Fern a´ ndez-Mateos et al.
775, 735, 702 cm-1. 1H NMR CDCl
, δ: 0.67 (3H, s), 0.90-
1
3
6.1, 19.6, 21.4, 23.5, 26.6, 28.2 (2C), 28.8, 29.8, 33.8, 34.4,
3
9.6, 40.1, 56.6, 126.7, 136.7, 220.8. MS EI, m/z (relative
1.90 (6H, m), 1.05 (3H, s), 1.10 (3H, s), 1.84 (1H, s), 2.52 (1H,
dd, J ) 9.4, J ) 20 Hz), 2.76 (1H, dd, J ) 11, J ) 20 Hz),
3.66 (1H, dd, J ) 9.4, J ) 11 Hz), 7.15-7.40 (5H, m).
NMR CDCl , δ: 17.9, 24.0, 26.8, 29.6, 32.8, 33.0, 40.3, 42.0,
2.6, 45.3, 65.7, 126.6, 127.8 (2C), 129.0 (2C), 138.5, 220.1. MS
+
intensity): 246 (M , 100), 231 (20), 190 (51), 175 (65), 119 (30),
7
1
2
1
2
+
13
7 (37). HRMS (EI): 246.1990 (M , C17
H
26
O
2
); calcd, 246.1984.
1
2
C
Eluting with hexane/AcOEt (98/2) furnished 3a,6,6,9a-
3
4
tetramethyl-3a,4,5,5a,6,7,8,9,9a,9b-decahydrocyclopenta[a]naph-
thalen-1-one 9a (12 mg, 4 µmol, 25%).
+
EI, m/z (relative intensity): 256 (M , 30), 109 (100), 91 (13),
7
+
7 (19). HRMS (EI): 256.1795 (M , C18
H
24O); calcd, 256.1827.
Rea ction of 3a w ith 9-BBN. To a solution of 3a (600 mg,
.37 mmol) in THF (6 mL) was slowly added 9-BBN (411 mg,
.74 mmol). The reaction mixture was stirred under argon at
Anal. Calcd for C18
H, 9.11.
H24O: C, 84.32; H, 9.44. Found: C, 84.50;
3
6
room temperature for 15 min, and then MeOH was slowly
added, stirring for 1 h. Removal of the solvent afforded a crude
product, which was purified by flash chromatography. Eluting
3-P h en yl-3a,6,6,9a-tetr am eth yldodecah ydr ocyclopen ta-
[a ]n a p h th a len -1-on e 14a . Bromobenzene (1.49 mL, 14.2
mmol), zinc bromide (1.60 g, 7.1 mmol), and Li (199 mg, 28.4
mmol) in anhydrous diethyl ether (70 mL) under an argon
atmosphere were sonicated in a 250 mL Erlenmeyer flask
equipped with a magnetic stirring bar. The mixture turned
black almost immediately, and the lithium was totally con-
sumed within 60 min. Sonication was then discontinued, and
a mixture of enone 9a (350 mg, 1.42 mmol) and nickel
acetylacetonate (18 mg, 71 µmol) in diethyl ether (7 mL) was
then added and the resulting mixture magnetically stirred for
2 h at room temperature. Then, an aqueous solution of
with hexane/Et
2
O (95/5) furnished 3a,7,7-trimethyl-3a,4,5,6,7,-
7
a-tetrahydro-1H-inden-1-ol 11b (320 mg, 1.78 mmol, 53%) as
-
1 1
a colorless oil. IR, ν: 3447, 2940, 2864 cm . H NMR CDCl
δ: 1.07 (3H, s), 1.15-1.30 (2H, m), 1.17 (3H, s), 1.22 (3H, s),
.29 (1H, d, J ) 5.5 Hz), 1.45-1.90 (5H, m), 4.61 (1H, dd, J
3
,
1
1
)
2.7, J
2
) 5.5 Hz), 5.81 (1H, dd, J
1
) 2.7, J
2
) 5.7 Hz), 5.92
1
3
(
1H, d, J ) 5.7 Hz). C NMR CDCl
3
, δ: 19.5, 26.3, 28.8, 31.1,
3
2.6, 37.5, 39.0, 45.2, 57.8, 79.4, 129.4, 150.7. MS EI, m/z
+
(relative intensity): 180 (M , 5), 165 (10), 162 (23), 147 (100),
+
9
1
1 (94), 55 (84). HRMS (EI): 180.1522 (M , C12
H
20O); calcd,
4
saturated NH Cl was added and the heterogeneous mixture
80.1514. Eluting with hexane/Et O (93/7) furnished 3a,7,7-
2
was stirred for 5 min. The organic layer was separated and
the aqueous phase extracted with ether. The combined organic
extracts were washed with brine. Removal of the solvent
afforded a crude residue, which was purified by flash chro-
trimethyl-3a,4,5,6,7,7a-tetrahydro-1H-inden-1-ol 11a (279 mg,
1
3
.55 mmol, 46%) as a white solid, mp 58-60 °C. IR CHCl
3
, ν:
285, 2926, 2868 cm-1
. H NMR, CDCl , δ: 0.80-1.00 (2H,
1
3
m), 1.03 (3H, s), 1.07 (3H, s), 1.19 (3H, s), 1.20-1.40 (2H, m),
1
matography. Eluting with hexane/Et
2
O (98/2) furnished 14a
.33 (1H, d, J ) 7.7 Hz), 1.40-1.60 (2H, m), 1.75 (1H, m), 4.64
(3.87 g, 1.20 mmol, 84%) as a colorless solid, mp (tBuOMe/
-
1
(
5
3
1H, d, J ) 7.7 Hz), 5.53 (1H, d, J ) 5.7 Hz), 5.64 (1H, d, J )
hexane) 118-120 °C. IR, ν: 2926, 2882, 1732, 731, 702 cm .
