Synthesis of novel dihydroxydiphosphines and dihydroxydicarboxylic acids having a tetra(thio-1,3-phenylene-2-yl) backbone

Article abstract of DOI:10.1080/10610278.2010.514913

Novel tetradentate PPh2-OH hybrid ligands 5 and CO2H-OH hybrid ligands 6 have been successfully synthesised from tetra(thio-5-tert-butyl-2-hydroxy-1,3- phenylene) (24) by replacing the hydroxy groups at both the 2-position and either the 2′-, 2″- or 2?-po

Full text of DOI:10.1080/10610278.2010.514913

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Synthesis of novel dihydroxydiphosphines and
dihydroxydicarboxylic acids having a tetra(thio-1,3-
phenylene-2-yl) backbone
Yuki Akahira a , Kazutoshi Nagata a , Naoya Morohashi a & Tetsutaro Hattori a
a Department of Biomolecular Engineering , Graduate School of Engineering, Tohoku
University , 6-6-11 Aramaki-Aoba, Aoba-ku, Sendai, 980-8579, Japan
Published online: 22 Feb 2011.
To cite this article: Yuki Akahira , Kazutoshi Nagata , Naoya Morohashi & Tetsutaro Hattori (2011) Synthesis of novel
dihydroxydiphosphines and dihydroxydicarboxylic acids having a tetra(thio-1,3-phenylene-2-yl) backbone, Supramolecular
Chemistry, 23:01-02, 144-155, DOI: 10.1080/10610278.2010.514913
To link to this article: http://dx.doi.org/10.1080/10610278.2010.514913
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Supramolecular Chemistry
Vol. 23, Nos. 1–2, January–February 2011, 144–155
Synthesis of novel dihydroxydiphosphines and dihydroxydicarboxylic acids having
a tetra(thio-1,3-phenylene-2-yl) backbone
Yuki Akahira, Kazutoshi Nagata, Naoya Morohashi* and Tetsutaro Hattori*
Department of Biomolecular Engineering, Graduate School of Engineering, Tohoku University, 6-6-11 Aramaki-Aoba, Aoba-ku,
Sendai 980-8579, Japan
(Received 5 July 2010; final version received 6 August 2010)
Novel tetradentate PPh2–OH hybrid ligands 5 and CO2H–OH hybrid ligands 6 have been successfully synthesised from
tetra(thio-5-tert-butyl-2-hydroxy-1,3-phenylene) (24) by replacing the hydroxy groups at both the 2-position and either the
20-, 200- or 2000-position with diphenylphosphino or carboxy groups, after converting into bistriflates 8; the substitution
positions of newly introduced substituents are denoted hereafter by superscript 1,n as 51,n. Bistriflates 81,3 and 81,4 can be
readily prepared by the regioselective detriflation of tetrakistriflate 7 with tetrabutylammonium fluoride (TBAF),
conducted under different conditions. On the other hand, the preparation of bistriflate 81,2 requires a four-step process
through protection/deprotection. Thus, the silylation of tetraol 24 with an excess of 1,3-dichloro-1,1,3,3-
tetraisopropyldisiloxane gives O,O0- and O00,O000-disiloxane-1,3-diyl-capped derivative 9. One of the two disiloxane
bridges is removed by the treatment with 0.5 mol equiv. of TBAF to give diol 10. Triflation of diol 10, followed by the
removal of the remaining disiloxane bridge, affords bistriflate 81,2. Bistriflates 8 are subjected to palladium-catalysed
phosphorylation, followed by the reduction of the resulting phosphine oxide 121,n to give PPh2–OH hybrid ligands 51,n
(n ¼ 2–4), while CO2H–OH hybrid ligands 61,n (n ¼ 3,4) are obtained from 8 via acetylation of the remaining hydroxy
groups, followed by palladium-catalysed methoxycarbonylation of the TfO moieties, and subsequent hydrolysis of the
resulting tetraesters 14. X-ray structural analyses of dicarboxylic acids 61,3 and 61,4 reveal that they form quite different
3D network structures to each other. Interestingly, 61,4 constructs a porous channel with a potential for serving as a
supramolecular host, by the stacking of its cyclic dimer that is formed by intermolecular hydrogen bondings between the
carboxy groups.
Keywords: tetra(thio-m-phenylene); regioselective synthesis; hydroxyphosphine; hydroxyacid
Introduction
only in relatively high pH regions due to the low acidity
of the phenolic hydroxy groups. (2) They are not suitable
as ligands for late transition metal catalysts, such as
palladium and rhodium complexes, because the for-
mation of strong OZmetal bonds prevents necessary
changes in the oxidation number of the metal centre
during catalytic cycles. One solution for these difficulties
may be to replace the hydroxy groups with other
functions, such as carboxy or sulpho groups in the
former case and phosphino or secondary amino groups in
the latter case. However, the cleavage of the aryl-oxygen
bonds of calix[4]arenes is quite difficult even by
employing conventional CZO bond cleavage reactions
of aryl triflates or other esters by using palladium or
nickel catalysts because of steric hindrance caused by the
sterically crowded cyclic structure (19–21).
The design of multidentate ligands has been a subject of
intense research activity in the fields of developing
sensors, metal extractants, catalysts and so on (1–5).
Thiacalix[4]arene 1 (6–8), and its sulphur-oxidised
derivatives, sulphinyl and sulphonylcalix[4]arenes are
known to serve as multidentate ligands with high metal-
binding ability, due to the cooperative coordination of
the phenolic hydroxy groups with the bridging sulphur
atomic groups (9), and have successfully been utilised
for extractants (10–13), sensing reagents (8, 14, 15),
ligands for cluster complexes (9) and catalysts (16–18),
and so on. In some applications of thiacalix[4]arene 1
and its sulphur-oxidised derivatives as multidentate
ligands, however, there are still problems to be
addressed. For example, (1) they can extract metal ions
*Corresponding authors. Email: morohashi@orgsynth.che.tohoku.ac.jp; hattori@orgsynth.che.tohoku.ac.jp
ISSN 1061-0278 print/ISSN 1029-0478 online
q 2011 Taylor & Francis
DOI: 10.1080/10610278.2010.514913
http://www.informaworld.com

