1-(2-Indenyl)-2-(3-indenyl)ethane
mL of a 2.32 M solution in hexane, 163 mmol). The reaction
mixture was stirred 2 h at -78 °C and 0.5 h at 0 °C, and then
recooled to -78 °C whereupon a solution of ethylene oxide (7.16
g, 163 mmol) in THF (325 mL) at -78 °C was added dropwise
via cannula. The reaction was slowly warmed to room tem-
perature, stirred 15 h, and then quenched by addition of
saturated aqueous NH4Cl. The reaction mixture was extracted
with three portions of EtOAc and the combined organic extract
was washed successively with H2O and brine and then dried
(MgSO4). The solvents were removed by rotary evaporation.
Recrystallization of the residue from 95% EtOH yielded 32.6
in THF (200 mL) at -78 °C was added dropwise n-BuLi (43.1
mL of a 2.32 M solution in hexane, 100.1 mmol). The yellow
slurry was stirred 10 min, warmed to room temperature, and
stirred 45 min, and then cooled to -40 °C before addition of
HMPA (44.6 mL). The reaction solution was then added
dropwise via cannula to a stirred solution of iodo-sulfone 10b
(20.0 g, 49.0 mmol) in THF (245 mL) at -78 °C. The amber
reaction mixture turned deep red as it was allowed to warm
to room temperature over 4 h. The reaction was quenched by
addition of aq NH4Cl and then extracted with two portions of
EtOAc. The combined organic extract was washed with H2O
and brine, and then dried (MgSO4). The solvents were removed
by rotary evaporation. The crude residue was dissolved in a
minimum amount of CH2Cl2 and crystallization was induced
by addition of EtOH, yielding 15.8 g (81%) of 6 as a white
powder; mp 137-139 °C; 1H NMR δ 2.20 (m, 2H), 2.43 (m,
2H), 3.01 (d, J ) 17.0 Hz, 2H), 3.19 (s, 2H), 3.84 (d, J ) 17.0
Hz, 2H), 7.05-7.17 (m, 7H), 7.33-7.52 (m, 4H), 7.83-7.85 (m,
2H); 13C NMR δ 22.7, 34.2, 37.7, 39.3, 72.2, 118.7, 123.7, 124.1,
124.7, 126.0, 127.2, 127.9, 128.8, 130.0, 133.6, 136.5, 139.7,
143.2, 144.2, 144.7; IR (KBr) 3066, 2931, 1446, 1297, 1143
cm-1. Anal. Calcd for C26H24O2S: C, 77.97; H, 6.04. Found:
C, 77.85; H, 6.09.
1
g (70%) of 12a as white crystals; mp 163-166 °C; H NMR δ
1.93 (s, 1H), 2.16 (t, J ) 6.2 Hz, 2H), 3.03 (d, J ) 17.0 Hz,
2H), 3.64 (t, J ) 6.5 Hz, 2H), 3.81 (d, J ) 16.4 Hz, 2H), 7.07-
7.10 (m, 4H), 7.50-7.60 (m, 3H), 7.88-7.91 (m, 2H); 13C NMR
δ 38.4, 39.6, 58.8, 71.6, 124.1, 127.2, 128.9, 130.0, 133.8, 136.0,
139.2; IR (KBr) 3516, 3060, 2949, 1446, 1294, 1141 cm-1. Anal.
Calcd for C17H18O3S: C, 67.52; H, 6.00. Found: C, 67.49; H,
6.05.
P r ep a r a tion of 2-(2-Hyd r oxyp r op yl)-2-(p h en ylsu lfo-
n yl)in d a n e (12b). Epoxide adduct 12b was prepared analo-
gously to 12a from 7 (3.0 g, 11.6 mmol) with propylene oxide
(0.73 g, 12.5 mmol): yield 76% (2.78 g) as a white solid; mp
174.5-175.5 °C; 1H NMR δ 1.15 (d, J ) 5.9 Hz, 3H), 1.97-
2.12 (m, 2H), 2.33 (d, J ) 4.1 Hz, 1H), 3.12 (d, J ) 17.0 Hz,
1H), 3.20 (d, J ) 17.0 Hz, 1H), 3.74 (d, J ) 17.0 Hz, 1H), 3.83
(d, J ) 17.0 Hz, 1H), 4.05-4.12 (m, 1H), 7.01-7.08 (m, 4H),
7.46 (m, 2H), 7.57 (m, 1H), 7.88 (m, 2H); 13C NMR δ 24.9, 39.9,
40.4, 44.5, 64.4, 72.4, 124.1, 124.2, 127.1, 127.2, 128.8, 130.1,
133.7, 136.2, 139.4, 139.6; IR (KBr) 3542, 3052, 2969, 1448,
1267, 1137 cm-1. Anal. Calcd for C18H20O3S: C, 68.33; H, 6.24.
