Tubular structures bearing channels in organic crystals composed of adamantane-based macrocycles

Article abstract of DOI:10.1016/j.tet.2014.02.006

Five macrocyclic molecules (1-5) were efficiently synthesized from the dimerization and trimerization of di-substituted adamantane derivatives, which were composed of three different aromatic units and two different linker groups. Three single-crystals were obtained from these macrocyclic molecules, including a set of pseudopolymorphs (3a and 3b) of macrocycle 3 and another macrocycle 5 (5a). Single crystal X-ray analysis revealed that the three monocyclic compounds were rectangular or square in shape with solvent molecules in the cavity. Macrocycle 3 in 3a formed stacks to produce tubular structures with channels that assembled into three-dimensional networks through CH/π interactions.

Full text of DOI:10.1016/j.tet.2014.02.006

Tetrahedron 70 (2014) 2576e2581
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Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Tubular structures bearing channels in organic crystals composed
of adamantane-based macrocycles
,
a
a
a
Masahide Tominaga a , Hiroyuki Ukai , Kosuke Katagiri , Kazuaki Ohara ,
*
Kentaro Yamaguchi a, Isao Azumaya b
,
*
a Faculty of Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, 1314-1 Shido, Sanuki, Kagawa 769-2193, Japan
b Faculty of Pharmaceutical Sciences, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 22 July 2013
Received in revised form 1 February 2014
Accepted 4 February 2014
Available online 2 March 2014
Five macrocyclic molecules (1e5) were efficiently synthesized from the dimerization and trimerization of
di-substituted adamantane derivatives, which were composed of three different aromatic units and two
different linker groups. Three single-crystals were obtained from these macrocyclic molecules, including
a set of pseudopolymorphs (3a and 3b) of macrocycle 3 and another macrocycle 5 (5a). Single crystal X-
ray analysis revealed that the three monocyclic compounds were rectangular or square in shape with
solvent molecules in the cavity. Macrocycle 3 in 3a formed stacks to produce tubular structures with
Keywords:
channels that assembled into three-dimensional networks through CH/
p interactions.
Macrocycle
Adamantane
Channel
Ó 2014 Elsevier Ltd. All rights reserved.
Tubular structure
CH/
p interaction
1. Introduction
tubular structures from macrocycle compounds without hydrogen-
bonding functional groups through weaker interaction, including
During the course of the last three decades, significant research
efforts have been directed toward the development of molecular-
based tubular structures, with these materials being used in
a number of different areas including ion sensors and molecular
sieves, as well as heterogeneous catalysis in materials science and
biochemistry.1,2 The development of tubular assemblies can be
achieved by the self-assembly of a wide variety of different organic
molecules through weak noncovalent interactions, such as hydro-
CH/p and halogen/halogen interactions, however, are scarce. We
recently reported the synthesis of an adamantane-based macro-
cycle, where two di-substituted adamantane molecules bearing
2,6-dimethoxyphenyl moieties were covalently linked to each
other through 1,6-dioxahexa-2,4-diyne spacers with relatively rigid
and directional properties.11 Unfortunately, however, this macro-
cycle afforded a columnar structure without channels through CH/
p
and CH/O interactions in the solid state (Fig. S1). We have sub-
gen bonding and
p
/
p
interactions. As a general method, macrocy-
sequently designed a variety of different adamantane-based mac-
rocycles using novel aromatic units and linkers to construct tubular
structures in solid crystalline materials. In this paper, we report the
facial synthesis of five adamantane-based macrocycles of different
shapes and sizes. Single crystals X-ray analysis revealed that mac-
rocycles exhibited nearly rectangular or square shapes when guest
molecules were present in the cavity. Tubular structures with 1D
channels were also constructed from the stacking of these macro-
clic frameworks containing a central cavity3,4 can be directly
stacked into tubular architectures along one axis to form one-
dimensional (1D) channels.5e7 Ghadiri et al. demonstrated that
peptide-based macrocycles can be aligned into tubular structures
via the formation of hydrogen bonds from the amide groups.8
Shimizu et al. described the construction of tubular architectures
built from macrocycles bearing urea groups.9 These tubular as-
semblies based on macrocycles exhibited a range of interesting
practical applications, including gas adsorption and selective
chemical transformation.10 Reports pertaining to the assembly of
cycles through CH/p interactions in the solid state.
