5982 J. Am. Chem. Soc., Vol. 122, No. 25, 2000
de Armas et al.
conocene dichloride was purchase from Boulder Scientific and recrys-
tallized from anhydrous toluene. Alkyl bromides were purchased from
Aldrich and distilled from anhydrous calcium chloride. Indene and
styrene were purchased from Aldrich and distilled over calcium hydride.
20.0, 17.5. HRMS Calcd for C19
Calcd for C19
Tetracycle 25: IR (NaCl) 3018 (m), 2907 (m), 1598 (m), 1490 (s),
H
16: 244.1252. Found: 244.1250. Anal.
H
16: C, 93.40; H, 6.60. Found: C, 93.43; H, 6.83.
1
1462 (m), 1456 (m), 1441 (w). H NMR (400 MHz, CDCl
3
) δ 7.53
(
7
1H, d, J ) 5.6 Hz), 7.45-7.40 (2H, m), 7.38-7.32 (2H, m), 7.30-
Representative Experimental Procedure for the Zr-Catalyzed
Alkylation of Indene. A 10 mL flame-dried round-bottom flask was
charged with 100 mg (0.86 mmol) of indene 14, 194 mg (0.86 mmol)
of tosylate 15, and 3.36 mL of THF. To this mixture was added 12.6
.14 (4H, m), 4.24-4.20 (1H, m), 3.85-3.78 (2H, m), 2.99-2.91 (1H,
13
m), 2.87-2.77 (2H, m), 1.99-1.92 (1H, m). C NMR (400 MHz,
CDCl ) δ 181.2, 147.6, 141.9, 133.7, 132.1, 129.5, 129.1, 128.9, 128.6,
27.7, 126.3, 125.9, 60.2, 54.0, 44.5, 32.1, 30.0.
2-(2-Methoxyphenyl)-decane (28b): IR (NaCl) 2962 (m), 2930 (s),
2855 (m), 1602 (w), 1495 (m), 1464 (w), 1287 (w), 1237 (m), 1036
3
1
2 2
mg (0.043 mmol) Cp ZrCl and 0.95 mL (1.72 mmol) of a 1.8 M
solution of n-BuMgCl (tetrahydrofuran) in a dropwise fashion. The
resulting mixture was allowed to stir at 22 °C for 4.5 h. The solution
was then cooled to 0 °C (ice bath). At this point, the reaction was
quenched by the dropwise addition of 3 mL of a saturated solution of
1
(w). H NMR (400 MHz, CDCl ) δ 7.20-7.12 (2H, m), 6.92 (1H, t, J
3
) 7.3 Hz), 6.85 (1H, d, J ) 8.0 Hz), 3.81 (3H, s), 3.22-3.12 (1H, m),
1.66-1.42 (2H, m), 1.34-1.08 (12H, m), 0.87 (3H, t, J ) 6.8 Hz).
NaHCO
3
. The resulting mixture was washed with 3 × 25 mL of Et
2
O.
1
3
The combined organic layers were dried over MgSO
4
, filtered, and
C NMR (400 MHz, CDCl
56.1, 37.8, 32.6, 32.4, 30.5, 30.3, 30.0, 28.4, 23.4, 21.7, 14.8. HRMS
Calcd for C17 28O: 248.2140. Found: 248.2147. Anal. Calcd for
28O: C, 82.20; H, 11.36. Found: C, 81.86; H, 11.37.
-(1-Octylprop-2-enyl)-phenol (41): IR (NaCl) 3471 (br), 2930
3
) δ 157.7, 137.0, 127.4, 127.1, 121.2, 111.1,
concentrated in vacuo to afford a pale yellow oil. Preparative thin-
layer chromatography with pentane as the eluant afforded 135 mg (0.79
mmol, 92%) of the desired alkylation product 16.
