P e´ rez-Serrano et al.
purified and/or separated by flash chromatography (hexane/
EtOAc mixtures).
Meth od C.The enyne (2.00 mmol) was dissolved in dry
toluene (40 mL) at room temperature under argon. To this
Hz); 5.27 (d, 1H, J ) 13.5 Hz), 6.10 (s, 1H), 6.36 (s, 1H), 7.10
(t, 1H, J ) 7.7 Hz), 7.25 (t, 1H, J ) 8.2 Hz), 7.38 (d, 1H, J )
8.2 Hz), 7.57 (d, 1H, J ) 7.7 Hz); 13C NMR (CDCl
) 207.8,
3
174.6, 141.2, 136.6, 131.9, 127.1, 121.9, 120.9, 119.5, 108.5,
solution was added 2.40 mmol of Co
2
(CO)
8
, and the resulting
101.0, 66.9, 44.2, 42.8, 41.4, 38.4, 25.7, 18.0, -5.1, -5.4; IR
mixture was stirred for 2 h until total complexation of the
enyne (TLC). The reaction was refluxed for 18 h. After
filtration and solvent elimination the crude was purified and/
or separated by flash chromatography (hexane/EtOAc mix-
tures).
Meth od D.The enyne (2.00 mmol) was dissolved in dry
toluene (40 mL) at room temperature under argon. To this
2 8
solution was added 2.40 mmol of Co (CO) , and the resulting
mixture was stirred for 2 h until total complexation of the
enyne (TLC). The reaction was then cooled to -10 °C with an
ice/salt bath, and a suspension of Me NO (18.00 mmol) in
3
toluene at 0 °C was added dropwise. After 18 h of stirring,
the mixture was filtered, the solvent was evaporated under
vacuum, and the crude was purified and/or separated by flash
chromatography (hexane/EtOAc mixtures).
Meth od E.The enyne (2.00 mmol) was dissolved in dry
toluene (40 mL) at room temperature under CO atmosphere
2
(neat) 2920, 1710, 1460. Anal. Calcd for C22H29NO Si: C. 71.89;
H. 7.95; N. 3.81. Found: C. 71.96; H. 7.88; N. 3.86.
(3a S*,5R*)-5-(ter t-Bu tyld im eth ylsilyloxy)-6-m eth yl-3,-
3a ,4,5-t et r a h yd r o-6H -ciclop en t a [c]ca r b a zol-2-on e, 36.
Method A: From 0.34 g of 32 and after purification by flash
chromatography (hexane/EtOAc 4:1), 0.24 g (65%) of 36 was
obtained as a white solid, mp >190 °C dec (hexane/AcOEt).
Method B: 0.31 g (85%) of 36 was obtained. Method E: 0.18 g
1
3
(45%) of 36 was obtained: H NMR (CDCl ) 0.24 (s, 6H), 0.90
(s, 9H), 1.94 (td, 1H, J 1 ) 13.7 Hz, J 2 ) 3.3 Hz), 2.17 (dd, 1H,
J 1 ) 17.6 Hz, J 2 ) 4.4 Hz), 2.41 (dt, 1H, J ) 13.7 Hz, J ) 2.7
1
2
Hz), 2.68 (dd, 1H, J 1 ) 17.6 Hz, J ) 7.2 Hz), 3.54-3.64 (m,
2
1H), 3.79 (s, 3H), 5.17 (t, 1H, J ) 2.7 Hz), 6.33 (d, 1H, J ) 1.1
Hz), 7.28-7.37 (m, 2H), 7.39 (d, 1H, J ) 7.1 Hz), 7.76 (d, 1H,
J ) 7.7 Hz); 13C NMR (CDCl ) 207.7, 170.4, 142.6, 138.0, 124.0,
3
123.4, 121.9, 120.3, 119.0, 110.0, 108.6, 62.0, 40.2, 38.8, 34.4,
29.7, 25.6, 18.0, -3.8, -4.5; IR (KBr) 2920, 2820, 1690, 1670,
1600. Anal. Calcd For C H NO Si: C. 71.89; H. 7.95; N. 3.81.
(
1 atm), in a flask containing two times the mass of the enyne
of powdered 4 Å molecular sieves. To this solution was added
.20 mmol of Co (CO) , and the resulting mixture was stirred
2
2
29
2
Found: C. 71.99; H. 8.06; N. 3.69.