Supramolecular Chemistry
145
X-ray structural analyses of CO2H–OH hybrid ligands
61,n (n ¼ 3,4) are also reported.
Results and discussion
First, regioselective synthesis of bistriflates 81,n (n ¼ 2–4)
was investigated with the intention of applying palladium-
catalysed phosphorylation and methoxycarbonylation to
the cleavage of the aryl-oxygen bonds of tetraol 24. It is
well known in calixarene chemistry that the dialkylation
of calix[4]arenes with alkyl halides in the presence of a
base preferentially proceeds at the distal hydroxy groups
by virtue of a circular intramolecular hydrogen bonding in
the monoalkylated intermediate (31, 32), which provides
an easy access to O,O00-dialkylated calix[4]arenes.
The preferential O,O00-disubstitution is also the case with
the bistriflation of thiacalix[4]arene 1 with triflic
anhydride in the presence of pyridine (33). However,
attempts to selectively esterify two hydroxy groups of
tetraol 24 with triflic anhydride under various reaction
conditions were not fruitful. We then tried detriflation of
readily preparable tetrakistriflate 7 (25). To our pleasure,
the reaction of tetrakistriflate 7 with 8.0 mol equiv. of
tetrabutylammonium fluoride (TBAF) in THF at room
temperature gave bistriflate 81,3 as a major product (64%),
while the same reaction carried out under refluxing
conditions using a reduced amount of TBAF gave
bistriflate 81,4 in 56% yield (Scheme 1). The reaction
mechanisms for the selective formation of 81,3 and 81,4 are
not clear at present. The fast atom bombardment (FAB)
mass spectra of 81,3 and 81,4 exhibited the molecular ion
peak at 954 (Mþ), indicating that both of them are
We have recently reported that an acyclic analogue of
thiacalix[4]arene 24 exhibits comparable complexation
ability to thiacalix[4]arene 1 towards soft to intermediate
metal ions in solvent extraction experiments (22, 23). We
have also reported that diphosphine 3 (24) and
tetracarboxylic acid 4 (25) are readily prepared from
acyclic dimer 22 and tetramer 24 by using palladium-
catalysed phosphorylation (26, 27) and methoxycarbony-
lation (28–30) as a key step, respectively. Diphosphine 3
was found to bind to a palladium(II) ion with different
coordination modes, i.e. bidentate P–P and tridentate
P–S–P, depending on the electron density of the
palladium centre (24). In addition, the epithio linkage
could coordinate to two palladium ions by using its two
lone pairs, which enabled diphosphine 3 to serve as a P–S
ligand to form a dinuclear palladium complex. These
properties are of special interest for catalytic applications.
On the other hand, tetracarboxylic acid 4 extracted
lanthanide ions even at pH 3.0 in solvent extraction
experiments (25), indicating that 4 has higher extractabi-
lity towards lanthanide ions than sulphonylcalix[4]arene.
These observations indicate that acyclic oligo(thio-1,3-
phenylene)s provide useful scaffolds for developing
diverse multidentate ligands with a coordination mode,
binding ability and metal selectivity that are suitable for
serving their respective purposes. Herein, we report the
synthesis of novel tetradentate PPh2–OH hybrid ligands
51,n (n ¼ 2–4) and CO2H–OH hybrid ligands 61,n
(n ¼ 3,4), having a tetra(thio-1,3-phenylene) skeleton by
converting two hydroxy groups of tetraol 24 into
diphenylphosphino and carboxy groups, respectively.
1
bistriflates. The H NMR spectrum of 81,3 exhibited four
singlets (9H each) for the tert-butyl protons, two pairs of
doublets (1H each) for the aryl protons on the internal
benzene rings and two sets of two doublets (1H each) and
one double-doublet (1H) for the aryl protons on the
terminal benzene rings. The unsymmetrical spectral
pattern indicates that it is 1,2- or 1,3-bistriflate. However,
the comparison of the physical properties of bistriflate 81,3
with those of authentic 1,2-bistriflate 81,2 prepared by a
four-step process through protection/deprotection (vide
infra) revealed that they are not the same compound.
Therefore, 81,3 was assigned to be 1,3-bistriflate, which
coincides with the assignment based on an X-ray
crystallographic analysis after conversion into dicar-
1
boxylic acid 61,3 (vide infra). On the other hand, the H
NMR spectrum of 81,4 exhibited two singlets (18H each)
for the tert-butyl protons, a pair of doublets (2H each) for
the aryl protons on the internal benzene rings and a set of
two doublets (2H each) and one double-doublet (2H) for
the aryl protons on the terminal benzene rings; the
magnetic equivalences suggest a C2-symmetric structure,
i.e. 1,4- or 2,3-bistriflate. Compound 81,4 was finally
assigned to be 1,4-bistriflate by chemical correlation with

146
Y. Akahira et al.
Scheme 1. Synthesis of 1,3- and 1,4-bistriflates 81,3 and 81,4
.
bis(phosphine oxide) 121,4, as well as an X-ray crystal-
lographic analysis after conversion into dicarboxylic acid
61,4 (vide infra).
of NaH afforded O,O0- and O00,O000-disiloxane-1,3-diyl-
capped derivative 9 in a good yield. One of the two
disiloxane bridges could be removed from 9 by a short
treatment with 0.5 mol equiv. of TBAF, giving diol 10 in
42% yield with the recovery of 9 (39%). Increasing the
amount of TBAF and/or prolonging the reaction time
caused further desilylation of diol 10. Triflation of diol 10
followed by the deprotection of the remaining disiloxane
gave 1,2-bistriflate 81,2 in a total of 25% yield based on the
starting tetraol 24.
It has been reported from our laboratory that two
adjacent hydroxy groups of calix[4]arenes can be
protected with 1,3-dichloro-1,1,3,3-tetraisopropyldisilox-
ane (TIPDSCl), which enables otherwise difficult regio-
and stereoselective synthesis of syn- and anti-O,O0-
dialkylated calix[4]arenes via dialkylation of the remain-
ing hydroxy groups, followed by the deprotection of the
TIPDS moiety (34). We supposed that a similar process
through protection/deprotection would provide an easy
access to 1,2-bistriflate 81,2 (Scheme 2). The treatment of
tetraol 24 with 2.4 mol equiv. of TIPDSCl in the presence
As the desired bistriflates 8 were in hand, their
transformation into diphosphines 5 was investigated.
Bistriflates 8 were submitted to palladium-catalysed
phosphorylation (26, 27) with Ph2P(O)H to give bis(pho-
Scheme 2. Synthesis of 1,2-bistriflate 81,2
.

Supramolecular Chemistry
147
i
Scheme 3. Synthesis of diphosphines 51,2, 51,3 and 51,4. Reagents and conditions: (i) Ph2P(O)H, Pd(OAc)2, dppb, Pr2EtN, DMSO,
1208C and (ii) HSiCl3, Et3N, toluene, reflux.
sphine oxide)s 12, which were then reduced with HSiCl3
to give diphosphines 5 in varying yields, depending on the
substitution positions of the two diphenylphosphino
moieties (Scheme 3). Bis(phosphine oxide) 121,4 exhibited
a resonance pattern agreeable to the C2-symmetric
might prevent the reaction. The hydroxy groups of 81,4
were then acetylated with acetic anhydride and the
resulting diacetate 131,4 was submitted to the methoxy-
carbonylation, which proceeded smoothly to give dimethyl
ester 141,4 in 80% yield (Scheme 4). Alkaline hydrolysis
of 141,4 gave the desired 1,4-dicarboxylic acid 61,4 in
quantitative yield. In the same manner, 1,3-dicarboxylic
acid 61,3 could be prepared from bistriflate 81,3 in a total of
68% yield. On the contrary, the diacetate of 1,2-bistriflare
81,2 resisted the methoxycarbonylation, presumably due to
steric reasons, and we could not find any good synthetic
1
structure in the H NMR spectrum. The signals for the
two adjacent protons on the terminal benzene ring (2H
each) were found to be coupled to the phosphorus atom
4
(3JH – P ¼ 12.7 and JH – P ¼ 1.9 Hz, respectively),
although another signal for the terminal benzene ring
was unclear because of overlapping with the signals for the
diphenylphosphinoyl moieties. The H–P couplings
allowed us to assign the compound to be 1,4-bis(phosphine
oxide), which coincides with the assignment based on the
X-ray crystallographic analysis of dicarboxylic acid 61,4
(vide infra). Diphosphines 5, bearing three different types
of coordination sites, are expected to serve as multidentate
ligands for the construction of heteronuclear multimetallic
complexes (16, 24).
route to 1,2-dicarboxylic acid 61,2
.
X-ray crystallographic analyses of dicarboxylic acids
61,3 and 61,4 were carried out to determine the
regiochemistries of 61,3 and 61,4, as well as those of
bistriflates 81,3 and 81,4, and to understand how the
arrangement of the carboxy and hydroxy groups effects on
the stereostructures of 6. Single crystals of 61,3 and 61,4
were grown by diffusion of hexane vapour into an acetone
solution of 61,3 or diffusion of cyclohexane vapour into a
benzene solution of 61,4. The X-ray structure of 61,3
revealed that the two carboxy groups reside at the 2, 200-
positions (Figure 1), which established the regiochemistry
The methoxycarbonylation (28–30) of bistriflate 81,4
was first attempted in the presence of 0.4 mol equiv.
of Pd(OAc)2, 0.8 mol equiv. of dppb and a large excess of
Hunig’s base in a 2:1 mixture of DMSO and methanol
under 1 atm of CO atmosphere at 708C. However, the
reaction was sluggish and did not afford the desired
dimethyl ester but a trace amount of monomethyl ester
with the recovery of most of the starting bistriflate.
We assumed that the phenolic hydroxy groups of 81,4
of dicarboxylic acid 61,3, as well as that of bistriflate 81,3
,
to be 1,3. The molecule of 61,3 adopts a bent structure, in
which an intramolecular hydrogen bonding is observed
between the hydroxy group at the 20-postion and the
carboxy group at the 200-postion; the interatomic distance