H
17
C H
2
Representative Experimental Procedure for the Zr-Catalyzed
Alkylation of Chromenes. A 10 mL flame-dried round-bottom flask
was charged with 100 mg (0.76 mmol) of chromene 40, 216 mg (0.76
mmol) of tosylate 20, and 3.37 mL of THF. To this mixture was added
1
(
s), 2855 (m), 1590 (w), 1457 (m), 1331 (w), 1212 (w), 916 (w). H
NMR (400 MHz, CDCl ) δ 7.14-7.09 (2H, m), 6.90 (1H, ddd, J )
.6, 7.3, 1.1 Hz), 6.89 (1H, dd, J ) 7.8, 0.9 Hz), 6.04-5.96 (1H, m),
.15-5.11 (2H, m), 4.93 (1H, s), 3.52-3.46 (1H, m), 1.75 (2H, dd, J
3
7
5
)
1
1.1 mg (0.038 mmol) of Cp
2 2
ZrCl and 0.980 mL (1.52 mmol) of a
1
3
15.1, 7.4 Hz), 1.40-1.19 (12H, m), 0.87 (3H, t, J ) 7.0 Hz).
) 154.4, 142.3, 130.2, 129.2, 128.1, 121.6,
16.9, 115.5, 44.4, 34.0, 32.6, 30.3, 30.2, 30.0, 28.2, 23.3, 16.0. HRMS
C
1
.55 M solution of n-BuMgCl (tetrahydrofuran) in a dropwise fashion.
NMR (400 MHz, CDCl
3
The flask was equipped with a condenser, and the resulting mixture
was heated at 55 °C for 12 h. The reaction mixture was then allowed
to cool slowly to 0 °C. Once at 0 °C, the reaction was quenched by the
1
Calcd for C17H26O: 246.1984. Found: 246.1980. Anal. Calcd for
C
17
H
26O: C, 82.87; H, 10.64. Found: C, 83.04; H, 10.90.
-(1-(1-Methylethyl)prop-2-enyl)-phenol (44): IR (NaCl) 3069
br), 2962 (s), 2873 (m), 1590 (w), 1501 (m), 1457 (s), 1381 (w), 1331
dropwise addition of 3 mL of a saturated solution of NaHCO
resulting mixture was then washed with 3 × 25 mL of Et O. The
combined organic layers were dried over MgSO , filtered, and
concentrated in vacuo to afford a pale yellow oil. Silica gel chroma-
tography (20:1 pentanes:Et O) afforded 143 mg (0.58 mmol, 77%) of
the desired alkylation product 41.
-(3-Butenyl)-indene (16): IR (NaCl) 3069 (m), 2930 (m), 1640
3
. The
2
2
(
(
(
4
1
w), 916 (m). H NMR (400 MHz, CDCl
1H, dd, J ) 7.6, 7.6 Hz), 6.77 (1H, d, J ) 8.4 Hz), 6.05 (1H, ddd, J
17.2, 9.6, 9.6 Hz), 5.14-5.04 (2H, m), 4.72 (1H, s), 3.22 (1H, dd,
J ) 8.8, 8.8 Hz), 2.14-2.02 (1H, m), 1.08 (3H, d, J ) 6.8 Hz), 0.80
) δ 153.0, 140.1,
29.7, 128.8, 126.9, 120.8, 115.8, 115.4, 51.7, 31.2, 21.2, 21.0. HRMS
3
) δ 7.16-7.04 (2H, m), 6.91
2
)
3
(
1
3H, d, J ) 6.8 Hz). 13C NMR (400 MHz, CDCl
3
1
(
m), 1464 (m) 1369(w), 916 (s). H NMR (400 MHz, CDCl
3
) δ 7.43
(1H, dd, J ) 7.6, 0.8 Hz), 7.36 (1H, dd, J ) 7.6, 0.8 Hz), 7.26 (1H,
Calcd for C12H16O: 176.1201. Found: 176.1205. Anal. Calcd. for
ddd, J ) 7.6, 7.6, 0.8 Hz), 7.20 (1H, ddd, J ) 7.6, 7.6, 0.8 Hz), 6.82
1H, d, J ) 5.6 Hz), 6.56 (1H, dd, J ) 5.6, 1.6 Hz), 5.92-5.80 (1H,
m), 5.09-4.96 (2H, m), 3.50 (1H, m), 2.25-2.08 (2H, m), 2.07-1.96
C
12
H
16O: C, 81.77; H, 9.15. Found: C, 81.94; H, 8.85.
