Xi et al.
10.30 (CH3), 14.17 (CH3), 14.52 (CH3), 18.25 (CH2), 22.99 (CH2),
28.72 (CH2), 32.37 (CH2), 49.50 (CH), 118.16 (CH), 121.47 (CH),
125.40 (CH), 126.61 (CH), 127.18 (2CH), 128.67 (2CH), 131.97
(C), 136.86 (C), 142.21 (C), 146.28 (C), 146.74 (C), 147.48 (C).
HRMS calcd for C22H26, 290.2035; found, 290.2027.
1,2-Dip r op yl-3,4-d im eth ylin d en e (4e): light yellow liq-
uid; isolated yield 40% (182 mg), GC yield 58%; 1H NMR
(CDCl3, Me4Si) δ 0.80 (t, J ) 7.2 Hz, 3H), 0.84-0.90 (m, 1H),
0.93 (t, J ) 7.2 Hz, 3H), 0.97-1.11 (m, 1H), 1.38-1.67 (m, 3H),
1.84-1.96 (m, 1H), 2.14-2.24 (m, 4H), 2.40-2.51 (m, 1H), 2.58
(s, 3H), 3.20-3.40 (br, 1H), 6.95-7.02 (m, 2H), 7.16-7.24 (m,
1H); 13C NMR (CDCl3, Me4Si) δ 14.26 (2CH3), 14.60 (CH3),
17.81 (CH2), 20.44 (CH3), 23.16 (CH2), 28.47 (CH2), 32.53 (CH2),
49.06 (CH), 120.49 (CH), 123.58 (CH), 129.25 (CH), 129.97 (C),
133.65 (C), 144.31 (C), 146.05 (C), 147.59 (C). HRMS calcd for
(m, 6H), 1.20-1.68 (m, 5H), 1.72-1.82 (m, 1H), 1.94-2.10 (br,
3H), 2.24-2.60 (m, 2H), 2.87-3.76 (br, 1H), 6.98 (d, J ) 4.8
Hz, 1H), 7.10 (d, J ) 4.8 Hz, 1H); 13C NMR (CDCl3, Me4Si) δ
11.84 (CH3), 14.13 (CH3), 14.35 (CH3), 20.01 (CH2), 23.56 (CH2),
28.92 (CH2), 32.30 (CH2), 47.73 (CH), 122.30 (CH), 122.44 (CH),
128.76 (C), 147.04 (C), 148.09 (C), 148.61 (C). HRMS calcd for
C
14H20S, 220.1286; found, 220.1282.
1,2-Dip r op yl-3-m eth ylben zo[g]in d en e (4l): light yellow
liquid; isolated yield 63% (332 mg), GC yield 88%; 1H NMR
(CDCl3, Me4Si) δ 0.39-0.59 (m, 1H), 0.66 (t, J ) 7.2 Hz, 3H),
0.71-0.86 (m, 1H), 0.88-1.07 (m, 3H), 1.35-1.76 (m, 2H),
1.91-2.10 (m, 4H), 2.24-2.36 (m, 2H), 2.48-2.67 (m, 1H),
3.69-3.96 (br, 1H), 7.23-7.56 (m, 3H), 7.72 (d, J ) 7.8 Hz,
1H), 7.86 (d, J ) 7.8 Hz, 1H), 8.02 (d, J ) 7.8 Hz, 1H); 13C
NMR (CDCl3, Me4Si) δ 10.43 (CH3), 14.21 (CH3), 14.41 (CH3),
16.39 (CH2), 23.29 (CH2), 28.67 (CH2), 32.90 (CH2), 49.16 (CH),
118.09 (CH), 123.25 (CH), 123.58 (CH), 125.72 (CH), 127.13
(CH), 129.15 (CH), 129.56 (C), 131.51 (C), 132.60 (C), 141.50
(C), 144.39 (C), 146.36 (C). HRMS calcd for C20H24, 264.1878;
found, 264.1881.
C
17H24, 228.1878; found, 228.1871.
1,2-Dip r op yl-3,4,6-tr im eth ylin d en e (4f): light yellow
liquid; isolated yield 52% (252 mg), GC yield 70%; 1H NMR
(CDCl3, Me4Si) δ 0.29-1.23 (m, 8H), 1.26-2.02 (m, 4H), 2.16-
3.12 (m, 11H), 3.22-3.73 (br, 1H), 6.79 (s, 1H), 7.01 (s, 1H);
13C NMR (CDCl3, Me4Si) δ 14.14 (2CH3), 14.54 (CH3), 17.83
(CH2), 20.19 (CH3), 21.15 (CH3), 23.07 (CH2), 28.35 (CH2), 32.55
(CH2), 48.82 (CH), 121.35 (CH), 129.49 (CH), 129.98 (C), 132.95
(C), 133.33 (C), 141.61 (C), 144.86 (C), 147.90 (C). HRMS calcd
for C18H26, 242.2035; found, 242.2027.