2. Results and discussion
2.1. Syntheses
* Corresponding authors. Tel.: þ81 87 899 7432; fax: þ81 87 894 0181 (M.T.); tel./
fax: þ81 47 472 1589 (I.A.); e-mail addresses: tominagam@kph.bunri-u.ac.jp (M.
Tominaga), isao.azumaya@phar.toho-u.ac.jp (I. Azumaya).
The adamantane-based macrocycles discussed in this study
were derived from three different macrocycles bearing one of three
0040-4020/$ e see front matter Ó 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2014.02.006

M. Tominaga et al. / Tetrahedron 70 (2014) 2576e2581
2577
different aromatic units as well as two different linker groups
macrocyclic structures of 1e5 were examined from their 1H and 13
C
NMR spectra, which showed only one signal for the methine proton
and carbon of the adamantane moieties, respectively. The peaks
corresponding to the aromatic protons supported the notion that
each aromatic ring could rotate freely within the macrocyclic
framework at room temperature.
(1e5). In two of these macrocycles (1e4), phenyl or 2,6-
dimethylphenyl groups were selected as the aromatic units to re-
place the 2,6-dimethoxyphenyl units used in our previously re-
ported adamantane-based macrocycles. In the other type of
macrocycle (5), a flexible 1,4-dioxabutane linker was used instead
of the 1,6-dioxahexa-2,4-diyne spacer used in our previous report,
although 2,6-dimethoxyphenyl units were used as the aromatic
units. A variety of different macrocyclic frameworks were then
readily synthesized in two steps from the starting materials as
shown in Schemes 1 and 2. Briefly, two different binary molecules
based on adamantane bearing the required aromatic units (6 and 7)
were treated with propargyl bromide to afford the corresponding
di-substituted adamantanes (8 and 9) in high yields. These com-
pounds were then subjected to a Hay acetylene coupling reaction
under high-dilution conditions to provide the dimerized macro-
cycle 1 (42%) and trimerized macrocycle 2 (10%) from 8, and the
dimerized macrocycle 3 (54%) and trimerized macrocycle 4 (17%)
from 9. The reaction of the diaryladamantane derivative possessing
2,6-dimethoxyphenol units 10 and aryl bromide gave the di-
substituted adamantane 11 in 88% yield. The macrocyclization of
this material using Grubbs second-generation catalyst followed by
hydrogenation provided the dimerized macrocycle 5 (25%). The
structures of macrocycles 1e5 were confirmed by 1H and 13C NMR
spectroscopy, elemental analysis, and fast atom bombardment
(FAB) mass spectroscopy. The results of these characterizations
were in full agreement with the proposed structures. The
2.2. Crystals structures
Single crystals of macrocycle 3 (3a) were obtained from the
diffusion of hexane vapor into a chloroform solution of 3. The
resulting crystal 3a crystallized in the triclinic system with space
group Pꢀ1, and contained one molecule of 3 in its unit cell together
with two molecules of chloroform. X-ray crystallographic analysis
showed that the macrocyclic structure of 3 was rectangular in
shape, and that the distances between the centroids of the op-
ꢀ
posing rings were 14.82 and 10.64 A, respectively (Fig. 1a and b).
Two chloroform molecules were included in the cavity of macro-
cycle 3. Examination of the crystal packing indicated that individual
molecules of macrocycle 3 had been regularly stacked to form
a tubular structure directly along the a axis of the unit cell. These
tubular structures were formed through CH/p interactions between
the methylene protons of the adamantane groups and the diethynyl
moieties of the linker units (the distance between the carbon atom
ꢀ
and the center of the diethynyl moieties was 3.82 A). These tubes
were assembled into three-dimensional (3D) networks via in-
termolecular CH/p interactions between the methylene protons of
the linker units and the aromatic rings, with the distances between
the carbon atom and the ring center of the phenyl ring of 3.53 and
ꢀ
3.51 A along the b and c axes, respectively (Fig. 2a and b).
Scheme 1. Synthesis of macrocycles 1e4.
Fig. 1. The thermal ellipsoid (a) and space-filling (b) models of macrocycle 3 in crystal
3a. The chloroform molecules have been omitted for clarity.
Single crystals of 3b as a pseudopolymorph for 3a were obtained
from a mixture of macrocycle 3 in tetrahydrofuran and methanol.