1
3
1
.7 Hz). C NMR CDCl
3
, δ: 18.0, 27.7, 30.1, 31.6 (2C), 36.4,
H NMR CDCl
0.92 (3H, s), 1.09 (3H, s), 1.10-1.30 (3H, m), 1.40-1.65 (5H,
m), 1.78 (1H, s), 1.90 (1H, dt, J ) 3.2, J ) 14 Hz), 2.10 (1H,
dd, J ) 1.7, J ) 13 Hz), 2.48 (1H, dd, J ) 9.1, J ) 20 Hz),
2.74 (1H, ddd, J ) 1.6, J ) 11, J
9.1, J ) 11 Hz), 7.15-7.35 (5H, m). C NMR CDCl
3
, δ: 0.68 (3H, s), 0.88 (1H, m), 0.90 (3H, s),
7.1, 46.0, 65.1, 79.4, 130.2, 145.4. MS EI, m/z (relative
+
intensity): 180 (M , 3), 165 (10), 162 (21), 147 (100), 91 (81),
5 (61). Anal. Calcd for C12 20O: C, 79.94; H, 11.18. Found:
C, 79.66; H, 11.05.
a,6,6,9a-Tetr am eth yl-3a,4,5,5a,6,7,8,9,9a,9b-decah ydr o-
H-cyclop en ta [a ]n a p h th a len -1-ol 12. To a solution of ke-
tone 9b (75 mg, 0.30 mmol) in dry ethyl ether (2.7 mL) cooled
to 0 °C was added LiAlH (75 mg, 0.30 mmol). The reaction
mixture was vigorously stirred under argon for 30 min, after
which the reaction was quenched with Na SO ‚10H O. The
t
d
5
H
1
2
1
2
1
2
3
) 20 Hz), 3.68 (1H, dd, J
1
1
3
)
2
3
, δ:
3
1
4
2
1
7.0, 18.1 (2C), 22.0, 27.3, 33.3, 33.5, 34.6, 37.5, 41.4, 41.7,
2.5, 42.9, 46.1, 53.8, 71.7, 126.7, 127.9 (2C), 129.2 (2C), 138.4,
1
+
20.7. MS EI, m/z (relative intensity): 324 (M , 44), 309 (5),
4
+
73 (95), 123 (32), 104 (100). HRMS (EI): 324.2487 (M ,
C
23
H
32O); calcd, 324.2453. Anal. Calcd for C23
H32O: C, 85.13;
2
4
2
H, 9.94. Found: C, 85.23; H, 10.13.
