Ni-Catalyzed Cyclotrimerization of Alkyne/CO Compounds
J . Org. Chem., Vol. 64, No. 10, 1999 3669
136.94 (s), 136.31 (s), 130.95 (s), 127.61 (d), 122.47 (s), 67.44
(t), 29.70 (t), 28.91 (t), 27.47 (t), 22.83 (t), 22.70 (t). IR (neat):
1719.55 cm-1. HRMS: calcd C13H14O2 202.0990, found 202.0990.
The H NMR data of the intermediate dienes 10a -d were
also obtained and are listed bellow.
(t), 37.98 (d), 35.21 (s), 31.38 (q), 22.81 (q). IR (neat): 1709.26
cm-1. HRMS: calcd for C36H32O 480.2445, found 480.2473.
4,5,6,7-Tet r a p h en yl-2,3,3a ,7a -t et r a h yd r o-1H -1-in d en -
1
1
on e (13c). H NMR (400 Hz, CDCl3): δ 7.15-6.97 (m, 10 H,
phenyl), 6.96-6.74 (m, 10 H, phenyl), 3.94 (d d, J ) 6.4 Hz, J
) 7.4 Hz, 1 H), 3.26 (d, J ) 8.0 Hz, 1 H), 2.26 (d d, J ) 7.2 Hz,
J ) 17.6 Hz, 1 H), 2.04 (m, 1 H), 1.88 (m, 2 H, CH2). 13C{1H}
NMR (75 Hz, CDCl3): δ 181.49 (s, CdO), 141.73 (s), 140.17
(s), 140.13 (s), 139.63 (s), 139.59 (s), 132.14 (d), 131.26 (d),
130.85 (d), 129.46 (d), 128.73 (d), 127.77 (d), 127.56 (d), 126.95
(d), 126.72 (d), 126.17 (d), 126.11 (d), 125.59 (d), 125.37 (d),
1-(2,3,5,6,7,8-H exa h yd r o-2-n a p h t h a len yl)-1-et h a n on e
1
(10a ). H NMR (300 MHz, CDCl3): δ 4.46 (br d, J ) 3.5 Hz, 1
H), 4.23 (dd, J ) 3.2 Hz, J ) 8.0 Hz, 1 H), 2.75 (m, 1 H), 2.17
(s, 3 H, CH3), 2.10 (m, 2 H), 1.82-1.72 (m, 4 H), 1.60 (m, 4 H).
1-(2,3,5,6-Tetr a h yd r o-1H-5-in d en yl)-1-eth a n on e (10b).
1H NMR (400 MHz, CDCl3): δ 4.54 (br d, J ) 3.6 Hz, 1 H),
4.27 (dd, J ) 3.2 Hz, J ) 8.0 Hz, 1 H), 2.87 (m, 1 H), 2.18 (m,
2 H), 2.15 (s, 3 H, CH3), 2.03-1.96 (m, 4 H), 1.68 (m, 2 H).
Diet h yl 5-Acet yl-2,3,5,6-t et r a h yd r o-1H -2,2-in d en ed i-
ca r boxyla te (10c). 1H NMR (400 MHz, CDCl3): δ 4.54 (br d,
J ) 3.6 Hz, 1 H), 4.28 (dd, J ) 2.8 Hz, J ) 8.0 Hz, 1 H), 4.21
(q, 4 H, CH2), 2.99 (s, 4 H), 2.88 (m, 1 H), 2.14 (s, 3 H, CH3),
2.04 (m, 2 H), 1.26 (t, 6 H, CH3).
57.07 (d), 41.93 (d), 35.99 (t), 26.50 (t). IR (KBr): 1735.68 cm-1
HRMS: calcd for C33H26O 438.1983, found 438.1958.
.
1,2,3,4-Tetr a p h en yl-5,6,7,8,9,9a -h exa h yd r o-4a H-ben zo-
[a ]cycloh ep ten -5-on e (13d ). 1H NMR (300 Hz, CDCl3): δ
7.19-6.68 (m, 20 H, phenyl), 4.47 (d, J ) 5.4 Hz, 1 H, CO-
CH), 2.85 (d t, J ) 4.6 Hz, J ) 10.4 Hz, 1 H), 2.24 (m, 2 H,
CH2), 1.75 (m, 3 H), 1.59 (m, 2 H, CH2), 1.23 (m, 1 H). 13C{1H}
NMR (75 Hz, CDCl3): δ 187.23 (s, CdO), 141.57 (s), 140.79
(s), 139.92 (s), 139.24 (s), 138.98 (s), 137.93 (s), 136.74 (s),
131.53 (s), 131.00 (d), 130.90 (d), 129.15 (d), 129.03 (d), 127.68
(d), 127.55 (d), 126.95 (d), 126.83 (d), 126.53 (d), 126.28 (d),
125.6 (d), 125.48 (d), 61.90 (d), 43.41 (t), 42.67 (d), 30.68 (t),
26.54 (t), 22.29 (t). IR (neat): 1689.67 cm-1. HRMS: calcd for
5,5-Dim eth yl-4′-a cetylsp ir o[h exa n e-1,3-d ion e-2,1′-4′,5′-
1
d ih yd r oin d a n e] (10d ). H NMR (300 MHz, CDCl3): δ 4.53
(br d, J ) 3.5 Hz, 1 H), 4.27 (dd, J ) 3.1 Hz, J ) 8.1 Hz, 1 H),
3.39 (s, 3 H), 3.35 (s, 1 H), 2.68 (m, 1 H), 2.49 (m, 4 H), 2.23 (s,
3 H, CH3), 1.95 (m, 2 H), 1.06 (t, 6 H, CH3).
5,5-Dim et h yl-4′-a cet ylsp ir o[h exa n e-1,3-d ion e-2,1′-in -
C
35H30O 466.2289, found 466.2286.