Rep r esen ta tive P r oced u r e for th e P r ep a r a tion of
In d en e Der iva tives fr om Tw o Molecu les of Alk yn es.
P r ep a r a tion of 1,2-Dip h en yl-3-m eth ylin d en e (4n ). A 20-
mL Schlenk tube under dried nitrogen was charged with
Cp2ZrCl2 (350 mg, 1.2 mmol) and THF (5 mL). The mixture
was cooled to -78 °C (dry ice/acetone bath), and then n-BuLi
(1.51 mL, 1.59 M, 2.4 mmol) was added dropwise via a syringe.
The reaction mixture was stirred at -78 °C for 1 h. After the
addition of methyldiphenylphosphine (200 mg, 1.0 mmol), the
reaction mixture was stirred at room temperature for 1 h.
Phenyltrimethylsilylacetylene (0.197 mL, 1.0 mmol) was then
added, and the reaction mixture was stirred for 1 h. After the
addition of diphenylacetylene (178 mg, 1.0 mmol), the reaction
mixture was gradually warmed to 50 °C and was stirred for 3
h. The reaction mixture was then cooled to 0 °C and quenched
with concentrated sulfuric acid (0.7 mL). After it was stirred
for 48 h at room temperature, the reaction mixture was
extracted with hexane. The extract was washed with brine and
dried over MgSO4. The solvent was evaporated in vacuo.
Column chromatography on silica gel (100:1 hexane/AcOEt)
afforded the product 4n as a yellow oil:17 isolated yield 71%
1,2-Dip r op yl-3-m eth yl-6-m eth oxyin d en e (4g): light yel-
low liquid; isolated yield 67% (327 mg), GC yield 90%; 1H NMR
(CDCl3, Me4Si) δ 0.82 (t, J ) 7.2 Hz, 3H), 0.96-1.08 (m, 4H),
1.17-1.56 (m, 2H), 1.62-1.96 (m, 3H), 2.03-2.17 (br, 3H),
2.26-2.56 (m, 2H), 3.16-3.55 (br, 1H), 3.88 (s, 3H), 6.79-6.97
(m, 1H), 7.05 (s, 1H), 7.11-7.24 (m, 1H); 13C NMR (CDCl3,
Me4Si) δ 10.23 (CH3), 14.08 (CH3), 14.43 (CH3), 17.92 (CH2),
22.94 (CH2), 28.55 (CH2), 32.36 (CH2), 49.22 (CH), 55.46
(OCH3), 109.90 (CH), 110.75 (CH), 117.99 (CH), 131.55 (C),
140.13 (C), 143.62 (C), 148.51 (C), 157.26 (C). HRMS calcd for
C
17H24O, 244.1827; found, 244.1826.
1,2-Dip r op yl-3-m eth yl-6-ch lor oin d en e (4h ): light yellow
liquid; isolated yield 51% (252 mg), GC yield 72%; 1H NMR
(CDCl3, Me4Si) δ 0.72 (t, J ) 7.3 Hz, 3H), 0.88-0.97 (m, 4H),
1.00-1.19 (m, 1H), 1.32-1.84 (m, 4H), 1.94-2.08 (br, 3H),
2.08-2.60 (m, 2H), 3.10-3.60 (br, 1H), 7.06 (dd, J ) 7.8, 1.2
Hz, 1H), 7.20 (d, J ) 7.8 Hz, 1H), 7.30 (s, 1H); 13C NMR (CDCl3,
Me4Si) δ 10.22 (CH3), 14.16 (CH3), 14.44 (CH3), 17.98 (CH2),
22.92 (CH2), 28.64 (CH2), 32.08 (CH2), 49.41 (CH), 118.72 (CH),
122.91 (CH), 126.24 (CH), 129.67 (C), 131.64 (C), 145.38 (C),
146.54 (C), 148.57 (C). HRMS calcd for C16H21Cl, 248.1332;
found, 248.1324.
1
(201 mg), GC yield 80%; H NMR (CDCl3, Me4Si) δ 2.33 (d, J
) 2.0 Hz, 3H), 4.92-4.96 (m, 1H), 7.01-7.40 (m, 14H); 13C
NMR (CDCl3, Me4Si) δ 11.90, 57.79, 119.16, 123.62, 125.44,
126.44, 126.53, 126.84, 128.07, 128.14, 128.46, 128.99, 129.37,
135.57, 136.34, 139.99, 144.97, 145.90, 148.02. HRMS calcd
for C22H18, 282.1409; found, 282.1418.
