7156 J . Org. Chem., Vol. 64, No. 19, 1999
Sugimoto et al.
trans-2-bromoindanol (Aldrich, 1.0 g, 4.7 mmol) as described
above for the synthesis of 2a , after purification by silica gel
column chromatography (AcOEt/hexane, 1:19): 1H NMR (270
MHz, CDCl3) δ 7.68-7.14 (m, 14 H), 6.60 (dd, 1 H, J ) 20.2,
15.0 Hz), 6.33 (dd, 1 H, J ) 15.0, 3.8 Hz), 5.92 (dd, 1 H, J )
20.2, 3.8 Hz), 5.46 (d, 1 H, J ) 4.7 Hz), 4.40 (ddd, 1 H, J )
6.5, 6.0, 4.7 Hz), 3.65 (dd, 1 H, J ) 16.5 Hz, 6.5 Hz), 3.16 (dd,
1 H, J ) 16.5, 6.0 Hz); EI MS m/z 420, 422 (M+). Anal. Calcd
for C23H21BrOSi: C, 65.55; H, 5.02; Br, 18.96. Found: C, 65.56;
H, 5.20; Br, 18.61.
(()-tr a n s-1-Diph en ylvin ylsiloxy-2-iodocycloh exan e (8).
Compound 8 (2.79 g, 91%) was obtained as an oil from (()-
trans-2-iodocyclohexanol18 (1.60 g, 7.08 mmol) as described
above for the synthesis of 2a , after purification by silica gel
column chromatography (Et2O/hexane 1:100): 1H NMR (270
MHz, CDCl3) δ 7.68-7.30 (m, 10 H), 6.55 (dd, 1 H, J ) 20.5,
15.2 Hz), 6.30 (dd, 1 H, J ) 15.2, 4.0 Hz), 5.90 (dd, 1 H, J )
20.5, 4.0 Hz), 4.15 (ddd, 1 H, J ) 9.9, 7.9, 4.0 Hz), 3.92 (ddd,
1 H, J ) 8.6, 7.9, 4.0 Hz), 2.45-2.35 (m, 1 H), 2.05-1.85 (m,
2 H), 1.76-1.73 (m, 1 H), 1.52-1.28 (m, 4 H); EI HRMS calcd
for C20H23IOSi 434.0563, found 434.0593 (M+).
(()-t r a n s-1-Dip h e n ylvin ylsiloxy-2-p h e n ylse le n oin -
d a n (2c). Compound 2c (0.25 g, quant) was obtained as an
oil from (()-trans-2-phenylselenoindanol16 (0.15 g, 0.50 mmol)
as described above for the synthesis of 2a , after purification
by silica gel column chromatography (Et2O/hexane 1:50): 1H
NMR (270 MHz, CDCl3) δ 7.72-7.11 (m, 19 H), 6.54 (dd, 1 H,
J ) 20.5, 15.2 Hz), 6.31 (dd, 1 H, J ) 15.2, 4.0 Hz), 5.98 (dd,
1 H, J ) 20.5, 4.0 Hz), 5.47 (d, 1 H, J ) 5.9 Hz), 4.10 (dt, 1 H,
J ) 5.9, 5.3 Hz), 3.18 (d, 2 H, J ) 5.3 Hz); EI HRMS calcd for
(()-cis-1-Hyd r oxy-2-vin ylin d a n e (3). A stirring solution
of 2a (103 mg, 0.220 mmol) and (Bu3Sn)2 (10 µL, 20 mmol) in
benzene (2 mL) was irradiated with a high-pressure mercury
lamp (300 W) for 1 h. To the resulting mixture was added
TBAF (1 M in THF, 0.30 mL, 0.30 mmol), and the whole was
stirred at room temperature for 20 min. The solvent was
evaporated, and the residue was purified by silica gel column
chromatography (AcOEt/hexane 1:5) to give 3 (29 mg, 82%)
as an oil: 1H NMR (400 MHz, CDCl3) δ 7.44-7.22 (m, 4 H),
5.97 (ddd, 1 H, J ) 17.1, 10.5, 7.8 Hz), 5.30-5.25 (m, 2 H),
5.09 (m, 1 H), 3.17-3.10 (m, 1 H), 3.00 (d, 2 H, J ) 7.3 Hz),
C
29H26OSeSi 498.0916, found 498.0918 (M+).
(()-t r a n s-2-Dip h e n ylvin ylsiloxy-1-p h e n ylse le n oin -
d a n (4). A mixture of NaH (60%, 0.24 g, 6.0 mmol) and (()-
trans-2-bromoindanol (Aldrich, 1.07 g, 5.02 mmol) in THF (25
mL) was stirred at room temperature for 2 h. To the resulting
mixture was added a solution prepared from (PhSe)2 (3.12 g,
10.0 mmol) and NaBH4 (1.14 g, 30.1 mmol) in EtOH (25 mL),
and the whole was stirred at room temperature for 10 min.