Crystal 3b crystallized in the triclinic system with space group Pꢀ1,
and included one molecule of 3 in its unit cell together with two
molecules of tetrahydrofuran. X-ray crystallographic analysis
revealed that the macrocyclic structure of 3 was rectangular in
shape, and that the distances between the centroids of the op-
ꢀ
posing rings were 15.76 and 9.27 A, respectively (Fig. 3a and b). The
macrocycle 3 was found to possess two independent and identical
cavities in the macrocyclic framework, with the tetrahydrofuran
molecules being trapped by intermolecular CH/O interactions be-
tween the methylene protons of the linker units and the oxygen
atom of the tetrahydrofuran guest (the distance between the
Scheme 2. Synthesis of a macrocycle 5.

2578
M. Tominaga et al. / Tetrahedron 70 (2014) 2576e2581
Fig. 4. Packing diagram of crystal 3b. Side view (a) and top view (b) of the network
structure. The neighboring molecules are colored blue. The tetrahydrofuran molecules
have been omitted for clarity.
Fig. 2. Packing diagram of crystal 3a. Side view (a) and top view (b) of the 3D network
structure. The neighboring molecules are colored blue. The chloroform molecules have
been omitted for clarity.
showed that the macrocyclic structure of 5 was square in shape,
and that the distances between the centroids of the opposing rings
ꢀ
were 9.91 and 11.07 A, respectively (Fig. 5a,b). Two chloroform
molecules were accommodated in the cavity of macrocyclic
framework. The packing of macrocycle 5 occurred along each of the
Fig. 3. The thermal ellipsoid (a) and space-filling (b) models of macrocycle 3 in crystal
3b. The tetrahydrofuran molecules have been omitted for clarity.
ꢀ
carbon atom and the oxygen atom was 3.43 A). Examination of the
crystal packing demonstrated that the individual molecules of
macrocycle 3 were aligned into 1D tapes through multiple in-
termolecular CH/O interactions between the methylene protons of
the adamantane units and the oxygen atoms of linker units (the
distance between the carbon atom and the oxygen atom was
ꢀ
3.49 A). These 1D channels were formed directly along the a axis in
Fig. 5. The thermal ellipsoid (a) and space-filling (b) models of macrocycle 5 in crystal
5a. The chloroform molecules have been omitted for clarity.
the crystalline lattices (Fig. 4a and b).
Single crystals of macrocycles 5 (5a) were obtained from the
vapor diffusion of hexane into a chloroform solution of 5. The
resulting crystal 5a crystallized in the triclinic system with space
group Pꢀ1, and included one molecule of 1 in its unit cell as well as
two molecules of chloroform. X-ray crystallographic analysis
three axis, with a channel structure observed along the a axis of the
unit cell (Fig. 6a and b).
The macrocycle 3 was found to exist in a similar rectangle shape
to that observed in our previously reported macrocycle containing

M. Tominaga et al. / Tetrahedron 70 (2014) 2576e2581
2579
as the crystal packing of the component molecules. Crystallographic
analysis of the macrocycles revealed that the macrocyclic frame-
works were rectangle or square in shape with cavities. In crystal 3a,
the individual molecules of macrocycle 3 were arranged into 1D
tubular structures through intermolecular CH/p interactions in the
solid state. These adamantane-based macrocycles therefore repre-
sent useful building blocks for the construction of tubular structures
with channels via CH/
methylene and methine protons to interact with
p
interactions, because they possess multiple
p
-moieties.14 The
selective inclusion properties of these macrocyclic materials toward
small organic molecules and gases are currently being investigated
in our laboratory.
4. Experimental section
4.1. General
1H and 13C NMR spectra were recorded on a Bruker AV-400M
spectrometer at 27 ꢁC using CDCl3 as a solvent and TMS as an in-
ternal reference. Melting points were determined on an ASONE
ATM-01 melting point apparatus and were uncorrected. FAB mass
spectroscopy was performed on a JEOL JMS-700 using an m-
nitrobenzylalcohol matrix. Elemental analyses were performed
with a PerkineElmer 2400 elemental analyzer. IR spectra were
recorded on a Jasco FT/IR-6300 instrument. Column chromatogra-
phy was performed using Wakogel C200, and thin-layer chroma-
tography was carried out on 0.25 mm Merck precoated silica gel
glass plates. Gel permeation Chromatography was performed using
recycling preparative HPLC (LC-9204, Japan Analytical Industry Co.,
Ltd.) and a JAIGEL H series column (Japan Analytical Industry Co.,
Ltd.). The three different types of adamantane-based bisphenols 6,
7, and 10 were synthesized using methods previously reported in
the literature.15
Fig. 6. Packing diagram of crystal 5a. Side view (a) and top view (b) of the network
structure. The neighboring molecules are colored blue. The chloroform molecules have
been omitted for clarity.