148
Y. Akahira et al.
Scheme 4. Synthesis of dicarboxylic acids 61,3 and 61,4. Reagents and conditions: (i) Ac2O, pyridine, CH2Cl2, rt; (ii) CO (1 atm),
MeOH, Pd(OAc)2, dppb, iPr2EtN, DMSO, 708C and (iii) KOH, EtOH–H2O (10:1), reflux.
˚
between the two oxygen atoms is 3.129 (3) A. In addition,
one molecule is connected with two neighbouring
molecules by intermolecular hydrogen bondings between
each other’s carboxy groups at the same position, by which
a zigzag structure is created along the a-axis (Figure 2);
the average bond length of the C(vO)OZHZOvC
˚
hydrogen bondings is 1.721 A. On the other hand, the
X-ray structure of 61,4 revealed that the two carboxy
groups reside at the 2, 2000-positions (Figure 3), which
established the regiochemistry of dicarboxylic acid
61,4, as well as that of triflate 81,4, to be 1,4. In the crystal
of 61,4, an intramolecular hydrogen bonding is observed
between the hydroxy groups at the 20- and 200-positions;
the interatomic distance between the two oxygen
Figure 1. X-ray structure of 61,3. Hydrogen atoms except those
of carboxy groups, disordered carbon atoms and included solvent
molecules are omitted for clarity. Dotted line represents
intramolecular hydrogen bonding.
1,4
˚
atoms is 2.853 (5) A. The two molecules of 6
are
associated by intermolecular hydrogen bondings between
the carboxy groups to form a cyclic dimer; the average
Figure 2. Crystal packing of 61,3 along the [001] plane. Included solvent molecules, disordered carbon atoms and hydrogen atoms
except those of carboxy groups are omitted for clarity. Dotted lines represent intermolecular hydrogen bondings.

Supramolecular Chemistry
149
Figure 4. Crystal packing of 61,4 viewed along the [100] plane
(a) and the [001] plane. (b) Included solvent molecules being out
of the channel, disordered carbon atoms and hydrogen atoms
except those of carboxy groups are omitted for clarity. Molecules
are colour coded to make the packing structure easily
understandable.
Figure 3. X-ray structure of dimeric 61,4. Top view (a) and side
view. (b) Included solvent molecules, disordered carbon atoms
and hydrogen atoms except those of carboxy groups are omitted
for clarity. Dotted lines represent intermolecular hydrogen
bondings.
bond length of the C(vO)OZHZOvC hydrogen
˚
bondings is 1.898 A. Furthermore, the dimers construct a
Experimental
General
porous channel along the a-axis and each one molecule
of benzene and cyclohexane are included in each unit
(Figure 4). This indicates that dicarboxylic acid 81,4 has a
potential for serving as a supramolecular host, which can
selectivity adsorb particular molecules in the solid state.
In summary, sulphur-bridged tetrakisphenol 24 could
be regioselectively converted into bistriflates 81,3 and 81,4
via triflation to tetrakistriflate 7, followed by regioselective
detriflation with TBAF and into bistriflate 81,2 via a four-
step process using a disiloxane protecting group (TIPDS).
The bistriflates served as precursors for preparing novel
tetradentate PPh2–OH hybrid ligands 51,2, 51,3 and 51,4
and CO2H–OH hybrid ligands 61,3 and 61,4. The X-ray
analyses of 61,3 and 61,4 revealed that the arrangement of
the carboxy and hydroxy groups greatly affected the
association of the molecules and, as a result, the 3D
packing structure in crystals. Studies to bring out inherent
functions of these ligands and to synthesise other hybrid
ligands bearing an oligo(thio-1,3-phenylene) skeleton are
in progress.
Melting points were taken using the Stuart SMP3 melting
1
point apparatus. H NMR and 13C NMR spectra were
measured using tetramethylsilane as an internal standard
and CDCl3 as a solvent, unless otherwise noted. IR
spectra were recorded on a Shimazu FTIR-8300
spectrometer. Microanalyses were carried out in the
Microanalytical Laboratory of the Institute of Multi-
disciplinary Research for Advanced Materials, Tohoku
University. HRMS spectra were measured using a Bruker
Daltonics APEX III in Research and Analytical Center for
Giant Molecules, Graduate School of Science, Tohoku
University. Silica gel 60 (63–200 mm) was used for
column chromatography. Water- and air-sensitive reac-
tions were routinely carried out under nitrogen. DMF
(CaSO4), DMSO (CaSO4), CH2Cl2 (CaH2) and MeOH
(Mg) were distilled from dehydrating agents and stored
under nitrogen. Dry THF (water ,20 ppm) was used as
purchased. Compound 24 was prepared as described in the
literature (35).