Et2O and aqueous saturated NH4Cl were added, and the
resulting mixture was partitioned. The aqueous layer was
extracted with Et2O, and the organic layer combined was
washed with brine, dried (Na2SO4), and evaporated. The
residue was purified by silica gel column chromatography
(AcOEt/hexane 1:4) to give (()-trans-1-phenylselenoindan-2-
ol (1.42 g, 98%) as an oil: 1H NMR (500 MHz, CDCl3) δ 7.53-
7.21 (m, 9 H, aromatic), 4.66 (d, 1 H, H-1, J 1,2 ) 1.7 Hz), 4.60
(m, 1 H, H-2), 3.30 (dd, 1 H, H-3a, J ) 16.6, 5.6 Hz), 2.82 (dd,
1 H, J ) 16.6, 2.1 Hz), 1.85 (d, 1 H, 2-OH J ) 5.9 Hz), the
assignments were in agreement with H-H COSY spectrum;
13C NMR (125 MHz, CDCl3) δ 140.7, 140.6, 134.2, 129.4, 129.1,
128.0, 127.7, 127.1, 125.7, 125.3, 79.0, 53.9, 40.0; EI HRMS
calcd for C15H14OSe 290.0209, found 290.0195 (M+). Anal.
Calcd for C15H14OSe: C, 62.29; H, 4.88. Found: C, 62.18; H,
4.92.
1.70 (d, 1 H, J ) 5.1 Hz); EI HRMS calcd for C11H12
160.0888, found 160.0873.
O
(()-cis-2-Hyd r oxy-1-vin ylin d a n e (5). Compound 5 (17
mg, 53%) was obtained as an oil from 4 (100 mg, 0.201 mmol)
as described above for the synthesis of 3, after purification by
silica gel column chromatography (AcOEt/hexane 1:5): 1H
NMR (500 MHz, CDCl3) δ 7.28-7.17 (m, 4 H, aromatic), 6.02
(ddd, 1 H, CHdCH2, J ) 17.7, 10.4, 8.4 Hz), 5.39 (dd, 1 H,
CHdCH2, J ) 10.4, 1.7, Hz), 5.34 (dd, 1 H, CHdCH2, J ) 17.7,
1.7 Hz), 4.60 (ddd, 1 H, H-2, J 1,2 ) 5.4 Hz, J 2,3a ) 5.4 Hz, J 2,3b
) 3.0 Hz,), 3.82 (dd, 1 H, H-1, J 1,1′ ) 8.4 Hz, J 1,2 ) 5.4 Hz),
3.15 (dd, 1 H H-3a, J ) 16.1, 5.4 Hz), 2.96 (dd, 1 H, H-3b, J )
16.1, 3.0 Hz), 1.69 (d, 1 H, 2-OH, J ) 5.2 Hz), the assignments
were in agreement with H-H COSY spectrum; NOE (CDCl3,
400 MHz) irradiated H-2, observed H-1 (2.0%); 13C NMR (125
MHz, CDCl3) δ 142.6, 140.9, 135.1, 127.1, 126.7, 125.1, 124.9,
119.2, 75.4, 54.8, 41.0; EI HRMS calcd for C11H12O 160.0888,
found 160.0897. Anal. Calcd for C11H12O: C, 82.46; H, 7.55.
Found: C, 82.19; H, 7.32.
(()-cis-1-Ben zoyloxy-2-vin ylcyclop en ta n e (7). A stirring
solution of 6 (210 mg, 0.500 mmol) and (n-Bu3Sn)2 (25 µL, 49
µmol) in benzene (2.5 mL) was irradiated with high-pressure
mercury lamp (300 W) for 30 min. To the resulting mixture
was added TBAF (1 M in THF, 0.30 mL, 0.30 mmol)), and the
whole was stirred at room temperature for 20 h. After the
solvent was evaporated, the residue and BzCl (0.60 mL, 5.2
mmol) were dissolved in pyridine (2 mL), and the resulting
mixture was stirred at room temperature for 2 h. Et2O and
water were added, and the resulting mixture was partitioned.
