Synthesis of Tricyclic Aromatic Compounds
J . Org. Chem., Vol. 65, No. 11, 2000 3519
0.36 g (1.04 mmol) of Co2(CO)8, 1.20 g of molecular sieves and
sieves. To this solution was added 1.20 mmol of Co2(CO)8, and
the resulting mixture was stirred for 2 h until total complex-
ation of the enyne (TLC). The reaction was then cooled to -10
°C with an ice/salt bath, and a suspension of Me3NO (9.00
mmol) in MeCN at 0 °C was added dropwise. After 18 h of
stirring, the mixture was filtrated, the solvent was evaporated
under vacuum, and the crude product was purified by flash
chromatography (hexane/EtOAc mixtures).
0.59 g (7.83 mmol) of TMANO, 0.09 g (50%) of 6h was obtained
as a colorless oil: 1H NMR δ 1.75 (s, 3H), 2.51 (dd, 1H, J 1
)
18.1 Hz, J 2 ) 2.7 Hz), 2.98 (dd, 1H, J 1 ) 18.1 Hz, J 2 ) 6.6
Hz), 3.92-4.03 (m, 1H), 4.94 (d, 1H, J ) 14.8 Hz), 5.06 (d, 1H,
J ) 14.8 Hz), 6.89 (d, 1H, J ) 7.8 Hz), 6.96 (t, 1H, J ) 7.8
Hz), 7.07 (d, 1H, J ) 7.7 Hz), 7.16 (t, 1H, J ) 7.7 Hz); 13C
NMR δ 206.9, 163.9, 153.6, 134.5, 128.1, 126.8, 125.8, 121.8,
116.9, 64.7, 40.0, 37.1, 7.9; IR (neat) ν 1710, 1660, 1600, 1580,
1480 cm-1. Anal. Calcd for C13H12O2: C, 77.98; H, 6.04.
Found: C, 77.69; H, 5.98.
4-Br om o-2-vin ylph en ol, 5c. Following the general method,
from 0.10 g (0.42 mmol) of 2c, 0.17 g (0.50 mmol) of Co2(CO)8,
0.80 g of molecular sieves, and 0.28 g (3.78 mmol) of TMANO,
0.04 g (65%) of 5c was obtained as a pale yellow oil: 1H NMR
δ 5.37 (d, 1H, J ) 11.3 Hz), 5.74 (d, 1H, J ) 17.6 Hz), 5.83
(bs, 1H), 6.69 (d, 1H, J ) 8.8 Hz), 6.88 (dd, 1H, J 1 ) 17.6 Hz,
J 2 ) 11.3 Hz), 7.21 (dd, 1H, J 1 ) 8.8 Hz, J 2 ) 2.2 Hz), 7.50 (d,
1H, J ) 2.2 Hz); 13C NMR δ 152.1, 149.1, 131.3, 130.3, 129.6,
9b -Met h yl-4,9b -d ih yd r o-1H -cyclop en t a [c]ch r om en -2-
on e, 6k . Following method B, from 0.15 g (0.87 mmol) of 2k ,
0.36 g (1.05 mmol) of Co2(CO)8, and 1.20 g of molecular sieves,
0.07 g (40%) of 6k was obtained as a colorless oil: 1H NMR δ
1.58 (s, 3H), 2.75 (d, 1H, J ) 18.1 Hz), 2.86 (d, 1H, J ) 18.1
Hz), 5.05 (d, 1H, J ) 14.8 Hz), 5.13 (d, 1H, J ) 14.8 Hz), 6.04
(s, 1H), 6.88 (d, 1H, J ) 8.8 Hz), 6.98 (t, 1H, J ) 7.1 Hz), 7.12-
7.19 (m, 2H); 13C NMR δ 207.0, 171.4, 146.2, 132.7, 127.7,
120.4, 117.8, 115.4, 115.1, 46.7, 39.9, 36.7, 29.7; IR (neat) ν
1710, 1640, 1575 cm-1. Anal. Calcd for C13H12O2: C, 77.98; H,
6.04, Found: C, 77.87; H, 5.96.
117.5, 116.6, 112.8; IR (neat) ν 3400, 1630, 1480, 1405 cm-1
.
Gen er a l Meth od for th e Obten tion of Coba lt Hexa c-
a r bon yl-Alk yn e Com p lexes of En yn es 2. A 1.00 mmol
sample of the enyne 2 was dissolved in dry toluene (40 mL) at
room temperature under argon. To this solution was added
1.20 mmol of Co2(CO)8, and the resulting mixture was stirred
for 2 h until total complexation of the enyne (TLC). The
mixture was filtrated through Celite and the solvent evapo-
rated under vacuum to obtain pure cobalt hexacarbonylalkyne
complexes.