150
Y. Akahira et al.
added and the mixture was refluxed for 1 h. After being
Synthesis
quenched with 2 M HCl (2.0 ml), the mixture was poured
into water and extracted with CH2Cl2 (5.0 ml £3).
The organic layer was dried over MgSO4 and evaporated
to leave a residue, which was chromatographed on silica
gel with CHCl3–hexane (1:1) as the eluent to give 81,4
(22.0 mg, 56%) as a colourless powder, mp 1078C
Compound 7
A solution of 24 (0.500 g, 0.723 mmol) and pyridine
(510 ml, 6.34 mmol) in CH2Cl2 (20 ml) was stirred at room
temperature for 1 h. Triflic anhydride (1.88 ml, 11.5 mmol)
was added to the mixture at 08C and the resulting mixture
was stirred at room temperature for 2 h. After being
quenched with 2 M HCl (10 ml), the mixture was poured
into water and extracted with CHCl3 (100 ml£3). The
organic layer was dried over MgSO4 and evaporated to
leave a residue, which was chromatographed on silica gel
with CHCl3–hexane (1:1) as the eluent to give 7 (0.786 g,
89%) as a colourless powder, mp 128.2–130.98C; FAB-
MS 1218 (Mþ); 1H NMR (400 MHz) d 1.08 (s, 18H,
C(CH3)3), 1.25 (s, 18H, C(CH3)3), 7.23 (d, 2H, J ¼ 2.4 Hz,
ArH), 7.24 (d, 2H, J ¼ 2.4 Hz, ArH), 7.26 (d, 2H,
J ¼ 8.7 Hz, ArH), 7.41 (dd, 2H, J ¼ 8.7, 2.4 Hz, ArH),
7.46 (d, 2H, J ¼ 2.4 Hz, ArH); 13C NMR (100 MHz) d
30.6, 31.0, 34.9, 117.0, 120.2, 121.7, 123.4, 127.2, 127.3,
130.0, 130.1, 131.1, 131.3, 132.2, 145.3, 146.9, 152.7,
152.7; IR (KBr) 2970, 1427, 1211, 1138 cm21. Anal.
Calcd for C44H46F12O12S7: C, 43.34; H, 3.80. Found: C,
43.15; H, 3.80.
1
(decomp.); FAB-MS 954 (Mþ); H NMR (400 MHz) d
1.14 (s, 18H, C(CH3)3), 1.20 (s, 18H, C(CH3)3), 6.96 (s,
2H, OH), 7.04 (d, 2H, J ¼ 2.3 Hz, ArH), 7.18 (d, 2H,
J ¼ 8.6 Hz, ArH), 7.26 (dd, 2H, J ¼ 8.6, 2.3 Hz, ArH),
7.37 (d, 2H, J ¼ 2.3 Hz, ArH), 7.42 (d, 2H, J ¼ 2.3 Hz,
ArH); 13C (100 MHz) d 31.0, 31.2, 34.3, 34.8, 116.2,
117.0, 119.8, 120.2, 121.3, 125.6, 128.4, 129.0, 132.6,
133.5, 144.7, 145.4, 155.2, 153.7; IR (KBr) 3458, 2964,
1213 cm21. HRMS Calcd for C42H48F6O8S5Na: 977.1749.
Found: 977.1747.
Compound 9
To a solution of 24 (1.00 g, 1.45 mmol) in DMF (25 ml)
NaH (208 mg, 6.88 mmol) was added and the mixture was
stirred at room temperature for 2 h. To the mixture a
solution of TIPDSCl (1.36 ml, 3.44 mmol) in DMF (15 ml)
was added dropwise and the resulting mixture was stirred
at room temperature for 12 h. After being quenched with
2 M HCl (10 ml), the mixture was poured into water and
extracted with Et2O (20 ml£3). The organic layer was
dried over MgSO4 and evaporated to leave a residue,
which was chromatographed on silica gel with CHCl3–
hexane (1:3) as the eluent to give 9 (1.14 g, 67%) as a
colourless powder, mp 103–1058C; FAB-MS 1131
([M 2 iPr]þ); 1H NMR (500 MHz) d 0.68–0.96 (m,
28H, CH(CH3)2), 1.10–1.20 (m, 28H, CH(CH3)2), 1.15 (s,
18H, C(CH3)3), 1.18 (s, 18H, C(CH3)3), 6.82 (d, 2H,
J ¼ 8.4 Hz, ArH), 7.04–7.09 (m, 4H, ArH), 7.16 (d, 2H,
J ¼ 2.5 Hz, ArH), 7.49 (d, 2H, J ¼ 2.5 Hz, ArH); 13C
NMR (125 MHz) d 13.8, 13.8, 17.3, 17.3, 17.5, 17.7, 31.3,
31.3, 34.2, 34.2, 120.6, 124.6, 124.8, 127.0, 127.1, 128.4,
128.9, 133.1, 144.8, 145.2, 150.8, 152.2; IR (KBr) 2951,
1486, 933 cm21. Anal. Calcd for C64H102O6S3Si4: C,
65.36; H, 8.74. Found: C, 65.34; H, 8.53.
Compound 81,3
To a solution of 7 (50.0 mg, 41.0 mmol) in THF (3.0 ml), a
1.0 M solution of TBAF in THF (328 ml, 0.328 mmol) was
added and the mixture was stirred at room temperature for
1 h. After being quenched with 2 M HCl (2.0 ml), the
mixture was poured into water and extracted with CH2Cl2
(5.0 ml £3). The organic layer was dried over MgSO4 and
evaporated to leave a residue, which was chromatographed
on silica gel with CHCl3–hexane (1:1) as the eluent to give
81,3 (25.5 mg, 64%) as an oil, FAB-MS 954 (Mþ); H
1
NMR (400 MHz) d 0.94 (s, 9H, C(CH3)3), 1.18 (s, 9H,
C(CH3)3), 1.23 (s, 9H, C(CH3)3), 1.30 (s, 9H, C(CH3)3),
6.31 (s, 1H, OH), 6.62 (d, 1H, J ¼ 2.3 Hz, ArH), 6.76 (s,
1H, OH), 6.85 (d, 1H, J ¼ 2.3 Hz, ArH), 7.02 (d, 1H,
J ¼ 8.6 Hz, ArH), 7.17 (d, 1H, J ¼ 8.6 Hz, ArH), 7.19 (d,
1H, J ¼ 8.6 Hz, ArH), 7.29 (dd, 1H, J ¼ 8.6, 2.3 Hz, ArH),
7.40 (d, 1H, J ¼ 2.3 Hz, ArH), 7.43 (dd, 1H, J ¼ 8.6,
2.3 Hz, ArH), 7.45 (d, 1H, J ¼ 2.3 Hz, ArH), 7.51 (d, 1H,
J ¼ 2.3 Hz, ArH); 13C (100 MHz) d 30.6, 31.0, 31.2, 31.4,
34.2, 34.4, 34.7, 34.8, 113.3, 115.7, 117.3, 117.3, 117.4,
117.5, 119.9, 121.4, 124.9, 126.0, 126.7, 128.5, 129.2,
130.2, 130.2, 131.8, 133.6, 133.8, 134.0, 141.7, 144.6,
144.9, 145.8, 152.1, 152.3, 154.0, 155.2; IR (KBr) 3457,
2962 cm21. Anal. Calcd for C42H48F6O8S5: C, 52.81; H,
5.07. Found: C, 52.98; H, 5.18.
Compound 10
To a solution of 9 (50.0 mg, 42.5 mmol) in THF (3 ml) a
1.0 M solution of TBAF in THF (21.3 ml, 21.3 mmol) was
added and the mixture was stirred at room temperature for
45 min. After being quenched with 2 M HCl (5 ml), the
mixture was poured into water and extracted with CH2Cl2
(2 ml £3). The organic layer was dried over MgSO4 and
evaporated to leave an oil, which was chromatographed on
silica gel with CHCl3–hexane (1:1) as the eluent to
recover 9 (19.3 mg, 39%) and give 10 (16.7 mg, 42%) as a
Compound 81,4
To a solution of 7 (50.0 mg, 41.0 mmol) in THF (3.0 ml), a
1.0 M solution of TBAF in THF (123 ml, 0.123 mmol) was
1
colourless powder, mp 83–858C; FAB-MS 933 (Mþ); H