resulting mixture was filtered, and then the filtrate was
evaporated under reduced pressure to afford a white solid
identified as 12 (76 mg, 0.30 mmol, 100%), mp (t-BuOMe/
3-P h en yl-3a,6,6,9a-tetr am eth yldodecah ydr ocyclopen ta-
[a ]n a p h th a len -1-on e 14b. Bromobenzene (0.43 mL, 4.1
mmol), zinc bromide (450 mg, 2 mmol), and Li (57 mg, 8.2
mmol) in anhydrous diethyl ether (4 mL) under an argon
atmosphere were sonicated in a 250 mL Erlenmeyer flask
equipped with a magnetic stirring bar. The mixture turned
black almost immediately, and the lithium was totally con-
sumed within 60 min. Sonication was then discontinued, and
a mixture of enone 9b (100 mg, 0.41 mmol) and nickel
acetylacetonate (5 mg, 0.02 µmol) in diethyl ether (4 mL) was
then added and the resulting mixture magnetically stirred for
2 h at room temperature. Then, an aqueous solution of
-
1 1
hexane) 115-117 °C. IR Nujol, ν: 3320, 2928, 2868 cm . H
NMR CDCl , δ: 0.80-1.80 (13, m), 0.83 (3H, s), 0.87 (3H, s),
.11 (3H, s), 1.28 (3H, s), 4.80 (1H, d, J ) 7.8 Hz), 5.49 (1H, d,
3
1
1
3
J ) 5.7 Hz), 5.64 (1H, d, J ) 5.7 Hz) ppm. C NMR CDCl
1
4
3
, δ:
8.0, 18.3, 22.0, 23.8, 28.0, 33.0, 33.5, 36.2, 39.6, 40.0, 42.3,
6.1, 49.7, 71.2, 78.7, 129.4, 145.7 ppm. MS EI, m/z (relative
+
intensity): 248 (M , 10), 233 (7), 215 (9), 191 (8), 152 (25), 97
100), 69 (23). Anal. Calcd for C17 28O: C, 82.20; H, 11.36.
Found: C, 82.54; H, 11.13.
a,7,7-Tr im eth yl-3-ph en yloctah ydr oin den -1-on e 13. Bro-
(
H
3
mobenzene (1.17 mL, 11.2 mmol), zinc bromide (1.26 g, 5.6
mmol), and Li (157 mg, 22.4 mmol) in anhydrous diethyl ether
4
saturated NH Cl was added, and the heterogeneous mixture
was stirred for 5 min. The organic layer was separated and
the aqueous phase extracted with ether. The combined organic
extracts were washed with brine. Removal of the solvent
afforded a crude residue, which was purified by flash chro-
(55 mL) under an argon atmosphere were sonicated in a 250
mL Erlenmeyer flask equipped with a magnetic stirring bar.
The mixture turned black almost immediately, and the lithium
was totally consumed within 60 min. Sonication was then
discontinued, and a mixture of enone 3 (200 mg, 1.2 mmol)
and nickel acetylacetonate (14 mg, 56 mmol) in diethyl ether
matography. Eluting with hexane/Et
2
O (80/20) furnished 14b
(107 mg, 0.33 mmol, 80%) as a white solid, mp 132-134 °C.
-
1
1
IR, ν: 2922, 2870, 1726, 756, 702 cm
3
. H NMR CDCl , δ:
(
5.5 mL) was then added and the resulting mixture magneti-
cally stirred for 3 h at room temperature. Then, an aqueous
solution of saturated NH Cl was added and the heterogeneous
0.80 (3H, s), 0.86 (3H, s), 0.92 (3H, s), 1.01 (3H, s), 1.07 (1H,
m), 1.15-1.75 (9H, m), 1.94 (1H, s), 2.48 (1H, d, J ) 19 Hz),
4
2.81 (1H, d, J ) 10 Hz), 2.90 (1H, m), 2.95 (1H, dd, J
1
) 10, J
2
1
3
mixture stirred for 5 min. The organic layer was separated,
and the aqueous phase was extracted with ether. The com-
bined organic extracts were washed with brine. Removal of
the solvent afforded a crude residue, which was purified by
) 19 Hz), 7.05-7.15 (2H, m), 7.20-7.35 (3H, m). C NMR
CDCl
3
, δ: 18.1, 19.6, 21.6, 23.2, 26.8, 32.9, 33.2, 34.5, 38.0,
39.2, 42.0, 44.7, 45.2, 49.6, 50.0, 64.1, 126.4, 128.1 (2C), 128.4
+
(2C), 143.6, 220.2. MS EI, m/z (relative intensity): 324 (M ,
flash chromatography. Eluting with hexane/Et
the phenyl ketone 13 (212 mg, 0.83 mmol, 74%) as a colorless
solid, mp (tBuOMe/hexane) 95-97 °C. IR, ν: 2924, 2868, 1730,
2
O (96/4) gave
3), 230 (14), 153 (43), 89 (55), 77 (100). HRMS (EI): 324.2429
+
(M , C23
H
32O); calcd, 324.2453. Anal. Calcd for C23
H
32O: C,
85.13; H, 9.94. Found: C, 85.54; H, 9.87.
3
590 J . Org. Chem., Vol. 68, No. 9, 2003