4.2. 1,3-Bis(4-propargyloxyphenyl)adamantane (8)
A mixture of 1,3-bis(4-hydroxyphenyl)adamantane (1.60 g,
5.00 mmol), propargyl bromide (0.98 mL, 13.0 mmol), and potas-
sium carbonate (1.79 g, 13.0 mmol) in dry DMF (50 mL) was stirred
for 2 days at room temperature under an argon atmosphere. The
reaction mixture was then poured into water and the resulting
mixture was extracted with CHCl3. The extract was washed se-
quentially with H2O and brine before being dried over Na2SO4.
Evaporation of the solvent followed by sequential silica gel column
chromatography (eluent: CHCl3/hexane¼1:1) and gel permeation
chromatography (JAIGEL 1Hþ2H, CHCl3) afford the title compound
as a white solid (1.80 g, 4.55 mmol) in 91% yield. Mp 91e93 ꢁC. FT-IR
(ATR, cmꢀ1): 3256, 2920, 2846, 1577, 1508, 1444, 1215, 1188, 1027,
the dimethoxyphenyl aromatic units, whereas macrocycle
exhibited a square shape. Tubular structures were generated from
the stacking of macrocycle 3 through CH/ interactions in crystal
5
p
3a. The packing of the macrocycles in crystals 3b and 5a produced
channels in the crystalline lattices of these materials. The specific
weak intermolecular interactions formed along the axes of these
channels to produce the tubular structures were not observed be-
tween the individual macrocycles. Based on these observations of
three single-crystals, it became clear that the aromatic and linker
moieties in the macrocycles played essential roles in not only de-
fining the shapes and sizes of macrocyclic frameworks but also in
determining the network structures in the solid state.12 It is note-
worthy that the pseudopolymorphs 3a and 3b were formed from
different conformations of aromatic units in the 3.13 All four of the
aromatic rings were positioned perpendicular to the plane of the
macrocyclic framework in crystal 3a, whereas two of the four ar-
omatic rings were oriented parallel to the plane of the macrocycle
in crystal 3b. Chloroform molecules in crystal 3a and the tetrahy-
drofuran molecules in crystal 3b were accommodated within the
cavities of the macrocycles. The shapes of macrocycles therefore
originated from differences in the conformation that were induced
by the two different types of structural networks in the solid state.
815, 690. 1H NMR (400 MHz, CDCl3, 27 ꢁC)
d
7.29 (d, J¼8.8 Hz, 4H),
6.91 (d, J¼8.8 Hz, 4H), 4.62 (d, J¼2.4 Hz, 4H), 2.47 (t, J¼2.4 Hz, 2H),
2.27 (s, 2H), 1.95e1.74 (m, 12H). 13C NMR (100 MHz, CDCl3, 27 ꢁC)
d
155.42, 143.77, 125.79, 114.37, 78.78, 75.31, 55.70, 49.26, 42.32,
36.62, 35.75, 29.49. MS (FAB, m/z) calcd for C28H29O2 [MþH]þ
397.21, found 396.9. Anal. Calcd for C28H28O2$0.02CHCl3: C, 84.44;
H, 7.09. Found: C, 84.37; H, 7.15.
