5,11,17,23-Tet r a -ter t-b u t yl-25,26,27,28-t et r a m et h oxy-
2,8,14,20-tetr ath iapen tacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en e-r -
2,c-8,c-14,c-20-tetr a on e [16(r ccc)]: yield 83%; mp 322-324
1
°C; IR (KBr) 1051 cm-1; H NMR (500 MHz) δ 1.15 (36H, s),
4.18 (12H, s), 7.69 (8H, s); 13C NMR (125 MHz) δ 31.0, 35.3,
63.9 (br), 124.9 (br), 138.8, 149.9 (br), 151.2 (br); FAB-MS m/z
841 [(M + 1)+]. Anal. Calcd for C44H56O8S4: C, 62.83; H, 6.71;
S, 15.25. Found: C, 62.54; H, 6.60; S, 15.03.
Da ta for 16(r ccc): C44H56O8S4‚CH3OH‚H2O, M ) 891.23,
monoclinic, a ) 19.650(2) Å, b ) 13.8900(6) Å, c ) 33.6300(5)
Å, â ) 91.5800(3)°, V ) 9175.4(8) Å3, T ) 220 K, space group
5,11,17,23-Tet r a -ter t-b u t yl-25,26,27,28-t et r a m et h oxy-
2,8,14,20-tetr ath iapen tacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-d od eca en e-r -
C2/c (No. 15), Z ) 8, Dcalc ) 1.296 g/cm3, µ(Mo KR) ) 2.64 cm-1
,
data collection 1024 images at 30.0 s, number of measured
reflections ) 31508 (2θ < 55.0°), independent reflections )
2332 J . Org. Chem., Vol. 68, No. 6, 2003

Stereoisomers of Sulfinylcalix[4]arenes
9512 (Rint ) 0.021), final R ) 0.045, Rw ) 0.050 for 6328
observed reflections [I0 > 3.0σ(I0)], GOF ) 1.36.
102.7716(6)°, V ) 5073.4(6) Å3, T ) 230 K, space group P21/n
(No. 14), Z ) 4, Dcalc ) 1.257 g/cm3, µ(Mo KR) ) 3.92 cm-1
data collection 754 images at 30.0 s, number of measured
reflections ) 36079 (2θ < 52°), independent reflections ) 9672
(Rint ) 0.053), final R ) 0.066, Rw ) 0.069 for 4621 observed
reflections [I0 > 2.0σ(I0)], GOF ) 1.22.
,
Da ta for 16(r cct): C44H56O8S4‚CHCl3, M ) 960.54, triclinic,
a ) 11.430(2) Å, b ) 14.940(3) Å, c ) 16.120(5) Å, R ) 90.730-
(8)°, â ) 105.340(3)°, γ ) 99.450(3)°, V ) 2640.1841 Å3, T )
230 K, space group P1h(No. 85), Z ) 2, Dcalc ) 1.208 g/cm3, µ(Mo
KR) ) 3.77 cm-1, data collection 480 images at 30.0 s, number
of measured reflections ) 20493 (2θ < 54.2°), independent
reflections ) 10004 (Rint ) 0.052), final R ) 0.067, Rw ) 0.087
for 4529 observed reflections [I0 > 5.0σ(I0)], GOF ) 2.205.
Da ta for 16(r ctt): C44H56O8S4‚CH3OH, M ) 873.20, mono-
clinic, a ) 11.2043(6) Å, b ) 15.275(2) Å, c ) 14.901(1) Å, â )
96.4206(9)°, V ) 2534.3(4) Å3, T ) 230 K, space group P21/m
Ack n ow led gm en t. This work was supported by
J SPS Research for the Future Program and by a Grant-
in-Aid for Scientific Research on Priority Areas (no.
1020820) from the Ministry of Education, Science,
Sports and Culture, J apan.
(No. 11), Z ) 2, Dcalc ) 1.144 g/cm3, µ(Mo KR) ) 2.35 cm-1
,
data collection 750 images at 30.0 s, number of measured
reflections ) 21335 (2θ < 52°), independent reflections ) 5090
(Rint ) 0.036), final R ) 0.060, Rw ) 0.075 for 2765 observed
reflections [I0 > 3.0σ(I0)], GOF ) 2.15.
Da ta for 16(r tct): C44H56O8S4‚CHCl3, M ) 960.54, mono-
clinic, a ) 15.7107(6) Å, b ) 21.633(2) Å, c ) 15.285(1) Å, â )
Su p p or tin g In for m a tion Ava ila ble: CIF files for 5C, 12,
14, and four stereoisomers 16. This material is available free
of charge via the Internet at http://pubs.acs.org.
J O026801X
J . Org. Chem, Vol. 68, No. 6, 2003 2333