Supramolecular Chemistry
151
NMR (500 MHz) d 0.95–1.08 (m, 14H, CH(CH3)2), 1.04
(s, 9H, C(CH3)3), 1.08–1.14 (m, 14H, CH(CH3)2), 1.15 (s,
9H, C(CH3)3), 1.20 (s, 9H, C(CH3)3), 1.29 (s, 9H,
C(CH3)3), 6.47 (d, 1H, J ¼ 2.4 Hz, ArH), 6.71 (s, 1H, OH),
6.81 (s, 1H, OH), 6.82 (d, 1H, J ¼ 8.5 Hz, ArH), 6.95 (d,
1H, J ¼ 8.5 Hz, ArH), 7.10 (d, 1H, J ¼ 2.3 Hz, ArH), 7.11
(dd, 1H, J ¼ 8.4, 2.4 Hz, ArH), 7.20 (d, 1H, J ¼ 2.4 Hz,
ArH), 7.29 (d, 1H, J ¼ 2.4 Hz, ArH), 7.32 (d, 1H,
J ¼ 2.3 Hz, ArH), 7.35 (dd, 1H, J ¼ 8.5, 2.4 Hz, ArH),
7.57 (d, 1H, J ¼ 2.4 Hz, ArH); 13C NMR (125 MHz) d
13.6, 14.2, 17.4, 17.4, 17.5, 31.0, 31.2, 31.3, 31.4, 34.2,
34.2, 34.3, 115.0, 116.2, 116.3, 120.7, 121.6, 124.4, 125.0,
125.3, 126.2, 127.1, 129.0, 129.2, 130.1, 131.2, 132.4,
133.4, 144.0, 144.8, 145.3, 145.3, 149.8, 151.2, 152.8,
155.0; IR (KBr) 3432, 2962, 1487, 1266, 931 cm21. Anal.
Calcd for C52H76O5S3Si2: C, 66.90; H, 8.21. Found: C,
66.55; H, 8.24.
into water and extracted with CH2Cl2 (10 ml £3).
The organic layer was dried over MgSO4 and evaporated
to give a residue, which was chromatographed on silica gel
with CHCl3–hexane (1:1) as the eluent to give 81,2
(191 mg, 96%) as a colourless powder, mp 104–1058C;
1
FAB-MS 954 (Mþ); H NMR (500 MHz) d 0.98 (s, 9H,
C(CH3)3), 1.15 (s, 9H, C(CH3)3), 1.25 (s, 9H, C(CH3)3),
1.29 (s, 9H, C(CH3)3), 6.57 (s, 1H, OH), 6.74 (d, 1H,
J ¼ 2.3 Hz, ArH), 6.89 (s, 1H, OH), 6.95 (d, 1H,
J ¼ 8.6 Hz, ArH), 7.05 (d, 1H, J ¼ 2.3 Hz, ArH), 7.08
(d, 1H, J ¼ 2.3 Hz, ArH), 7.26 (d, 1H, J ¼ 9.3 Hz, ArH),
7.36 (dd, 1H, J ¼ 8.6, 2.3 Hz, ArH), 7.38–7.43 (m, 3H,
ArH), 7.54 (d, 1H, J ¼ 2.4 Hz, ArH); 13C NMR (125 MHz)
d 30.6, 31.1, 31.1, 31.4, 34.2, 34.3, 34.8, 34.9, 114,6,
115.1, 115.9, 117.3, 119.9, 121.7, 122.7, 123.4, 127.1,
127.3, 129.2, 129.5, 129.6, 130.5, 131.4, 132.1, 132.6,
133.4, 143.0, 144.2, 145.0, 146.9, 152.4, 152.5, 155.7,
155.0; IR (KBr) 3433, 2965, 1210 cm21. Anal. Calcd for
C42H48F6O8S5: C, 52.81; H, 5.07. Found: C, 52.91;
H, 5.15.
Compound 11
A solution of 10 (235 mg, 0.252 mmol) and pyridine
(122 ml, 1.01 mmol) in CH2Cl2 (10 ml) was stirred at room
temperature for 30 min. To the mixture, triflic anhydride
(165 ml, 1.01 mmol) was added at 08C and the resulting
mixture was stirred at this temperature for 2 h. After being
quenched with 2 M HCl (10 ml), the mixture was poured
into water and extracted with CH2Cl2 (5.0 ml £3).
The organic layer was dried over MgSO4 and evaporated
to leave a residue, which was chromatographed on silica
gel with CHCl3–hexane (1:1) as the eluent to give 11
(280 mg, 93%) as a colourless powder, mp 84–858C;
FAB-MS 1197 ([M þ 1]þ); 1H NMR (400 MHz) d
0.78–1.00 (m, 14H, CH(CH3)2), 1.06 (s, 9H, C(CH3)3),
1.06–1.16 (m, 14H, CH(CH3)2), 1.18 (s, 9H, C(CH3)3),
1.19 (s, 9H, C(CH3)3), 1.24 (s, 9H, C(CH3)3), 6.83 (d, 1H,
J ¼ 8.5 Hz, ArH), 7.06 (d, 1H, J ¼ 2.4 Hz, ArH), 7.09 (d,
1H, J ¼ 2.4 Hz, ArH), 7.10 (dd, 1H, J ¼ 8.5, 2.4 Hz, ArH),
7.17 (d, 1H, J ¼ 2.4 Hz, ArH), 7.20 (d, 1H, J ¼ 2.4 Hz,
ArH), 7.25 (d, 1H, J ¼ 8.0 Hz, ArH), 7.38 (dd, 1H,
J ¼ 2.4, 8.7 Hz, ArH), 7.45 (d, 1H, J ¼ 2.4 Hz, ArH), 7.53
(d, 1H, J ¼ 2.4 Hz, ArH); 13C (100 MHz) d 13.7, 13.9,
17.2, 17.3, 17.4, 17.6, 30.7, 31.1, 31.2, 31.3, 34.2, 34.3,
37.8, 34.9, 117.0, 120.2, 120.8, 121.6, 123.4, 124.8, 125.3,
125.6, 126.3, 126.9, 127.8, 128.9, 129.2, 129.4, 130.0,
130.3, 131.8, 131.9, 133.9, 144.6, 145.3, 145.4, 146.8,
151.1, 152.1, 152.5, 152.7; IR (KBr) 2964, 1426, 1211,
859 cm21. HRMS Calcd for C54H74F6O9S5Si2Na:
1219.3271. Found: 1219.3263.
Compound 121,2
The mixture of Ph2P(O)H (143 mg, 0.706 mmol),
Pd(OAc)2 (16.7 mg, 74.4 mmol), dppb (31.7 mg,
i
74.4 mmol) and Pr2EtN (237 ml, 1.41 mmol) in DMSO
(5 ml) was stirred at 1208C for 30 min. To the mixture, a
solution of 81,2 (177 mg, 0.186 mmol) in DMSO (3 ml)
was added and the resulting mixture was stirred at 1208C
for 2 h. After being quenched with 2 M HCl (5 ml), the
mixture was poured into water and extracted with CHCl3
(7 ml £3) and washed with water (10 ml £3). The organic
layer was dried over MgSO4 and evaporated to give a
residue, which was chromatographed on silica gel with
AcOEt as the eluent to give 121,2 (86.3 mg, 44%) as a
colourless powder, mp 1418C (decomp.); FAB-MS 1060
([M þ 1]þ); 1H NMR (400 MHz) d 0.88 (s, 9H, C(CH3)3),
1.12 (s, 9H, C(CH3)3), 1.21 (s, 9H, C(CH3)3), 1.27 (s, 9H,
C(CH3)3), 6.39 (dd, 1H, J ¼ 2.4, 1.2 Hz, ArH), 6.89 (d,
1H, J ¼ 1.8 Hz, ArH), 6.91 (d, 1H, J ¼ 6.9 Hz, ArH), 7.06
(dd, 1H, J ¼ 2.4, 1.1 Hz, ArH), 7.28–7.37 (m, 12H, ArH),
7.40–7.48 (m, 5H, ArH), 7.52–7.59 (m, 5H, ArH), 7.59–
7.67 (m, 4H, ArH); 13C (100 MHz) d 16.4, 17.1, 17.3, 17.5,
20.1, 20.2, 20.8, 21.1, 101.1, 103.2, 106.0, 109.5, 114.4 (d,
J ¼ 12.1 Hz), 111.0 (d, J ¼ 11.9 Hz), 114.5 (d,
J ¼ 12.0 Hz), 114.6 (d, J ¼ 12.6 Hz), 114.7, 115.0, 116.6
(d, J ¼ 12.8 Hz), 117.5 (d, J ¼ 2.8 Hz), 117.9 (d,
J ¼ 2.8 Hz), 117.7, 118.0, 118.1 (d, J ¼ 13.1 Hz), 118.2,
118.2, 118.3, 118.5, 119.8, 121.1 (d, J ¼ 10.5 Hz), 128.8,
129.5 (d, J ¼ 10.0 Hz), 129.8, 130.1 (d, J ¼ 6.1 Hz),
140.7, 140.7, 141.7, 142.8 (d, J ¼ 2.6 Hz); IR (KBr) 3056,
2963, 1184 cm21. HRMS Calcd for C64H68O4P2S3Na:
1081.3647. Found: 1081.3641.
Compound 81,2
To a solution of 11 (250 mg, 0.209 mmol) in THF (10 ml),
TBAF (209 ml, 0.209 mmol) was added and the mixture
was stirred at room temperature for 15 min. After being
quenched with 2 M HCl (5.0 ml), the mixture was poured

