ortho or meta to I), 128.9 (PhC), 132.1 (PhC), 137.5 (PhCH ortho
or meta to I), 148.4 (PhC para to I); FT-IR (KBr, cm-1); 2927(m),
2896(m), 2851(m), 2156(w), 1485(s), 1390(w), 1355(w), 1247(s),
1187(w), 1067(w), 1002(s), 862(s), 842(s), 777(m), 756(m), 696(w),
647(w); MS (FAB) m/z 915 ([M+H]+); Anal. Calcd for C39H37I3Si:
C, 51.22; H, 4.08; Found: C, 51.04; H, 4.24.
Experimental
General
Melting points were recorded on a melting point apparatus
MP-21 (Yamato Scientific Co., Ltd., Tokyo, Japan) using open
capillary tubes and remain uncorrected. The H- and 13C-NMR
1
spectra were recorded on a Mercury plus 400 (Varian Inc., CA,
1
USA) at 400 MHz for H and 125 MHz for 13C, and in CDCl3
Trimethyl[4-[3,5,7-tris-[4-(4-acetylsulfanylmethylphenylethyny]-
phenyl]adamantan-1-yl]phenylethynyl]silane (4)
(Merck KGaA, Darmstadt, Germany) unless otherwise noted.
Chemical shifts are expressed in d units (ppm) with the residual
solvent peaks (1H CHCl3, d 7.26; 13C CHCl3, d 77.0) as internal
standards. Coupling constants (J) are reported in Hertz (Hz).
Mass spectra obtained via FAB-MS and MALDI-TOF-MS were
recorded respectively on a JMS-700 (JEOL Ltd., Tokyo, Japan)
and an AB4700 (Applied Biosystems Japan Ltd., Tokyo, Japan)
or a Bruker MALDI-TOF-TOF (Bruker, Billerica, MA, USA). IR
spectra were recorded on an FT/IR-460 plus (JASCO Co., Tokyo,
Japan). UV–Vis absorption spectra were recorded in CH2Cl2 on a
UV-265 (SHIMADZU Co., Kyoto, Japan). Column chromatog-
raphy and preparative thin-layer chromatography (TLC) were
To a mixture of 2 (0.38 g, 0.4 mmol), Pd(PPh3)2Cl2 (53.6 mg,
0.08 mmol), and PPh3 (10 mg, 0.04 mmol) in a Schlenk flask,
THF (20 mL) was added. The solution was degassed by freeze-
pump-thaw three times. After the addition of 3 (44 mg, 2.3 mmol),
Et3N (427 ml, 2.3 mmol) was added in succession by a gastight
syringe. After repetition of the freeze-pump-thaw for an additional
three times, CuI (3.5 mg, 0.02 mmol) was added. The flask was
immersed in a thermostated oil bath and refluxed for 5 days. The re-
action mixture was poured into water and extracted with CH2Cl2.
The combined organic extracts were washed with brine, dried over
anhydrous MgSO4, and concentrated in vacuo. The resulting red-
brown oil was purified by silica gel column chromatography with
hexane–CH2Cl2 (1 : 10) to give yellow crystals 4 (79 mg, 20%): Rf
0.3 (hexane–EtOAc (2 : 1)); mp 118–120 ◦C; 1H NMR (400 MHz,
CDCl3) d 0.25 (s, 9H, –CH3 in TMS), 2.16 (brs, 12H, –CH2–
in adamantane), 2.36 (s, 9H, –CH3 in SAc), 4.12 (s, 6H, –CH2–
SAc), 7.2–7.4 (m, 4H, ArH), 7.4–7.6 (m, 24H, ArH); 13C NMR
(125 MHz, CDCl3) d -0.0 (TMS), 30.3 (–CH3, in SAc), 33.3 (–
CH2–SAc), 39.3 (–CH2– in adamantane), 46.8 (quaternary C in
R
carried out on silica gel Wakogelꢀ C-200 (200 mesh, Wako Pure
R
Chemical Industries, Ltd.) and on silica plate Partisilꢀ PK6F
(16.0 nm, layer thickness 1000 mm, Whatman plc, Middlesex, UK),
respectively. Analytical TLC was performed on commercially
coated plastic plates Silica gel 60 mesh F254, (Merck KgaA).
Spots were rendered visible by exposing the plate to UV light. All
reagents were purchased from commercial suppliers as described
and used without further purification. Tetrahydrofuran (99.5%,
anhydrous, inhibitor free, Kanto Chemical Co., Inc., Tokyo,
Japan), triethylamine, dichloromethane, diethyl ether (Wako Pure
Chemical Industries, Ltd., Osaka, Japan), and other reagent-
grade solvents (chloroform, methanol, benzene, hexane, Kanto
Chemical Co., Inc.) were used as received. Brine refers to saturated
aqueous solution of NaCl.