4.3. 1,3-Bis(4-propargyloxy-3,5-dimethylphenyl)adamantane
(9)
Compound 9 was synthesized in 89% yield as a white solid in
a manner similar to that described for the preparation of 8. Mp
111e113 ꢁC. FT-IR (ATR, cmꢀ1): 3253, 2903, 2323, 2846, 1565, 1508,
1448, 1211, 1136, 1001, 830, 692. 1H NMR (400 MHz, CDCl3, 27 ꢁC)
3. Conclusion
In conclusion, we have achieved in the design and facial prepa-
ration of five adamantane-based macrocycles composed of different
aromatic units and linker groups, which played essential roles in
defining the shapes and sizes of the macrocyclic frameworks, as well
d
7.00 (s, 4H), 4.45 (d, J¼2.4 Hz, 4H), 2.47 (t, J¼2.4 Hz, 2H), 2.30 (s,
12H), 2.27 (s, 2H), 1.93e1.74 (m, 12H). 13C NMR (100 MHz, CDCl3,
27 ꢁC)
153.20, 146.51, 130.27, 125.29, 79.55, 74.77, 59.71, 49.31,
d

2580
M. Tominaga et al. / Tetrahedron 70 (2014) 2576e2581
42.24, 36.70, 35.83, 29.52, 16.72. MS (FAB, m/z) calcd for C32H37O2
[MþH]þ 453.27, found 453.9. Anal. Calcd for C32H36O2$0.02CHCl3:
C, 84.52; H, 7.98. Found: C, 84.35; H, 8.10.
4.7. Macrocycle 5
A
solution of 1,3-bis(4-allyloxy-3,5-dimethoxyphenyl)ada-
mantane (0.26 g, 0.50 mmol) in dry CH2Cl2 (50 mL) was added to
4.4. Macrocycles 1 and 2
a solution of Grubbs second-generation catalyst (42.4 mg,
0.05 mmol) in dry CH2Cl2 (200 mL) in drop-wise manner with
stirring over 3 h, and the resulting mixture was stirred for 2 days at
room temperature under an argon atmosphere. The solvents were
then removed under reduced pressure, and the resulting residue
purified by silica gel column chromatography (eluent: CHCl3). A 1,4-
dioxane solution (30 mL) of the resulting purified material then was
stirred in the presence of 10% Pd/C under a hydrogen atmosphere at
room temperature for 2 days. The reaction mixture was then fil-
tered to remove Pd/C and the filtrate was collected and evaporated
to dryness to give the crude product as a residue, which was pu-
rified by sequential silica gel column chromatography (eluent:
CHCl3) and gel permeation chromatography (JAIGEL 1Hþ2H, CHCl3)
to afford the title compound as a white solid (61.8 mg, 0.06 mmol)
in 25% yield. Mp 260e263 ꢁC. FT-IR (ATR, cmꢀ1): 2913, 2850, 1578,
1506, 1452, 1365, 1242, 1124, 973, 925. 1H NMR (400 MHz, CDCl3,
A solution of the 1,3-bis(4-propargyloxyphenyl)adamantane
(0.20 g, 0.25 mmol), copper(I) chloride (1.24 g, 12.5 mmol), and
N,N,N0,N0-tetramethylethylene diamine (1.87 mL, 12.5 mmol) in dry
CH2Cl2 (100 mL) was stirred for 24 h at room temperature under air.
The reaction mixture was then washed sequentially with water and
brine before being dried over anhydrous Na2SO4. Evaporation of the
solvent followed by sequential silica gel column chromatography
(eluent: CHCl3) and gel permeation chromatography (JAIGEL
1Hþ2H, CHCl3) afforded 1 (41.4 mg, 0.05 mmol, 42%) and 2
(9.87 mg, 0.01 mmol, 10%) as white powders. Macrocycle 1:
mp>300 ꢁC (decomposed). FT-IR (ATR, cmꢀ1): 2905, 2170, 1608,
1509, 1219, 1183, 1019, 818. 1H NMR (400 MHz, CDCl3, 27 ꢁC)
(d, J¼8.8 Hz, 8H), 6.89 (d, J¼8.8 Hz, 8H), 4.71 (s, 8H), 2.29 (s, 4H),
1.97e1.76 (s, 24H). 13C NMR (100 MHz, CDCl3, 27 ꢁC)
155.27,
d 7.31
d
144.07, 125.96, 114.49, 74.81, 71.02, 56.18, 49.37, 42.38, 36.73, 35.83,
29.58. MS (FAB, m/z) calcd for C56H53O4 [MþH]þ 789.39, found
789.3. Anal. Calcd for C56H52O4: C, 85.25; H, 6.64. Found: C, 85.13; H,
6.63. Macrocycle 2: mp>300 ꢁC (decomposed). FT-IR (ATR, cmꢀ1):
2911, 2172, 1608, 1508, 1219, 1184, 1027, 813. 1H NMR (400 MHz,
27 ꢁC)
d
6.54 (s, 8H), 4.01 (4, J¼6.0 Hz, 8H), 3.77 (s, 24H), 2.32 (s,
4H), 1.98e1.76 (m, 32H). 13C NMR (100 MHz, CDCl3, 27 ꢁC)
d
153.11,
146.13, 135.44, 102.69, 72.63, 56.19, 50.45, 42.11, 37.50, 35.82, 29.56,
26.04. MS (FAB, m/z) calcd for C60H77O12 [MþH]þ 989.53, found
989.9. Anal. Calcd for C60H76O12$0.1CHCl3: C, 72.10; H, 7.66. Found:
CDCl3, 27 ꢁC)
(s, 12H), 2.28 (s, 6H), 1.96e1.76 (s, 36H). 13C NMR (100 MHz, CDCl3,
d
7.30 (d, J¼8.8 Hz, 12H), 6.89 (d, J¼8.8 Hz, 12H), 4.71
C, 72.28; H, 7.79.