152
Y. Akahira et al.
134.4, 140.1 (d, J ¼ 9.0 Hz), 140.4 (d, J ¼ 6.7 Hz),
Compound 51,2
To a solution of 121,2 (90.0 mg, 85.0 mmol) and Et3N
(237 ml, 0.170 mmol) in toluene (10 ml), HSiCl3 (172 ml,
0.170 mmol) was added at 08C and the mixture was
refluxed for 2 h. After the reaction was quenched with
saturated aqueous NaHCO3 (5 ml), the resulting precipi-
tate was filtered off and the filtrate was poured into water
and extracted with CHCl3 (7 ml £3). The organic layer
was dried over MgSO4 and evaporated to give a residue,
which was chromatographed on silica gel with CHCl3–
hexane (1:1) as the eluent to give 51,2 (29.0 mg, 32%) as a
colourless powder, mp 99–1018C; FAB-MS 1028
([M þ 1]þ); 1H NMR (400 MHz) d 0.90 (s, 9H,
C(CH3)3), 1.13 (s, 9H, C(CH3)3), 1.20 (s, 9H, C(CH3)3),
1.27 (s, 9H, C(CH3)3), 6.58 (t, 1H, J ¼ 1.2 Hz, ArH),
6.70–6.75 (m, 3H, ArH), 6.93 (d, 1H, J ¼ 6.8 Hz, ArH),
7.02 (d, 1H, J ¼ 1.7 Hz, ArH), 7.12–7.20 (m, 6H, ArH),
7.24 (d, 1H, J ¼ 1.2 Hz, ArH), 7.26–7.32 (m, 11H, ArH),
7.33 (dd, 1H, J ¼ 6.8, 1.8 Hz, ArH), 7.43–7.49 (m, 4H,
ArH), 7.53 (d, 1H, J ¼ 1.8 Hz, ArH); 13C (100 MHz) d
30.5, 31.1, 31.2, 31.5, 34.2, 34.3, 34.7, 34.7, 115.0, 116.4,
121.8, 123.1 (d, J ¼ 3.5 Hz), 125.4, 125.8 (d, J ¼ 3.5 Hz),
128.1, 128.3 (d, J ¼ 12.7 Hz), 128.3, 128.5, 129.0, 129.9,
131.4 (d, J ¼ 2.3 Hz), 132.2 (d, J ¼ 18.4 Hz), 132.7,
133.4, 133.5, 133.9 (d, J ¼ 20.0 Hz), 134.5 (d,
J ¼ 10.9 Hz), 137.2 (d, J ¼ 11.7 Hz), 138.4 (d,
J ¼ 8.8 Hz), 143.9, 144.5, 145.0, 145.1, 148.4, 152.6,
152.9, 153.7, 155.2; IR (KBr) 3406, 2962 cm21. HRMS
Calcd for C64H68O2P2S3Na: 1049.3749. Found:
1049.3754.
142.1, 142.4, 145.2 (d, J ¼ 7.0 Hz), 154.6, 156.4 (d,
J ¼ 2.1 Hz), 156.1; IR (KBr) 3057, 2963, 1185 cm21
.
HRMS Calcd for C64H68O4P2S3Na: 1081.3647. Found:
1081.3642.
Compound 51,3
This compound was prepared by the same procedure as
used for the preparation of 51,2. Starting from 121,3
(92.2 mg), 51,3 (46.9 mg, 52%) was obtained as a
colourless powder, mp 1188C (decomp.); FAB-MS 1028
([M þ 1]þ); 1H NMR (400 MHz) d 0.85 (s, 9H, C(CH3)3),
1.16 (s, 9H, C(CH3)3), 1.18 (s, 9H, C(CH3)3), 1.27 (s, 9H,
C(CH3)3), 5.95 (s, 1H, OH), 6.58 (t, 1H, J ¼ 1.8 Hz, ArH),
6.68–6.76 (m, 2H, ArH), 6.90 (d, 1H, J ¼ 8.6 Hz, ArH),
7.00 (s, 1H, OH), 7.15 (dd, 1H, J ¼ 1.8, 8.1 Hz, ArH), 7.18
(d, 1H, J ¼ 2.3 Hz, ArH), 7.27–7.40 (m, 20H, ArH),
7.54–7.63 (m, 4H, ArH); 13C (100 MHz) d 30.5, 31.0,
31.5, 31.6, 34.2, 34.2, 34.7, 34.7, 115.1, 116.9 (d,
J ¼ 8.7 Hz), 119.5 (d, J ¼ 9.5 Hz), 121.0 (d, J ¼ 5.1 Hz),
122.7 (d, J ¼ 3.0 Hz), 124.3 (d, J ¼ 3.6 Hz), 126.1, 127.4,
127.5, 128.2, 128.5 (d, J ¼ 6.3 Hz), 128.6 (d, J ¼ 7.2 Hz),
128.8, 129.2, 132.2 (d, J ¼ 18.4 Hz), 133.3, 132.9, 133.9
(d, J ¼ 19.6 Hz), 134.0, 134.3, 134.4, 135.9 (d,
J ¼ 6.5 Hz), 136.5 (d, J ¼ 8.8 Hz), 139.6, 139.9, 143.8,
144.0, 146.2 (d, J ¼ 5.1 Hz), 146.3 (d, J ¼ 9.5 Hz), 152.8,
153.8 (d, J ¼ 8.0 Hz), 154.9; IR (KBr) 3420, 2962 cm21
.
HRMS Calcd for C64H68O2P2S3Na: 1049.3749. Found:
1049.3747.
Compound 121,4
Compound 121,3
This compound was prepared by the same procedure as
used for the preparation of 121,3. Starting from 81,4
(250 mg), 121,4 (178 mg, 64%) was obtained as a
colourless powder, mp 183–1858C; FAB-MS 1059
This compound was prepared by a similar procedure to
that used for the preparation of 121,2. Starting from 81,3
(434 mg), 121,3 (134 mg, 28%) was obtained as a
colourless powder, after column chromatography with
AcOEt–hexane (2:1) as the eluent, mp 1538C (decomp.);
1
(Mþ); H NMR (400 MHz) d 1.12 (s, 18H, C(CH3)3),
1
FAB-MS 1060 ([M þ 1]þ); H NMR (400 MHz) d 0.93
1.18 (s, 18H, C(CH3)3), 6.97 (dd, 2H, J ¼ 12.7, 8.1 Hz,
ArH), 7.11 (d, 2H, J ¼ 2.4 Hz, ArH), 7.18 (dt, 2H, J ¼ 8.1,
1.9 Hz, ArH), 7.36 (d, 2H, J ¼ 2.4 Hz, ArH), 7.43–7.59
(m, 14H, ArH), 7.68–7.78 (m, 8H, ArH), 10.0 (br, 2H,
OH); 13C (100 MHz) d 30.8, 31.3, 34.0, 35.0, 119.1, 121.7,
124.4 (d, J ¼ 11.9 Hz), 128.6 (d, J ¼ 12.3 Hz), 123.0,
131.2 (d, J ¼ 36.5 Hz), 131.8, 131.8, 131.8, 132.0 (d,
J ¼ 9.9 Hz), 132.7 (d, J ¼ 30.2 Hz), 133.7 (d,
J ¼ 13.3 Hz), 140.4 (d, J ¼ 6.9 Hz), 142.3, 155.0, 156.2
(d, J ¼ 2.2 Hz); IR (KBr) 3407, 2962, 1186 cm21. HRMS
Calcd for C64H68O4P2S3Na: 1081.3647. Found:
1081.3646.
(s, 9H, C(CH3)3), 1.15 (s, 9H, C(CH3)3), 1.19 (s, 9H,
C(CH3)3), 1.28 (s, 9H, C(CH3)3), 6.66 (d, 1H,
J ¼ 2.3 Hz, ArH), 6.86 (d, 1H, J ¼ 8.6 Hz, ArH), 6.86
(dd, 1H, J ¼ 12.8, 7.9 Hz, ArH), 7.03 (dd, 1H, J ¼ 3.6,
1.8 Hz, ArH), 7.19 (dt, 1H, J ¼ 8.1, 2.0 Hz, ArH), 7.26–
7.36 (m, 8H, ArH), 7.42 (d, 1H, J ¼ 2.3 Hz, ArH), 7.48–
7.60 (m, 7H, ArH), 7.62 (dd, 1H, J ¼ 3.4, 1.8 Hz, ArH),
7.66–7.81 (m, 8H, ArH), 9.54 (s, 1H, OH), 10.57 (s, 1H,
OH); 13C (100 MHz) d 30.4, 30.4, 30.8, 31.4, 34.0, 34.0,
34.7, 35.0, 116.3, 118.9 (d, J ¼ 12.5 Hz), 124.0, 124.7 (d,
J ¼ 11.9 Hz), 128.3 (d, J ¼ 12.6 Hz), 128.7 (d,
J ¼ 11.4 Hz), 128.7, 129.7 (d, J ¼ 8.2 Hz), 130.2 (d,
J ¼ 45.7 Hz), 130.2, 131.1 (d, J ¼ 8.0 Hz), 131.2 (d,
J ¼ 46.3 Hz), 131.5 (d, J ¼ 2.7 Hz), 131.6, 131.9 (d,
J ¼ 10.6 Hz), 132.0, 132.2 (d, J ¼ 10.5 Hz), 132.6, 132.8
(d, J ¼ 7.7 Hz), 133.3, 133.5 (d, J ¼ 8.8 Hz), 133.9,
Compound 51,4
This compound was prepared by the same procedure as
used for the preparation of 51,2. Starting from 121,4