Found: C, 67.96; H, 6.24.
P r ep a r a tion of 1-(2-In d en yl)-2-(3-in d en yl)eth a n e (5a ).
To a solution of sulfone 6 (13.5 g, 33.7 mmol) in THF (170 mL)
at -78 °C was added HMPA (17 mL) followed by dropwise
addition of n-BuLi (58.8 mL of a 2.32 M solution in hexane,
136.5 mmol). The deep red solution was stirred 2 h before
quenching by addition of 10% HCl. The reaction mixture was
extracted with two portions of Et2O and the combined organic
extract was washed with H2O and brine, and then dried
(MgSO4). The solvents were removed by rotary evaporation.
The crude product was recrystallized from EtOH-acetone
P r ep a r a t ion of 2-(2-P h en yl-2-h yd r oxyet h yl)-2-(p h e-
n ylsu lfon yl)in d a n e (12c). Epoxide adduct 12c was prepared
analogously to 12a from 7 (1.65 g, 6.4 mmol) with styrene oxide
(0.85 g, 7.0 mmol): yield 64% (1.56 g, recrystallized from
1
yielding 7.5 g (86%) of 5a ; mp 85-87 °C; H NMR δ 2.88 (s,
4H), 3.32 (s, 2H), 3.36 (s, 2H), 6.24 (s, 1H), 6.58 (s, 1H), 7.10-
7.47 (m, 8H); 13C NMR δ 27.1, 29.6, 37.8, 41.1, 118.8, 120.0,
123.4, 123.7, 123.8, 124.6, 126.0, 126.2, 126.4, 128.0, 143.0,
143.7, 144.4, 145.3, 145.5, 150.1; IR (KBr) 3062, 3016, 2898,
1610, 1461, 1392 cm-1. Anal. Calcd for C20H18: C, 92.98; H,
7.02. Found: C, 92.97; H, 7.01.
1
EtOH), as a white solid; mp 144.4-146.3 °C; H NMR δ 2.34
(d, J ) 5.8 Hz, 2H), 2.53 (d, J ) 3.5 Hz, 1H), 3.21 (d, J ) 11.7
Hz, 1H), 3.27 (d, J ) 11.1 Hz, 1H), 3.76 (d, J ) 17.0 Hz, 1H),
3.87 (d, J ) 17.0 Hz, 1H), 5.00 (m, 1H), 6.99-7.09 (m, 4H),
7.20-7.31 (m, 5H), 7.43 (m, 2H), 7.54 (dt, J ) 7.6, 1.2 Hz, 1H),
7.85 (m, 2H); 13C NMR δ 40.1, 40.2, 44.9, 70.9, 72.5, 124.1,
124.2, 125.6, 127.0, 127.1, 127.6, 128.5, 128.8, 130.1, 133.7,
136.2, 139.5, 139.6, 144.5; IR (KBr) 3511, 3027, 2942, 1448,
1282, 1135. Anal. Calcd for C23H22O3S: C, 72.99; H, 5.86.
Found: C, 72.21; H, 5.74.
P r ep a r a tion of [Eth ylen e-1-(η5-in d en -1-yl)-2-(η5-in d en -
2′-yl)]tita n iu m Dich lor id e (13). To a solution of bisindene
5a (797 mg, 3.08 mmol) in THF (20 mL) at -78 °C was added
n-BuLi (2.6 mL of a 2.32 M solution in hexane, 5.95 mmol).