27 ꢁC)
d 155.30, 144.08, 125.97, 114.48, 74.82, 71.01, 56.21, 49.35,
4.8. Single-crystal X-ray crystallography
42.39, 36.73, 35.83, 29.58. MS (FAB, m/z) calcd for C84H79O6 [MþH]þ
1183.58, found 1183.9. Anal. Calcd for C84H78O6$0.1CHCl3: C, 84.50;
H, 6.58. Found: C, 84.51; H, 6.62.
Crystallographic data were collected on a CCD detector using
ꢀ
graphite monochromated Mo K
a
(l
¼0.71073 A) radiation. Data
collection for the crystals was carried out at 100 K using liquid
nitrogen. The crystal structures were solved by direct methods
(SHELXS 2013, Sheldrick, 2013). Refinements were carried out by
full-matrix least squares (on F2) with anisotropic temperature fac-
tors for non-H atoms. In all of the structures H atoms were included
as their calculated positions. For refinement of the structure and
structure analysis, the program package SHELX64 was used.
4.5. Macrocycles 3 and 4
Macrocycles 3 and 4 were synthesized as white solids in 54 and
17% yields in a manner similar to that described for the preparation
of 1 and 2. Macrocycle 3: mp>300 ꢁC (decomposed). FT-IR (ATR,
cmꢀ1): 2918, 2899, 2195, 1482, 1447, 1358,1209, 1140, 992, 974, 865,
754. 1H NMR (400 MHz, CDCl3, 27 ꢁC)
d
7.00 (s, 8H), 4.57 (s, 8H), 2.30
(s, 4H), 2.27 (s, 24H), 2.00e1.74 (m, 24H). 13C NMR (100 MHz, CDCl3,
27 ꢁC)
152.56, 146.62, 130.37, 125.45, 75.47, 70.80, 60.01, 50.38,
Crystal
data
for
3a:
C
11H11.33ClO0.73
,
Mr¼190.64,
ꢀ
0.40ꢂ0.40ꢂ0.25 mm, triclinic, Pꢀ1, a¼11.0512(19), b¼12.166(3) A,
d
c¼13.818(2) A,
a
¼93.776(2)ꢁ,
b
¼112.463(2)ꢁ,
g
¼116.639ꢁ,
ꢀ
3
41.99, 36.78, 35.89, 29.60, 16.89. MS (FAB, m/z) calcd for C64H69O4
[MþH]þ 901.51, found 901.8. Anal. Calcd for C64H68O4$0.05CHCl3: C,
84.80; H, 7.56. Found: C, 84.86; H, 7.78. Macrocycle 4: mp>300 ꢁC
(decomposed). FT-IR (ATR, cmꢀ1): 2916, 2900, 2848, 2195, 1520,
1485, 1446, 1356, 1208, 1141, 994, 973, 864, 760. 1H NMR (400 MHz,
V¼1470.0(5) A , Z¼6, Dc¼1.292 Mg mꢀ3, 2qmax¼51.804ꢁ, T¼100 K,
ꢀ
12,415 reflections measured, 5162 unique.
m
¼0.341 mmꢀ1
,
Tmax¼0.920, Tmin¼0.876, The final R1 and wR2(F2) was 0.1117 and
0.3093 (I>2s(I)), 0.1214 and 0.3187 (all data). CCDC-949049.
