Synthetic Approach to a [1.1.6] Metapara Cyclophane Derivative
COMMUNICATIONS
1
Experimental Section
3b: colourless oil; H NMR (300 MHz, CDCl
3
): d¼4.02 (s,
4
7
H), 7.01 (s, 1H), 7.04 (d, 2H, J¼7.5 Hz), 7.25 (t, 1H, J¼
.5 Hz) 7.33 (d, 4H, J¼8 Hz), 7.8 (d, 4H, J¼8.2 Hz), 9.97 (s,
1
3
General Remarks
2H); C NMR (100.6 MHz, CDCl ): d¼42.1, 127.3, 129.2,
3
1
29.7, 129.8, 130.1, 134.9, 140.4, 148.3; HR-MS (QTOF):
Melting points are uncorrected. Analytical thin-layer chroma-
tography (TLC) was performed on glass plates coated with
m/z¼337.1208, calcd. for C H O Na (MþNa): 337.1204.
2
2
18
2
1
3
c: mp 114–1158C; H NMR (300 MHz, CDCl ): d¼4.0 (s,
3
Acmeꢁs silica gel G or GF 254 (containing 13% calcium sul-
4
phate as a binder). Visualization of the spots on TLC plates
7
H), 6.97 (s, 1H), 7.02 (d, 2H, J¼7.3 Hz), 7.23–7.27 (m, 5H),
.57 (d, 4H, J¼8 Hz); HR-MS (QTOF): m/z¼309.1398, calcd.
for C H N (MþH): 309.1392.
was achieved either by exposure to iodine vapour or UV light.
2
2
17
2
Flash chromatography was performed using Acmeꢁs silica gel
1
3
d: mp 818C; H NMR (300 MHz, CDCl ): d¼2.56 (s, 6H),
3
(
100–200 mesh). Petroleum ether refers to fraction having
3
.99 (s, 4H), 7.01 (s, 1H), 7.02 (d, 2H, J¼7.9 Hz), 7.20–7.26
boiling point 60–808C. Yields refer to the chromatographical-
st
nd
(m, 5H), 7.87 (d, 4H, J¼8.5 Hz); HR-MS (QTOF): m/z¼
ly isolated yield. 1 and 2 generation Grubbsꢁ catalysts were
purchased from Strem Chemicals, Inc. and Fluka, respectively.
All the commercial grade reagents were used without further
purification. Infrared spectra were recorded on a Nicolet 400
FT IR spectrometer in KBr/CHCl /CCl and the absorptions
3
65.1515, calcd. for C H O Na (MþNa): 365.1517.
2
4
22
2
1
5
b: mp 1988C; H NMR (300 MHz, CDCl ): d¼2.13 (s, 9H),
3
4
9
.24 (s, 6H), 7.20 (d, 6H, J¼8.1 Hz), 7.79 (d, 6H, J¼8.1 Hz),
1
3
.97 (s, 3H); C NMR (100.6 MHz, CDCl ): d¼17.1, 36.8,
3
3
4
ꢀ
1
1
128.6, 130.3, 134.5, 134.8, 135.3, 147.9, 192.1; HR-MS
are reported in cm . H NMR spectra were determined on a
(
4
QTOF): m/z¼475.2296, calcd. for C H O (MþH):
3
3
31
3
Bruker 300 MHz spectrometer as CDCl solutions. Coupling
3
75.2273.
5
constants (J values) are given in hertz (Hz). Chemical shifts
are expressed in parts per million (ppm) downfield from inter-
nal reference tetramethylsilane.
1
c: mp 2328C; H NMR (300 MHz, CDCl ): d¼2.09 (s, 9H),
3
13
4
.2 (s, 6H), 7.12 (d, 6H, J¼8.1 Hz), 7.56 (d, 6H, J¼8.1 Hz); C
NMR (100.6 MHz, CDCl ): d¼17.0, 36.6, 110.2, 119.0, 128.6,
3
1
32.5, 134.2, 135.4, 145.9; HRMS (QTOF): m/z¼466.2262,
calcd. for C H N (MþH): 466.2283.
3
3
28
3
1
General Procedure for Couplingof Arylboronic Acids
with a,a’-Dibromo-m-xylene (1)
7: mp 60–618C; H NMR (300 MHz, CDCl ): d¼2.04 (d,
3
2H, J¼4.4 Hz), 2.47–2.53 (m, 4H), 3.93 (s, 4H), 4.71 (t, 2H,
J¼6.2 Hz), 5.12–5.2 (m, 4H), 5.74–5.88 (m, 2H), 7.0–7.02
A mixture of a,a’-dibromo-m-xylene 1 (1 equiv.), arylboronic
13
(
m, 3H), 7.13–7.22 (m, 5H), 7.27 (d, 4H, J ¼ 8.1 Hz);
C
acid (3 equivs.), Pd(PPh ) (6–10 mol %), Na CO (4 equivs.)