[2-(2-P r opyn yloxy)styr en e]dicobalt Hexacar bon yl. From
0.05 g (0.32 mmol) of 2a , 0.13 g (0.38 mmol) of Co2(CO)8, and
0.40 g of molecular sieves, 0.14 g (quantitative) of the complex
was obtained as a red oil: 1H NMR δ 5.21 (s, 2H), 5.22 (dd,
1H, J 1 ) 11.0 Hz, J 2 ) 1.1 Hz), 5.69 (dd, 1H, J 1 ) 17.6 Hz, J 2
) 1.1 Hz), 6.11 (s, 1H), 6.91 (d, 1H, J ) 8.2 Hz), 6.98 (t, 1H, J
) 7.7 Hz), 7.16 (dd, 1H, J 1 ) 17.6 Hz, J 2 ) 11.0 Hz), 7.24 (m,
1H), 7.54 (d, 1H, J ) 7.7 Hz).
1-Met h yl-3a ,4-d ih yd r o-3H -cyclop en t a [c]ch r om en -2-
on e, 3l: Following method B, from 0.10 g (0.58 mmol) of 2l,
0.24 g (0.70 mmol) of Co2(CO)8, and 0.80 g of molecular sieves,
0.05 g (40%) of 3l was obtained as a yellow solid: mp 109-
111 °C (hexane/EtOAc); 1H NMR δ 1.97 (dd, 1H, J 1 ) 18.1
Hz, J 2 ) 3.8 Hz), 2.09 (d, 3H, J ) 1.6 Hz), 2.72 (dd, 1H, J 1
18.1 Hz, J 2 ) 6.6 Hz), 3.16-3.22 (m, 1H), 3.82 (dd, 1H, J 1
)
)
13.2 Hz, J 2 ) 10.4 Hz), 4.61 (dd, 1H, J 1 ) 10.4 Hz, J 2 ) 5.5
Hz), 6.97-7.06 (m, 2H), 7.34 (t, 1H, J ) 8.8 Hz), 7.68 (d, 1H,
J ) 8.2 Hz); 13C NMR δ 206,6, 159.5, 155.8, 132.0, 131.7, 128.2,
120.9, 119.0, 117.7, 70.5, 36.0, 34.7, 9.5; IR (KBr) ν 1685, 1615,
1600 cm-1. Anal. Calcd for C13H12O2: C, 77.98; H, 6.04.
Found: C, 78.12; H, 6.33.
[2-(3-Deu ter io-2-P r op yn yloxy)styr en e]d icoba lt h exa c-
a r bon yl: From 0.03 g (0.19 mmol) of 2r , 0.08 g (0.23 mmol)
of Co2(CO)8, and 0.24 g of molecular sieves, 0.08 g (quantita-
3,3a,4,5-Tetr ah ydr ocyclopen ta[c]qu in olin -2-on e, 3o. Fol-
lowing method A, from 0.06 g (0.38 mmol) of 2o, 0.16 g (0.46
mmol) of Co2(CO)8, 0.48 g of molecular sieves and 0.26 g (3.42
mmol) of TMANO, 0.04 g (55%) of 3o was obtained as a yellow
oil: 1H NMR δ 2.07 (dd, 1H, J 1 ) 18.1 Hz, J 2 ) 3.9 Hz), 2.71-
2.79 (m, 1H), 3.11-3.15 (m, 2H), 3.58-3.69 (m, 1H), 4.48 (brs,
1H), 6.30 (d, 1H, J ) 1.7 Hz), 6.63 (d, 1H, J ) 8.3 Hz), 6.74 (t,
1H, J ) 8.3 Hz), 7.21 (t, 1H, J ) 8.3 Hz), 7.50 (dd, 1H, J 1) 8.3
Hz); 13C NMR δ 207.0, 171.4, 146.2, 132.8, 127.7, 120.4, 117.8,
115.4, 115.1, 46.7, 39.9, 36.7; IR (neat) ν 3300, 1650, 1610,
1575 cm-1: Anal. Calcd for C12H11NO: C, 77.81; H, 5.99, N
7.56. Found: C, 77.61; H, 5.90, N 7.53.
3-Meth ylen cyclop en ten e-3′-sp yr o-4-ch r om a n e, 7p . Fol-
lowing method B, from 0.10 g (0.50 mmol) of 2p , 0.21 g (0.61
mmol) of Co2(CO)8, and 0.80 g of molecular sieves, 0.03 g (30%)
of 7p was obtained as a colorless oil: 1H NMR δ 2.09-2.27 (m,
2H), 2.36-2.57 (m, 2H), 4.59 (d, 1H, J ) 11.8 Hz), 4.65 (d,
1H, J ) 11.8 Hz), 4.99 (s, 1H), 5.05 (s, 1H), 5.53 (m, 1H), 6.13
(m, 1H), 6.83 (d, 1H, J ) 8.2 Hz), 6.90 (t, 1H, J ) 7.2 Hz),
7.06-7.15 (m, 2H); 13C NMR δ 153.8, 144.8, 136.0, 133.3, 130.2,
128.4, 127.4, 121.1, 116.5, 110.8, 69.4, 55.0, 43.9, 31.2; IR (neat)
ν 1650, 1600, 1480 cm-1. Anal. Calcd for C14H14O: C, 84.81;
H, 7.12. Found: C, 85.00; H, 7.21.