1,2-Dip h en yl-3,6-d im eth ylin d en e (4o). The procedure
was the same as that for the preparation of 4n . Column
chromatography on silica gel (100:1 hexane/AcOEt) afforded
4o as white crystals: isolated yield 73% (220 mg), GC yield
85%; mp 168.2-170.3 °C; 1H NMR (CDCl3, Me4Si) δ 2.45-
2.48 (m, 3H), 2.68 (s, 3H), 4.84-4.90 (m, 1H), 6.95-7.28 (m,
13H); 13C NMR (CDCl3, Me4Si) δ 15.65, 20.44, 57.97, 121.82,
125.26, 126.34, 126.48, 127.96, 128.20, 128.37, 129.26, 129.83,
131.19, 136.64, 136.91, 140.19, 143.15, 145.92, 148.83. Anal.
Calcd for C23H20: C, 93.20%; H, 6.80%. Found: C, 93.08%; H,
6.85%. HRMS calcd for C23H20, 296.1560; found, 296.1565.
1,2-Dip r op yl-3,6-d im eth ylin d en e (4c). 4c was obtained
1,2-Dip r op yl-3-m eth yl-6-flu or oin d en e (4i): colorless liq-
uid; isolated yield 33% (153 mg), GC yield 52%; 1H NMR
(CDCl3, Me4Si) δ 0.57-1.00 (m, 7H), 1.06-1.20 (m, 1H), 1.28-
1.74 (m, 3H), 1.78-1.92 (m, 1H), 1.98-2.12 (br, 3H), 2.16-
2.31 (m, 1H), 2.39-2.55 (m, 1H), 3.14-3.63 (br, 1H), 6.85-
6.99 (m, 1H), 7.01-7.15 (m, 2H); 13C NMR (CDCl3, Me4Si) δ
10.30 (CH3), 14.17 (CH3), 14.45 (CH3), 17.93 (CH2), 22.97 (CH2),
28.65 (CH2), 32.18 (CH2), 49.40 (d, J C-F ) 2.5 Hz, CH), 110.33
(d, J C-F ) 22.5 Hz, CH), 112.62 (d, J C-F ) 22.5 Hz, CH), 118.25
(d, J C-F ) 8.3 Hz, CH), 131.50 (C), 142.74 (C), 145.52 (C),
148.85 (d, J C-F ) 8.3 Hz, C), 161.03 (d, J C-F ) 239.3 Hz, C).
HRMS calcd for C16H21F, 232.1627; found, 232.1638.
1,2-Dipr op yl-3-m eth yl-4,5,6-tr im eth oxyin d en e (4j): yel-
low liquid; isolated yield 53% (321 mg), GC yield 80%; 1H NMR
(CDCl3, Me4Si) δ 0.67-1.17 (m, 7H), 1.20-1.46 (m, 2H), 1.52-
1.94 (m, 3H), 2.01-2.28 (m, 4H), 2.33-2.58 (m, 1H), 3.19-
3.37 (br, 1H), 3.86 (s, 3H), 3.88 (s, 3H), 3.91 (s, 3H), 6.75 (s,
1H); 13C NMR (CDCl3, Me4Si) δ 12.35 (CH3), 14.15 (CH2), 14.49
(CH2), 17.78 (CH2), 23.05 (CH2), 28.23 (CH2), 32.60 (CH2), 49.73
(CH), 56.49 (OCH3), 60.90 (OCH3), 61.58 (OCH3), 103.70 (CH),
131.53 (C), 131.76 (C), 141.31 (C), 143.35 (C), 143.69 (C),
147.29 (C), 150.77 (C). HRMS calcd for C19H28O3, 304.2038;
found, 304.2038.
in
a similar way. Column chromatography on silica gel
(hexane) afforded 4c as pale yellow liquid: isolated yield 60%
(151 mg), GC yield 70%.
1,2-Dip r op yl-3-m eth ylin d en e (4b). A 20-mL Schlenk tube
under dried nitrogen was charged with Cp2ZrCl2 (350 mg, 1.2
mmol) and THF (5 mL). The mixture was cooled to -78 °C
(dry ice/acetone bath), and then n-BuLi (1.51 mL, 1.59 M, 2.4
mmol) was added dropwise via a syringe. The reaction mixture
was stirred at -78 °C for 1 h. After the addition of phenyl-
trimethylsilylacetylene (0.197 mL, 1.0 mmol), the reaction
mixture was warmed to room temperature and stirred for 3
F u sed com p ou n d 4k : dark red liquid; isolated yield 50%
1
(220 mg), GC yield 68%. H NMR (CDCl3, Me4Si) δ 0.57-1.14
(17) Pettit, W. A.; Wilson, J . W. J . Am. Chem. Soc. 1977, 99, 6372.
1256 J . Org. Chem., Vol. 68, No. 4, 2003