3
4
2
3
NMR (75.4 MHz, CDCl ): d¼41.6, 43.9, 73.2, 118.5, 126.0,
3
in water and THF (1:1) was heated at 808C. The reaction mix-
ture was degassed with argon for 20 min prior to the addition of
the catalyst. At the conclusion of the reaction (TLC monitor-
ing), the reaction mixture was diluted with water and extracted
with ethyl acetate. The combined organic layer was washed
1
(
4
26.8, 128.6, 129.0, 129.6, 134.6, 140.5, 141.3, 141.7; HR-MS
EI): m/z¼421.2139, calcd. for C H O Na (MþNa):
2
8
30
2
21.2143.
: mp 222–2238C. The spectroscopic data given below are
8
1
for the major isomer. H NMR (300 MHz, CDCl ): d¼1.74
3
with water, brine and dried over anhydrous MgSO . The sol-
4
(
(
8
d, 2H, J¼4 Hz), 2.50–2.55 (m, 4H), 3.89 (s, 4H), 4.67–4.71
m, 2H), 5.10 (t, 2H, J¼3.7 Hz), 6.33 (s, 1H), 6.97 (d, 4H, J¼
vent was evaporated and the crude product was charged on a
silica gel column. Elution of the column with EtOAc/petrole-
um ether gave the desired cross-coupling product.
.4 Hz), 7.07 (d, 4H, J¼8.1 Hz), 7.14 (d, 2H, J¼8.4 Hz), 7.26
(
t, 1H, J¼7.5 Hz); HR-MS (QTOF): m/z¼393.1823, calcd.
for C H O Na (MþNa): 393.1831.
2
6
26
2
1
9
: mp 1748C; H NMR (300 MHz, CDCl ): d¼3.61 (dd, 4H,
3
RCM of 1,3-Bis-[4-(1-hydroxybut-3-enyl)-benzyl]-
J¼3.6, 1.5 Hz), 3.91 (s, 4H), 5.75 (tt, 2H, J¼3.6, 1.5 Hz), 6.01(s,
1H), 6.99 (d, 4H, J¼8.4 Hz), 7.14 (d, 2H, J¼7.7 Hz), 7.26 (t,
nd
benzene (7) using2 Generation Grubbsꢀ Catalyst
1
3
1
(
1
H, J¼7.5 Hz); 7.7 (d, 4H, J¼8.4 Hz);
C
NMR
A solution of compound 7 (90 mg, 0.23 mmol) in dry, degassed
DCM (60 mL) was added over a period of 1 h through an addi-
tion funnel to a solution of Grubbsꢁ catalyst 6 (13 mg, 7 mol %)
in dry, degassed DCM (10 mL). The reaction mixture was stir-
red at room temperature for 24 h and concentrated. The crude
product was purified bysilica gel column chromatography. Elu-
tion of the column with 20% EtOAc/petroleum ether gave the
compound 8 as a mixture of diastereomers as a white crystal-
line solid; yield: 28 mg (33%).
100.6 MHz, CDCl ): d¼41.2, 43.9, 126.4, 128.1, 128.3, 129,
3
29.6, 133.5, 140.8, 146.2, 197.1; HR-MS (EI): m/z¼366.1620,
calcd. for C H O : 366.1620.
2
6
22
2
X-Ray Crystallographic Study of 1,5(1,4),3(1,3)-
Tribenzenacycloundecaphan-8-ene-6,11-dione (9)
Crystal data for disordered structure (A): C H O , M¼
2
6
22
2
3
5
2
66.44, monoclinic, space group P2 /n, a¼11.868(2), b¼
1
3
.781(1), c¼28.980(4) , b¼97.62(3)8, V¼1970.7(4) , T¼
Spectral Data
ꢀ
1
93(2) K, Z¼4, m(Mo-K )¼0.077 mm , 8132 reflections
a
1
3
(
1
(
a: mp 738C; H NMR (300 MHz, CDCl ): d¼3.78 (s, 6H), 3.88
measured, 2841 unique (R ¼0.0406), observed with I>
3
int
s, 4H), 6.82 (d, 4H, J¼8.8 Hz), 6.98 (d, 2H, J¼8.1 Hz), 7.01 (s,
2s(I) which were used in all refinements. R ¼0.038, wR ¼
1
2
13
H), 7.08 (d, 4H, J¼8.8 Hz), 7.18 (t, 1H, J¼7.3 Hz); C NMR
0.073 for the observed data, CCDC 233847.
75.4 MHz, CDCl ): d¼41, 55.3, 113.9, 126.6, 128.6, 129.5,
Crystal data for ordered structure (B): C H O , M¼
3
26 22
2
1
29.9, 133.4, 141.7, 158.0; HR-MS (EI): m/z¼318.1612, calcd.
366.44, monoclinic, space group P2 /n, a¼11.828(2), b¼
1
3
for C H O : 318.1619.
5.742 (1), c¼28.555(6) , b¼97.47(1)8, V¼1922.9(6) ,
22
22
2
Adv. Synth. Catal. 2005, 347, 1215–1218
asc.wiley-vch.de
ꢀ 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1217