-(1-(4-Methylpent-3-enyl)-4-methylpent-2-enyl)-phenol (47): IR
NaCl) 3465 (br), 2962 (s), 1590 (w), 1451 (m), 1212 (w), 1092 (w),
(
2
(
1
3
(
1
3
1H, m), 1.68-1.56 (1H, m). C NMR (400 MHz, CDCl
3
) δ 147.5,
44.1, 138.8, 138.4, 130.6, 126.3, 124.6, 122.7, 120.9, 114.7, 49.9,
1.6, 30.8. HRMS Calcd for C13 14: 170.1096. Found: 170.1095. Anal.
14: C, 91.71; H, 8.21. Found: C, 91.46; H, 8.10.
-(3-Butynyl)-indene (18): IR (NaCl) 3308 (m), 3069 (w), 2930
1
9
3
66 (w). H NMR (400 MHz, CDCl ; cis and trans) δ 7.20-7.04 (4H,
m), 6.94-6.86 (2H, m), 6.82 (1H, d, J ) 7.2 Hz), 6.76 (1H, d, J ) 8.0
Hz), 5.66-5.48 (2H, m), 5.42-5.28 (2H, m), 5.18-5.08 (3H, m), 4.86
H
Calcd for C13
H
(
1H, s), 3.83 (1H, m), 3.38 (1H, m), 2.80-2.64 (1H, m), 2.38-2.24
3
(
1H, m), 2.30-1.86 (9H, m), 1.85-1.58 (9H, m), 1.56 (3H, d, J ) 5.2
1
(
m), 2118 (w), 1464 (m). H NMR (500 MHz, CDCl
3
) δ 7.45 (1H, d,
13
Hz), 1.04-0.92 (9H, m), 0.87 (3H, d, J ) 6.4 Hz). C NMR (400
J ) 6.0 Hz), 7.38 (1H, d, J ) 6.0 Hz), 7.29 (1H, dd, J ) 6.0, 5.6 Hz),
MHz, CDCl
3
; cis and trans) δ 153.9, 153.0, 138.6, 132.0, 131.2, 129.5,
27.8, 127.1, 126.6, 123.8, 120.4, 116.0, 115.5, 42.1, 36.6, 35.4, 33.4,
1.0, 26.9, 26.0, 25.6, 23.0, 22.7, 22.4, 17.6. HRMS Calcd for
26O: 258.1984. Found: 258.1992. Anal. Calcd for C18 26O: C,
3.67; H, )10.14. Found: C, 83.26; H, 10.09.
-(1-(Pent-2-enyl)-oct-8-enyl)-phenol (50): IR (NaCl) 3471 (br),
930 (s), 2861 (m), 1640 (w), 1596 (w), 1457 (m), 1325 (w), 1206
7
.22 (1H, dd, J ) 6.0, 6.0 Hz), 6.86 (1H, dd, J ) 4.6, 1.6 Hz), 6.57
1
3
C
(
2
1H, dd, J ) 4.6, 1.2 Hz), 3.69-3.64 (1H, m), 2.33-2.22 (1H, m),
1
3
.03 (1H, t, J ) 2.0 Hz), 1.88-1.78 (1H, m). C NMR (500 MHz,
) δ 147.6, 145.0, 138.9, 132.2, 127.4, 125.5, 123.6, 121.8, 84.8,
9.8, 49.9, 30.9, 17.1. HRMS Calcd for C13 12: 168.0939. Found:
67.0858. Anal. Calcd for C13 12: C, 92.81; H, 7.19. Found: C, 92.83;
18
H
H
CDCl
6
1
3
8
H
2
H
2
(
H, 7.01.