The organic layer was washed with brine, dried (Na2SO4), and
evaporated. The residue was purified by silica gel column
chromatography (Et2O/hexane 1:100) to give 7 (62 mg, 58%)
as an oil: 1H NMR (400 MHz, CDCl3) δ 8.02-7.42 (m, 5 H),
5.93 (ddd, 1 H, J ) 17.1, 10.5, 7.6 Hz), 5.43 (ddd, 1 H, J ) 5.1,
1.7 Hz), 5.12 (ddd, 1 H, J ) 17.1, 1.7, 1.5 Hz), 5.03 (dd, 1 H, J
) 10.5, 1.5 Hz), 2.72-2.65 (m, 1 H), 2.13-2.06 (m, 1 H), 1.95-
1.78 (m, 4 H), 1.74-1.66 (m, 1 H);13C NMR (100 MHz, CDCl3)
δ 165.9, 137.0, 132.6, 130.7, 129.4, 128.2, 115.7, 79.0, 48.5, 32.4,
29.5, 22.3; EI HRMS calcd for C14H16O2 216.1150, found
216.1146 (M+). Anal. Calcd for C14H16O2: C, 77.75; H, 7.46.
Found: C, 77.75; H,7.58.
Compound 4 (2.20 g, 98%) was obtained as an oil from (()-
trans-1-phenylselenoindan-2-ol (1.30 g, 4.49 mmol) as de-
scribed above for the synthesis of 2a , after purification by silica
gel column chromatography (Et2O/hexane 1:50): 1H NMR (500
MHz, CDCl3) δ 7.49-7.14 (m, 19 H), 6.31 (dd, 1 H, J ) 20.1,
14.9 Hz), 6.18 (dd, 1 H, J ) 15.0, 3.8 Hz), 5.76 (dd, 1 H, J )
20.3, 3.9 Hz), 4.79 (m, 1 H), 4.76 (s, 1 H), 3.13 (dd, 1 H, J )
16.3, 5.3 Hz), 2.87 (dd, 1 H, J ) 16.3, 1.4 Hz); 13C NMR (125
MHz, CDCl3) δ 141.3, 141.2, 137.3, 135.0, 134.7, 134.3, 134.2,
133.6, 130.0, 129.5, 128.9, 127.8, 127.7, 127.6, 126.8, 125.6,
125.0, 80.3, 54.6, 40.7; EI HRMS calcd for
C29H26OSeSi
498.0916, found 498.0912 (M+). Anal. Calcd for C29H26OSeSi:
C, 70.00; H, 5.27. Found: C, 70.03; H, 5.38.
(()-tr a n s-1-Diph en ylvin ylsiloxy-2-iodocyclopen tan e (6).
Compound 6 (1.84 g, 94%) was obtained as an oil from (()-
trans-2-iodocyclopentanol17 (987 mg, 4.66 mmol) as described
above for the synthesis of 2a , after purification by silica gel
column chromatography (Et2O/hexane 1:100): 1H NMR (400
MHz, CDCl3) δ 7.61-7.36 (m, 10 H), 6.49 (dd, 1 H, J ) 20.3,
14.9 Hz), 6.30 (dd, 1 H, J ) 14.9, 3.9 Hz), 5.88 (dd, 1 H, J )
20.3, 3.8 Hz), 4.61 (dt, 1 H, J ) 5.9, 2.9 Hz), 4.13 (dt, 1 H, J )
2.9 Hz), 2.46-2.37 (m, 1 H), 2.14-1.99 (m, 2 H), 1.92-1.75
(m, 2 H), 1.73-1.65 (m, 1 H); 13C NMR (100 MHz, CDCl3) δ
137.4, 134.9, 133.9, 133.4, 130.0, 127.8, 83.0, 35.8, 34.6, 32.2,
22.3; EI HRMS calcd for C19H21IOSi 420.0406, found 420.0384
(M+). Anal. Calcd for C19H21IOSi: C, 54.29; H, 5.04. Found:
C, 54.17; H, 5.08.
(()-cis-1-Ben zoyloxy-2-vin ylcycloh exa n e (9). Compound
9 (60 mg, 52%) was obtained as an oil from 8 (217 mg, 0.500
mmol) as described above for the synthesis of 7, after purifica-
tion by silica gel column chromatography (Et2O/hexane
1:100): 1H NMR (400 MHz, CDCl3) δ 8.08-7.42 (m, 5 H,
aromatic), 5.89 (ddd, 1 H, CH)CH2, J ) 17.3, 10.5, 6.8 Hz),
5.29 (m, 1 H, H-1, J 1,2 < 2.2 Hz), 5.06 (ddd, 1 H, CHdCH2, J
) 17.3, 1.5, 1.5 Hz), 5.01 (ddd, 1 H, CHdCH2, J ) 10.5, 1.5,
(16) Torii, S.; Ueyama, K.; Ono M. Tetrahedron Lett. 1980, 21, 2741-
2744.
(17) Barluenga, J .; Rodriguez, M. A.; Campos, P. J . J . Chem. Soc.,
Perkin Trans. 1 1990, 2807-2809.
(18) Palumbo, G.; Ferreri, C.; Caputo, R. Tetrahedron Lett. 1983,
24, 1307-1310.