Supramolecular Chemistry
153
(400 mg, 0.377 mmol), 51,4 (315 mg, 82%) was obtained as
a colourless powder, mp 117–1198C; FAB-MS 1027
(Mþ); 1H NMR (400 MHz) d 1.15 (s, 18H, C(CH3)3), 1.16
(s, 18H, C(CH3)3), 6.72 (dd, 2H, J ¼ 8.1, 3.5 Hz, ArH),
7.15 (dd, 2H, J ¼ 8.1, 1.8 Hz, ArH), 7.20 (d, 2H,
J ¼ 2.3 Hz, ArH), 7.26–7.41 (m, 22H, ArH), 7.47 (d,
2H, J ¼ 2.1 Hz, ArH); 13C (100 MHz) d 31.0, 31.3, 34.2,
34.7, 119.6, 120.2 (d, J ¼ 5.1 Hz), 120.1, 128.6 (d,
J ¼ 7.2 Hz), 128.9, 131.3, 132.0, 133.2, 133.8 (d,
J ¼ 19.6 Hz), 135.5 (d, J ¼ 5.8 Hz), 136.3 (d,
J ¼ 8.1 Hz), 139.7, 134.0, 143.8, 152.9, 153.4; IR (KBr)
3406, 2962 cm21. HRMS Calcd for C64H68O2P2S3Na:
1049.3749. Found: 1049.3752.
J ¼ 2.3 Hz, ArH), 7.04–7.07 (m, 2H, ArH), 7.14–7.17 (m,
2H, ArH), 7.31 (d, 1H, J ¼ 2.3 Hz, ArH), 7.35 (dd, 1H,
J ¼ 2.3, 8.4 Hz, ArH), 7.40 (d, 1H, J ¼ 2.3 Hz, ArH), 7.44
(d, 1H, J ¼ 2.3 Hz, ArH), 7.89 (d, 1H, J ¼ 8.4 Hz, ArH); 13C
NMR (100MHz, acetone-d7) d 20.5, 20.8, 31.1, 31.2, 31.5,
31.7, 35.4, 35.6, 35.8, 35.8, 52.5, 52.8, 123.2, 124.1, 126.2,
126.7, 127.8, 129.1, 129.1, 129.7, 131.5, 131.5, 132.2, 132.3,
133.8, 134.3, 135.7, 136.4, 141.2, 141.7, 144.5, 149.7, 150.9,
151.7, 155.0, 156.7, 167.1, 167.7, 169.1, 169.5; IR (KBr)
1769, 1716cm21. Anal. Calcd for C48H58O8S3: C, 67.10; H,
6.80. Found: C, 67.32; H, 6.84.
Compound 61,3
Compound 141,3 (331 mg, 0.385 mmol) was boiled with
KOH (2.16 g, 38.5 mmol) in EtOH–H2O (10:1; 22.0 ml)
for 3 days. The mixture was cooled in an ice water bath
and quenched with 2 M HCl (50 ml). The resulting
precipitate was collected by filtration, washed with water
and recrystallised from acetone–hexane to give 61,3
(226 mg, 85%) as a colourless powder, mp 147.2–
148.68C; FAB-MS 769 ([M þ Na]þ); 1H NMR
(400 MHz) d 1.06 (s, 9H, C(CH3)3), 1.19 (s, 9H,
C(CH3)3), 1.20 (s, 9H, C(CH3)3), 1.30 (s, 9H, C(CH3)3),
6.85 (d, 1H, J ¼ 1.7 Hz, ArH), 6.97 (d, 1H, J ¼ 8.6 Hz,
ArH), 7.25–7.27 (m, 3H, ArH), 7.36–7.41 (m, 3H, ArH),
7.56 (d, 1H, J ¼ 2.5 Hz, ArH), 7.87 (d, 1H, J ¼ 8.2 Hz,
ArH); 13C NMR (100 MHz) d 30.4, 30.6, 31.2, 31.4, 34.1,
34.3, 34.8, 35.0, 115.3, 115.7, 117.2, 119.6, 122.4, 123.1,
124.3, 124.5, 126.4, 128.9, 129.6, 132.2, 133.8, 134.7,
135.3, 135.8, 137.2, 140.9, 144.2, 144.9, 154.3, 155.3,
Compound 131,3
To a solution of 81,3 (413 mg, 0.433 mmol) in CH2Cl2
(10 ml), pyridine (599 mg, 7.62 mmol) and acetic anhy-
dride (292 mg, 2.86 mmol) were added and the mixture
was stirred for 2 h at room temperature. After being
quenched with 2 M HCl (10 ml), the mixture was extracted
with CHCl3 (20 ml £3). The organic layer was washed
with water (20 ml £3) and evaporated to give 131,3
(437 mg, 97%) as an oil, FAB-MS 1038 (Mþ); H NMR
1
(400 MHz) d 1.04 (s, 9H, C(CH3)3), 1.14 (s, 9H, C(CH3)3),
1.20 (s, 9H, C(CH3)3), 1.26 (s, 9H, C(CH3)3), 2.22 (s, 3H,
OCOCH3), 2.58 (s, 3H, OCOCH3), 6.97 (d, 1H,
J ¼ 2.4 Hz, ArH), 7.08–7.11 (m, 1H, ArH), 7.20–7.23
(m, 2H, ArH), 7.29–7.34 (m, 4H, ArH), 7.39–742 (m, 2H,
ArH); 13C NMR (100 MHz, acetone-d7) d 20.5, 20.7, 31.0,
31.3, 31.4, 31.6, 35.4, 35.5, 35.6, 35.6, 118.4, 120.9, 122.7,
124.4, 125.8, 128.1, 128.6, 129.1, 129.3, 130.6, 130.9,
131.9, 132.0, 132.1, 132.5, 132.7, 144.8, 147.3, 149.2,
150.2, 151.3, 151.9, 153.4, 153.7, 169.0, 169.5; IR (KBr)
155.3, 157.0, 171.7, 171.9; IR (KBr) 3421, 1690 cm21
.
Anal. Calcd for C42H50O6S3: C, 67.53; H, 6.75. Found: C,
67.28; H, 6.71.
1772, 1425, 1209, 1193 cm21
. Anal. Calcd for
C46H52F6O10S5: C, 53.16; H, 5.04. Found: C, 53.44;
H, 4.86.
Compound 131,4
This compound was prepared by the same procedure as
used for the preparation of 131,3. Starting from 81,4
(875 mg, 0.917 mmol), 131,4 (784 mg, 82%) was obtained
as a colourless powder, mp 155.8–157.58C; FAB-MS
1039 (Mþ); 1H NMR (400 MHz) d 1.13 (s, 18H,
C(CH3)3), 1.22 (s, 18H, C(CH3)3), 2.25 (s, 6H,
OCOCH3), 7.19–7.24 (m, 4H, ArH), 7.22 (dd, 2H,
J ¼ 6.7, 1.4 Hz, ArH), 7.29–7.33 (m, 4H, ArH); 13C NMR
(100 MHz) d 20.5, 31.1, 31.2, 34.9, 35.0, 121.4, 126.2,
127.5, 129.0, 130.4, 130.6, 130.8, 146.2, 147.7, 150.6,
Compound 141,3
To a solution of 131,3 (400 mg, 0.385 mmol) in DMSO–
MeOH (2:1; 24 ml), Pd(OAc)2 (17.2 mg, 77.0 mmol), dppb
i
(65.6 mg, 0.154 mmol) and Pr2NEt (438 mg, 3.38 mmol)
were added and the resulting mixture was stirred under 1
atm of CO atmosphere at 708C for 18 h. After cooling, the
mixture was quenched with 2 M HCl (20 ml), poured into
water (50 ml) and extracted with CHCl3 (30 ml£3). The
organic layer was dried over MgSO4 and evaporated to
give a residue, which was chromatographed on silica gel
with hexane–AcOEt (2:1) as the eluent to give 141,3
152.3, 168.5; IR (KBr) 1773, 1425, 1214, 1191 cm21
.
Anal. Calcd for C46H52F6O10S5: C, 53.16; H, 5.04. Found:
C, 53.25; H, 5.12.
1
(273 mg, 82%) as an oil, FAB-MS 859 ([M þ 1]þ); H
NMR (400 MHz) d 1.08 (s, 9H, C(CH3)3), 1.13 (s, 9H,
C(CH3)3), 1.17 (s, 9H, C(CH3)3), 1.26 (s, 9H, C(CH3)3),
2.20 (s, 3H, OCOCH3), 2.23 (s, 3H, OCOCH3), 3.88 (s,
3H, CO2CH3), 3.93 (s, 3H, CO2CH3), 6.97 (d, 1H,
Compound 141,4
This compound was prepared by a similar procedure to
that used for the preparation of 141,3. Starting from 131,4