0
2
8
4
-Tr iisop r op ylsilyl-4,6,6a ,7-tetr a h yd r oin d en o[6,5,4-cd ]-
for 18 h at 65 °C. After filtration through Celite, the solvent
was evaporated under vacuum, and the crude product was
purified by flash chromatography (hexane/EtOAc mixtures).
in d ol-8-on e, 38. Method A: From 0.33 g of 37 and after
purification by flash chromatography (hexane/EtOAc 4:1), 0.22
g (50%) of 38 was obtained as a pale yellow oil. Method B:
3
a ,4-Dih yd r o-3H -b en zo[e]cyclop en t a [a ]p yr r olizin -2-
0
3
1
2
3
.18 g (60%) of 38 was obtained. Method E: 0.10 g (37%) of
on e, 12. Following method A, from 0.362 g of 1 and after
purification by flash chromatography (hexane/EtOAc 6:1-4:
8 was obtained: 1H NMR (CDCl
3
) 1.14 (d, 18H, J ) 7.1 Hz),
.64-1.77 (m, 3H), 2.30 (dd, 1H, J
.65-2.76 (m, 1H), 2.88 (dd, 1H, J
1
) 18.1 Hz, J
) 18.1 Hz, J
2
) 3.8 Hz),
) 6.0 Hz),
1
1
1
J
1
6
J
1
2
1
), 0.182 g (45%) of 12 was obtained as a yellow solid, mp 148-
1
2
49 °C (hexane/EtOAc). Following method B, 0.404 g (70%) of
.31-3.41 (m, 2H), 6.53 (d, 1H, J ) 1.6 Hz), 7.06 (s, 1H), 7.22
1
2 was obtained: H NMR (CDCl
3
) 2.55 (dd, 1H, J
) 17.0 Hz J ) 6.6 Hz), 3.77 (t,
H, J ) 9.0 Hz), 4.02-4.16 (m, 1H), 4.64 (t, 1H, J ) 8.8 Hz),
.24 (d, 1H, J ) 2.2 Hz), 6.88 (s, 1H), 7.16 (dt, 1H, J ) 7.7 Hz
) 1.1 Hz), 7.30 (dt, 1H, J ) 7.7 Hz J ) 1.1 Hz), 7.35 (d,
1
) 17.0 Hz
(t, 1H, J ) 7.7 Hz), 7.38 (d, 1H, J ) 7.7 Hz), 7.51 (d, 1H, J )
2
) 5.5 Hz), 2.83 (dd, 1H, J
1
2
13
8
1
1
.2 Hz); C NMR (CDCl
24.0, 123.9, 122.5, 116.4, 116.1, 113.8, 42.6, 39.9, 28.0, 18.0,
31
2.6. IR (neat) 1700, 1620, 1450. Anal. Calcd For C23H -
3
) 208.6, 173.5, 139.4, 131.5, 126.9,
1
2
1
2
NOSi: C. 75.56; H. 8.55; N. 3.83. Found: C. 75.68; H. 8.69;
N. 3.75.
1
3
3
H, J ) 7.7 Hz), 7.70 (d, 1H, J ) 8.2 Hz); C NMR (CDCl )
07.7, 170.0, 134.7, 134.4, 132.7, 124.1, 122.5, 120.6, 120.0,
10.2, 99.6, 48.7, 48.3, 41.0. IR (KBr) 2870, 1705, 1630, 1330.
Ack n ow led gm en t. The authors are grateful to the
DGCYT (MEC Spain, BQU2002-00137) and the Uni-
versidad San Pablo-CEU (07/03) for financial support.
A predoctoral fellowship from the Universidad San
Pablo-CEU is gratefully acknowledged by L.P.-S.
Anal. Calcd for C14
C. 80.45; H. 5.56; N. 6.57.
11S*,12a R*)-11-(ter t-Bu tyld im eth ylsilyloxy)-4,11,12,-
H11NO: C. 80.36; H. 5.30; N. 6.69. Found:
(
1
2
2a -tetr a h yd r o-1H-cyclop en ta [5,6]a zep in e[1,2-a ]in d ole-
-on e, 21. Following method A, from 0.678 g of 9 and after
purification by flash chromatography (hexane/EtOAc 10:1),
.475 g (65%) of 21 was obtained as a pale yellow oil. Following
method B, 0.540 g (75%) of 21 was obtained. Following method
0
Su p p or tin g In for m a tion Ava ila ble: Full characteriza-
tion of compounds 26, 3, 8, 4, 27, 28, 5, 6, 9, 11, 29, 30, 7, 10,
1
C, 0.300 g (40%) of 21 was obtained: H NMR (CDCl
3
) -0.13
3
1, 32, 13, 14, 15, 16, 17, 19, 20, 22, 23, 33, 34, and 35. This
(s, 3H), 0.15 (s, 3H), 0.90 (s, 9H), 1.56 (dd, 1H, J
1
) 13.2. Hz,
material is available free of charge via the Internet at
http://pubs.acs.org.
J
2
3
2
) 12.6 Hz), 2.08 (dd, 1H, J
.63 (m, 1H), 2.77 (dd, 1H, J
.71 (m, 1H), 4.98 (d, 1H, J ) 13.5 Hz), 5.21 (d, 1H, J ) 6.0
1
) 19.2 Hz, J
) 19.2 Hz, J
2
) 2.2 Hz), 2.55-
) 6.6 Hz), 3.62-
1
2
J O049309H
5
418 J . Org. Chem., Vol. 69, No. 16, 2004