3-Meth ylen cycloh exen e-3′-sp yr o-4-ch r om a n e, 7q. Fol-
lowing method B, from 0.15 g (0.71 mmol) of 2q, 0.29 g (0.85
mmol) of Co2(CO)8, and 1.20 g of molecular sieves, 0.03 g (20%)
of 7q was obtained as a purple oil unpurified with a small
amount of an unidentified cobalt complex: 1H NMR δ 1.55-
1.80 (m, 4H), 1.81-2.00 (m, 2H), 2.04-2.40 (m, 2H), 4.50 (d,
1H, J ) 12.1 Hz), 4.70 (d, 1H, J ) 12.1 Hz), 5.08 (s, 1H), 5.26
(s, 1H), 5.39 (m, 1H), 6.07 (m, 1H), 6.80 (d, 1H, J ) 8.2 Hz),
6.91 (t, 1H, J ) 8.2 Hz), 7.10 (d, 1H, J ) 8.2 Hz), 7.19 (d, 1H,
J ) 8.2 Hz).
1
tive) of the complex was obtained as a red oil. H NMR δ 5.21
(s, 2H), 5.22 (d, 1H, J ) 11.5 Hz), 5.69 (d, 1H, J ) 17.6 Hz),
6.91 (d, 1H, J ) 8.2 Hz), 7.00 (t, 1H, J ) 7.7 Hz), 7.18 (dd, 1H,
J 1 ) 17.6 Hz, J 2 ) 11.5 Hz), 7.25 (m, 1H), 7.55 (d, 1H, J ) 7.7
Hz).
[2-(2-P ropynyloxy)-â,â-dideuteriostyrene]dicobalt Hexac-
a r bon yl. From 0.15 g (0.95 mmol) of 2s, 0.39 g (1.14 mmol) of
Co2(CO)8, and 1.20 g of molecular sieves, 0.42 g (quantitative)
of the complex was obtained as a red solid: mp 55-56 °C; 1H
NMR δ 5.20 (s, 2H), 6.10 (s, 1H), 6.90 (d, 1H, J ) 8.2 Hz),
6.98 (t, 1H, J ) 7.1 Hz), 7.16 (d, 1H, J ) 7.1 Hz), 7.23 (m,
1H), 7.53 (d, 1H, J ) 7.7 Hz).
[2-(3-Tr im et h ylsilyl-2-P r op yn yloxy)st yr en e]d icob a lt
Hexa ca r bon yl. From 0.02 g (0.09 mmol) of 2j, 0.04 g (0.10
mmol) of Co2(CO)8, and 0.16 g of molecular sieves, 0.05 g
(quantitative) of the complex was obtained as a red oil: 1H
NMR δ 0.06 (s, 3H), 0.30 (s, 6H), 5.21 (dd, 1H, J 1 ) 11.0 Hz,
J 2 ) 1.6 Hz), 5.22 (s, 2H), 5.67 (dd, 1H, J 1 ) 18.1 Hz, J 2 ) 1.6
Hz), 6.94 (d, 1H, J ) 8.2 Hz), 6.98 (t, 1H, J ) 7.7 Hz), 7.17
(dd, 1H, J 1 ) 18.1 Hz, J 2 ) 11.0 Hz), 7.25 (m, 1H), 7.54 (d,
1H, J ) 7.7 Hz).
Ack n ow led gm en t. We are grateful to the DGES
(MEC-Spain, Grant PB98-0053) and the Universidad
San Pablo-CEU (grant 02-1999) for financial support.
L.P.-S. acknowledges the Universidad San Pablo for a
predoctoral fellowship.
Su p p or tin g In for m a tion Ava ila ble: Spectroscopic and
analytical characterization of compounds 2b-t, 3b, 3e-g,
3m ,n , 4b,f, 5a ,f, and 6i. This material is available free of
Gen er a l Meth od for th e Obten tion of 5a , 5c, a n d 5f. A
1.00 mmol sample of the enyne 2 was dissolved in dry MeCN
(40 mL) at room temperature under argon, in a flask contain-
ing 8 times the mass of the enyne of powdered 4 Å molecular
J O0001232