154
Y. Akahira et al.
(400 mg), 141,4 (267 mg, 80%) was obtained as an oil,
after column chromatography with hexane–AcOEt (2:1)
R1 ¼ 0.0753, wR2 ¼ 0.2154 (observed), R1 ¼ 0.903,
wR2 ¼ 0.2339 (all data).
1
as the eluent, FAB-MS 858 (Mþ); H NMR (400 MHz) d
Crystallographic data for 61,4·(C6H6)1.5·(C6H12)1.5
:
ꢀ
˚
1.13 (s, 18H, C(CH3)3), 1.18 (s, 18H, C(CH3)3), 2.20 (s,
6H, OCOCH3), 3.92 (s, 6H, CO2CH3), 6.99 (d, 2H,
J ¼ 1.5 Hz, ArH), 7.16 (dd, 2H, J ¼ 6.6, 1.5 Hz, ArH),
7.34 (d, 2H, J ¼ 1.9 Hz, ArH), 7.45 (d, 2H, J ¼ 1.9 Hz,
ArH), 7.89 (d, 2H, J ¼ 6.6 Hz, ArH); 13C NMR
(100 MHz) d (ppm); 20.6, 30.9, 31.3, 34.9, 35.2, 52.3,
122.1, 124.8, 126.0, 127.9, 129.6, 130.8, 130.1, 133.5,
141.4, 149.6, 150.7, 156.0, 167.0, 168.7; IR (KBr) 1715,
1768 cm21. Anal. Calcd for C48H58O8S3: C, 67.10; H,
6.80. Found: C, 67.22; H, 6.83.
C54H65O6S3, fw ¼ 906.24, triclinic, P1, a ¼ 13.0529 (18)
˚
˚
A, b ¼ 14.404 (2) A, c ¼ 14.761 (2) A, a ¼ 93.880 (2)8,
3
˚
b ¼ 96.636 (2)8, g ¼ 100.681 (2)8, V ¼ 2697.6 (7) A ,
Z ¼ 2, T ¼ 223 (2) K, 30,252 reflections measured, 12,024
independent reflections, 6960 reflections were observed
(I . 2s(I)), R1 ¼ 0.0881, wR2 ¼ 0.2518 (observed),
R1 ¼ 0.1398, wR2 ¼ 0.3036 (all data).
References
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Compound 61,4
This compound was prepared by a similar procedure to
that used for the preparation of 61,3. Starting from 141,4
(267 mg), 61,4 (232 mg, quant.) was obtained as a
colourless powder, after recrystallisation from benzene–
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J ¼ 1.4 Hz, ArH), 7.20 (dd, 2H, J ¼ 1.4, 6.7 Hz, ArH),
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˚
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:
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C
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˚ ˚ ˚
˚
a ¼ 20.881 (3) A, b ¼ 9.5748 (12) A, c ¼ 22.624 (3) A,
3
b ¼ 91.327 (2)8, V ¼ 4521.9 (10) A , Z ¼ 4, T ¼ 173 (2)
K, 24,367 reflections measured, 10,108 independent
reflections, 8081 reflections were observed (I . 2s(I)),

Supramolecular Chemistry
155
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