1
3
w), 910 (m). H NMR (500 MHz, CDCl ; cis and trans) δ 7.17 (1H,
3
-(Octyl)-6,7-methoxyindene (23): IR (NaCl) 2924 (s), 2855 (m),
d, J ) 6.0 Hz), 7.14-7.02 (3H, m), 6.93-6.87 (2H, m), 6.80 (1H, d,
J ) 6.8 Hz), 6.76 (1H, d, J ) 6.4 Hz), 5.86-5.75 (2H, m), 5.62-5.56
1
1
489 (m), 1464 (w), 1300 (w), 1218 (m), 117 (w), 1073 (w). H NMR
(
1
3
400 MHz, CDCl ) δ 7.00 (1H, s), 6.92 (1H, s), 6.71 (1H, dd, J ) 5.5,
3
(
1H, m), 5.54-5.46 (1H, m), 5.12 (1H, s), 5.01-4.90 (4H, m), 4.86
.8 Hz), 6.46 (1H, dd, J ) 5.5, 1.8 Hz), 3.91 (3H, s), 3.90 (1H, s),
.42-3.36 (1H, m), 1.92-1.82 (1H, m), 1.50-1.21 (13H, m), 0.88
(1H, s), 3.84-3.77 (1H, m), 3.43-3.37 (1H, m), 2.20-1.98 (10H, m),
13
1
.80-1.56 (4H, m), 1.44-1.20 (20H, m), 0.94-0.84 (6H, m). C NMR
1
3
(3H, t, J ) 7.0 Hz). C NMR (400 MHz, CDCl
3
) δ 148.8, 147.8,
41.2, 138.9, 137.5, 131.0, 107.9, 105.3, 57.0, 56.8, 51.3, 32.6, 32.5,
0.6, 30.2, 30.0, 28.3, 23.4, 14.8. HRMS Calcd for C19 : 288.2089.
: C, 79.12; H, 9.78.
(
500 MHz, CDCl
3
; cis and trans) δ 153.9, 153.2, 139.2, 133.0, 132.7,
1
3
1
1
2
2
31.5, 131.1, 130.0, 128.3, 127.8, 127.3, 121.9, 120.9, 120.8, 116.2,
15.8, 114.1, 43.0, 37.0, 35.2, 34.6, 33.8, 33.6, 29.7, 29.5, 29.4, 29.1,
28 2
H O
Found: 288.2087. Anal. Calcd for C19
Found: C, 79.35; H, 9.75.
28 2
H O
9.0, 28.9, 27.5, 27.4, 22.7, 13.8, 13.6. HRMS Calcd for C20
H30O:
86.2297. Found: 286.2295. Anal. Calcd for C20 30O: C, 83.86; H,
H
3
-(4-Phenyl-3-butynyl)-indene (24): IR (NaCl) 3061 (m), 2925 (m),
10.56. Found: C, 83.59; H, 10.52.
2-(1-Octyl-3-phenyl-allyl)-phenol (52): IR (NaCl) 3522 (br), 3031-
1
1
490 (s), 1460 (m), 1441 (m). H NMR (400 MHz, CDCl
3
) δ 7.48
(
(
(
1H, d, J ) 6.8 Hz), 7.42-7.35 (3H, m), 7.32-7.18 (5H, m), 6.84
1H, dd, J ) 5.6, 1.2 Hz), 6.61 (1H, dd, J ) 5.6, 1.6 Hz), 3.74-3.68
1H, m), 2.49 (2H, t, J ) 7.2 Hz), 2.28-2.15 (1H, m), 1.94-1.82 (1H,
(m), 2924 (s), 2855 (s), 1602 (m), 1501 (s), 1457 (s), 1331 (m), 1243
1
(s), 972 (s). H NMR (400 MHz, CDCl
3
; cis and trans) δ 7.38-7.05
(14H, m), 6.96-6.74 (4H, m), 6.58 (1H, d, J ) 16.0 Hz), 6.47 (1H, d,
J ) 16.03 Hz), 6.40-6.27 (2H, m), 4.85 (1H, s), 4.82 (1H, s), 3.69
(1H, dd, J ) 14.4, 7.2 Hz), 3.42 (1H, dd, J ) 15.2, 8.2 Hz), 1.87-
1
3
m). C NMR (400 MHz, CDCl
1
3
) δ 146.9, 144.3, 138.4, 131.5, 131.4,
28.2, 127.6, 126.6, 124.8, 122.9, 121.1, 89.7, 81.5, 49.3, 30.5, 29.7,