The reaction mixture was stirred 15 min to result in a pink
slurry that was then warmed to room temperature. The
resultant deep red solution was stirred 12 h. In a separate
flask, TiCl4‚2THF (1.03 g, 3.10 mmol) was dissolved in THF
(55 mL). The bisindene dianion and TiCl4 solutions were
simultaneously added dropwise over 30 min via cannula to a
third flask containing 15 mL of THF cooled to -40 °C. The
reaction mixture was warmed to room temperature and stirred
an additional 1.5 h. The reaction solvent was removed by
distillation in vacuo. The dark red residue was redissolved in
CH2Cl2 and filtered through a pad of Celite. The filtrate was
condensed in vacuo and the solids washed with Et2O to afford
778 mg (67%) of the crude titanocene, which was used in the
next reaction without further purification; 1H NMR δ 3.46 (m,
2H), 3.85 (m, 2H), 6.19 (d, J ) 2.3 Hz, 1H), 6.48 (d, J ) 3.5
Hz, 1H), 6.50 (d, J ) 2.3 Hz, 1H), 6.97 (d, J ) 3.5 Hz, 1H),
7.24-7.69 (m, 8H); 13C NMR δ 28.2, 31.5, 107.1, 113.2, 115.7,
121.5, 122.7, 123.5, 125.7, 125.9, 126.4, 127.8, 127.9, 128.4,
128.8, 129.4, 129.8, 131.8, 133.2, 140.2.
P r ep a r a tion of [Eth ylen e-1-(η5-4,5,6,7-tetr a h yd r oin -
d en -1-yl)-2-(η5-4,5,6,7-t et r a h yd r o-in d en -2′-yl)]t it a n iu m
Dich lor id e (4). A mixture of titanocene 13 (600 mg, 1.60
mmol) and PtO2 (73 mg, 0.32 mmol) in THF (8.0 mL) was
stirred under hydrogen at room temperature and ambient
pressure for 36 h. The reaction mixture was filtered through
a pad of Celite and the filtrate was condensed in vacuo. The
deep red residue was dissolved in toluene and passed through
a short column of BioBeads SX-2 (∼4 g), eluting with toluene.
P r ep a r a tion of 2-(2-Iod oeth yl)-2-(p h en ylsu lfon yl)in -
d a n e (10b). To a solution of hydroxysulfone 12 (27.0 g, 89.3
mmol) in a 1:1 mixture of Et2O:CH3CN (446 mL) at room
temperature was added Ph3P (70.3 g, 268 mmol) and imidazole
(18.2 g, 268 mmol). The solution was cooled to 0 °C and I2 (68.0
g, 268 mmol) was added in one portion. The dark brown
reaction mixture was immediately warmed to room tempera-
ture and stirred 3 h before quenching by addition of aq NH4-
Cl. The reaction mixture was extracted with two portions of
EtOAc and the combined organic extract was washed succes-
sively with H2O and brine and then dried (MgSO4). The
solvents were removed by rotary evaporation. The crude
product was washed in a fritted glass funnel with cold absolute
ethanol and the retentate was collected. The ethanol filtrate
was evaporated and the solid residue was again washed in a
funnel with cold ethanol. The two retentate crops were
combined and recrystallized from ethanol to obtain 29.4 g
(80%) of 10b as fine white needles; mp 140-143 °C; 1H NMR
δ 2.49 (m, 2H), 2.94 (d, J ) 17.0 Hz, 2H), 3.02 (m, 2H), 3.81
(d, J ) 16.4 Hz, 2H), 7.07-7.105 (m, 4H), 7.52-7.67 (m, 3H),
7.87-7.90 (m, 2H); 13C NMR δ -2.24, 38.8, 41.2, 73.5, 124.2,
127.4, 129.1, 129.9, 134.0, 136.0, 139.0; IR (KBr) 3053, 2902,
1448, 1288, 1135 cm-1. Anal. Calcd for C17H17IO2S: C, 49.52;
H, 4.16. Found: C, 49.51; H, 4.15.
P r ep a r a tion of 2-(2-In d en -3-yleth yl)-2-(p h en ylsu lfo-
n yl)in d a n e (6). To a solution of indene (11.7 g, 100.5 mmol)
J . Org. Chem, Vol. 68, No. 22, 2003 8451