Crystal
data
for
3b:
C
13.33H16.67O1.33
,
Mr¼198.27,
CDCl3, 27 ꢁC)
d
7.01 (s,12H), 4.56 (s,12H), 2.29 (s, 42H),1.93e1.75 (m,
153.03, 146.70, 130.34,
0.40ꢂ0.40ꢂ0.20 mm, triclinic, Pꢀ1, a¼10.231(5), b¼12.089(6),
36H). 13C NMR (100 MHz, CDCl3, 27 ꢁC)
d
c¼14.912(7) A,
a
¼74.936(5)ꢁ,
b
¼74.936(5)ꢁ,
g
¼65.740(5)ꢁ,
ꢀ
3
ꢀ
125.44, 75.62, 70.80, 60.33, 49.46, 42.26, 36.78, 35.90, 29.60, 16.88.
MS (FAB, m/z) calcd for C96H103O6 [MþH]þ 1351.77, found 1351.1.
Anal. Calcd for C96H102O6$0.1CHCl3: C, 84.61; H, 7.40. Found: C,
84.90; H, 7.45.
V¼1595.3(13) A , Z¼6, Dc¼1.238 Mg mꢀ3, 2qmax¼51.358ꢁ, T¼100 K,
13,270 reflections measured, 5388 unique.
m
¼0.078 mmꢀ1
,
Tmax¼0.985, Tmin¼0.970, The final R1 and wR2(F2) was 0.1185 and
0.3163 (I>2s(I)), 0.1342 and 0.3314 (all data). CCDC-949050.
Crystal data for 5a:
C
15.50H19.50Cl1.50O3, Mr¼306.98,
4.6. 1,3-Bis(4-allyloxy-3,5-dimethoxyphenyl)adamantane (11)
0.40ꢂ0.40ꢂ0.40 mm, triclinic, Pꢀ1, a¼9.8166(14), b¼10.9736(16),
ꢀ
c¼14.045(2) A,
a
¼93.557(2)ꢁ,
b
¼103.229(2)ꢁ,
g
¼93.119(2)ꢁ,
The compound 11 was synthesized in 88% yield as a white solid
in a manner similar to that described for the preparation of 8,
where allyl bromide was used instead of propargyl bromide. Mp
112e114 ꢁC. FT-IR (ATR, cmꢀ1): 2901, 2848, 1583, 1511, 1455, 1412,
3
V¼1466.3(4) A , Z¼4, Dc¼1.391 Mg mꢀ3, 2qmax¼52.176ꢁ, T¼100 K,
ꢀ
12,546 reflections measured, 5208 unique.
m
¼0.356 mmꢀ1
,
Tmax¼0.871, Tmin¼0.871, The final R1 and wR2(F2) was 0.1087 and
0.2795 (I>2s(I)), 0.1237 and 0.2916 (all data). CCDC-949051.
1244, 1122, 986, 916, 825. 1H NMR (400 MHz, CDCl3, 27 ꢁC)
d 6.60 (s,
4H), 6.16e6.07 (m, 2H), 5.32 (d, J¼17.2 Hz, 2H), 5.19 (d, J¼10.0 Hz,
2H), 4.50 (d, J¼5.6 Hz, 4H), 3.86 (s, 12H), 2.33 (s, 2H), 1.93e1.78 (m,
Acknowledgements
12H). 13C NMR (100 MHz, CDCl3, 27 ꢁC)
d 152.60, 145.95, 134.61,
134.32, 116.78, 102.12, 73.59, 55.75, 49.18, 41.88, 37.12, 35.39, 29.15.
MS (FAB, m/z) calcd for C32H41O6 [MþH]þ 521.28, found 521.0. Anal.
Calcd for C32H40O6: C, 73.82; H, 7.74. Found: C, 73.55; H, 7.69.
This research was supported by a Grant-in-Aid for Scientific
Research (C) from the Ministry of Education, Culture, Sports, Sci-
ence, and Technology (MEXT) of Japan (Grant no. 25410133).

M. Tominaga et al. / Tetrahedron 70 (2014) 2576e2581
2581
€
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Supplementary data
1H and 13C NMR spectra for compounds 1e5, 8, 9, and 11; X-ray
crystallographic file (CIF) of 3a, 3b, and 5a. Supplementary data
related to this article can be found at http://dx.doi.org/10.1016/
j.tet.2014.02.006.
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