≡
≡
≡
adamantane), 88.9 (–C C–), 89.5 (–C C–), 94.2 (Ph–C ), 105.5
≡
( C–TMS), 121.1 (PhC), 122.3 (PhC), 124.9 (PhC), 125.1 (PhC),
125.1 (PhCH), 128.8 (PhCH), 131.7 (PhCH), 131.8 (PhCH), 132.0
=
(PhC), 137.8 (PhC), 149.2 (PhC), 149.4 (PhC), 195.0 (C O); FT-
IR (KBr, cm-1); 2924(m), 2850(w), 2211(w), 2154(w), 1686(s),
1509(m), 1411(w), 1353(m), 1246(w), 1132(m), 1101(w), 1018(m),
958(m), 833(s), 775(w), 699(w), 626(m). MS (FAB) m/z 1101
([M+H]+); Anal. Calcd for C72H64O3S3Si: C, 78.50, H, 5.86; S,
Trimethyl[4-[3,5,7-tris(4-iodophenyl)adamantan-1-
yl]phenylethynyl]silane (2)
8.73. Found: C, 78.75; H, 5.81; S, 8.60; UV–Vis (in CH2Cl2, lmax
,
A mixture of 1,3,5,7-tetrakis(4-iodophenyl)adamantane 1 (0.54 g,
0.6 mmol), Pd(PPh3)2Cl2 (9.0 mg, 0.01 mmol), and PPh3 (1.7 mg,
0.006 mmol) was placed in a Schlenk flask, degassed, and replaced
with Ar gas. The evacuation and flushing process was repeated
three times. THF (10 ml), TMSA (55 ml, 0.39 mmol), and Et3N
(72 ml, 0.39 mmol) were added to the mixture above in succession
by gastight syringes. After repetition of freeze-pump-thaw for
three times, CuI (0.6 mg, 0.003 mmol) was added. The flask
was immersed in a thermostated oil bath and refluxed for 4 days.
The reaction mixture was poured into water and extracted with
CH2Cl2. The combined organic extracts were washed with brine,
dried over anhydrous MgSO4, and concentrated in vacuo. The
resulting yellow oil was purified by silica gel chromatography with
hexane–EtOAc (10 : 1) to give a yellow solid 2 (0.45 g, 85%): Rf
0.9 (hexane–EtOAc (5 : 1)); mp 152–154 ◦C; 1H NMR (400 MHz,
CDCl3) d 0.25 (s, 9H, TMS), 2.06 (s, 12H, adamantane CH2), 7.19
(d, J = 8.6 Hz, 6H, ArH), 7.37 (d, J = 8.6 Hz, 2H, ArH), 7.45 (d,
J = 8.6 Hz, 2H, ArH), 7.67 (d, J = 8.8 Hz, 6H, ArH); 13C NMR
(125 MHz, CDCl3) d -0.0 (–TMS), 39.0 (adamantane CH2), 46.7
nm): 290 nm, 310 nm.
4-[3,5,7-Tris-[4-(4-acetylsulfanylmethylphenylethynyl)phenyl]-
adamantan-1-yl]phenylethyne (5)
A 1.0 M solution of Bu4NF (30.2 mg, 0.1 mmol) in THF (0.1 mL)
was added to a stirred solution of 4 (96 mg, 0.09 mmol) in
THF (10 mL) at -20 ◦C dropwise over ◦30 min. The solution was
subsequently stirred for 30 min at -20 C under Ar atmosphere.
The reaction mixture was poured into water and extracted with
CH2Cl2. The combined organic extracts were washed with brine,
dried over anhydrous MgSO4, and concentrated in vacuo. The
resulting orange oil was purified by silica gel column chromatog-
raphy with hexane–CH2Cl2 (1 : 10) to give a yellow solid 5 (50 mg,
56%): Rf 0.2 (hexane–EtOAc (2 : 1)); 1H NMR (400 MHz, CDCl3)
d 2.16 (s, 12H, –CH2– in adamantane), 2.36 (s, 9H, –CH3 in SAc),
≡
3.06 (s, 1H, CH), 4.12 (s, 6H, –CH2–SAc), 7.2-7.4 (m, 4H, ArH),
7.4-7.6 (m, 24H, ArH); FT-IR (KBr, cm-1); 2924(m), 2850(w),
2211(w), 1686(s), 1509(s), 1354(m), 1238(w), 1131(m), 1099(m),
1017(m), 956(m), 831(s), 773(m), 698(w), 624(s); MS (MALDI-
TOF) m/z 1028 (M+).
≡
(adamantane quaternary C), 90.9 (Ph–C ), 91.7 (PhC adjunct
≡
to I), 105.8 ( C–TMS), 124.6 (PhC), 127.1 (PhC), 127.1 (PhCH
This journal is
The Royal Society of Chemistry 2010
Org. Biomol. Chem., 2010, 8, 3655–3664 | 3661
©