1
d a n e] (11d ). H NMR (300 MHz, CDCl3): δ 6.97 (d, J ) 7.9
5,6,7,8-Tetr a p h en yl-3,4,4a ,8a -tetr a h yd r o-1H-1-isoch r o-
Hz, 1 H), 6.83 (s, 1 H), 6.82 (d, J ) 7.2 Hz, 1 H), 3.33 (s, 4 H),
3.10 (s, 2 H) 2.64 (s, 3 H, CH3), 1.89 (s, 2 H), 0.99 (s, 6 H,
CH3). 13C{1H} NMR (75 MHz, CDCl3): δ 195.12 (s, CdO),
189.66 (s, CdO), 139.78 (s), 138.28 (s), 137.87 (s), 129.68 (d),
126.49 (d), 123.99 (d), 71.41 (s), 54.54 (t), 51.43 (t), 44.57 (t),
38.42 (t), 30.55 (s), 28.68 (q), 28.39 (q), 28.33 (q). IR (neat):
1725, 1699.1 cm-1. HRMS: calcd C18H20O3 284.1441, found
284.1456.
1
m en on e (14a ). H NMR (300 MHz, CDCl3): δ 7.21-6.64 (m,
20 H, phenyl), 4.22 (m, 2 H), 3.81 (m, 1 H), 3.73 (d, J ) 7.3
Hz, 1 H), 2.19-2.01 (m, 2 H). 13C{1H} NMR (75 MHz, CDCl3):
δ 173.03 (s, CdO), 140.96 (s), 139.66 (s), 139.20 (s), 139.09 (s),
138.93 (s), 138.43 (s), 136.74 (s), 132.05 (s), 131.07 (d), 130.81
(d), 129.37 (d), 129.31 (d), 127.68 (d), 127.65 (d), 126.99 (d),
126.83 (d), 126.50 (d), 126.44 (d), 125.81 (d), 126.59 (d), 67.18
(t), 48.14 (d), 35.87 (d), 25.60 (t). IR (neat): 1736.95 cm-1
HRMS: calcd for C33H26O2 454.1926, found 454.1926.
.
Gen er a l P r oced u r e for th e Cocyclotr im er iza tion of
Cyclic En on es a n d La cton es w ith Dip h en yla cetylen e. To
a round-bottom sidearm flask (50 mL) were added diphenyl-
acetylene (0.356 g, 2.00 mmol), Ni(PPh3)2I2 (0.042 g, 0.0500
mmol), ZnI2 (0.0140 g, 0.0500 mmol), and zinc powder (0.180
g, 2.75 mmol). The system was evacuated and then purged
with nitrogen gas five times. To this system were added a
freshly distilled appropriate solvent (4.0 mL) and an R,â-
unsaturated cyclic enone or lactone (1.00 mmol). The reaction
was carried out at a specified temperature and time as shown
in Table 2. The reaction mixture was stirred in the air for 15
min at ambient temperature, filtered through Celite and silica
gel, and eluted with dichloromethane. The filtrate was con-
centrated, and the residue was purified on a silica gel column
using hexanes-ethyl acetate as eluent to afford the [2 + 2 +
2] products.
4,5,6,7-Tet r a p h en yl-1,3,3a ,7a -t et r a h yd r o-1-isob en zo-
fu r a n on e (14b). 1H NMR (300 MHz, CDCl3): δ 7.27 (m, 3 H,
phenyl), 7.13 (m, 6 H, phenyl), 6.93-6.81 (m, 9 H, phenyl),
6.65 (m, 2 H, phenyl), 4.40 (d d, J ) 5.1 Hz, J ) 8.8 Hz, 1 H),
4.23 (d d, J ) 1.2 Hz, J ) 8.8 Hz, 1 H), 4.08 (m, 1 H), 3.79(d,
J ) 8.3 Hz, 1 H). 13C{1H} NMR (75 MHz, CDCl3): δ 177.67 (s,
CdO), 140.61 (s), 140.29 (s), 139.33 (s), 139.04 (s), 131.41 (d),
131.09 (d), 130.71 (d), 129.43 (d), 128.79 (d), 128.73 (d), 128.25
(d), 127.72 (d), 127.05 (d), 126.89 (d), 126.75 (d), 126.61 (d),
126.54 (d), 125.91 (d), 125.70 (d), 125.15 (d), 71.37 (t), 47.03
(d), 42.69 (d). IR (KBr) 1767.86 (CdO), 1597.85 cm-1. HRMS:
calcd for C32H24O2 440.1776, found 440.1763.
Gen er a l P r oced u r e for th e Rea ction of Acr yla tes w ith
1-P h en yl-1-p r op yn e. A round-bottom sidearm flask (50 mL)
was charged with Ni(PPh3)2X2 or Ni(dppe)Cl2 (0.0720 mmol)
and zinc powder (0.0475 g, 0.720 mmol). The system was
evacuated and purged with nitrogen gas five times. Freshly
distilled toluene or CH2Cl2 (1.0 mL), acrylates (2.00 mmol)
were added, and the solution was stirred at ambient temper-
ature for 10 min to dissolve the catalyst completely. To this
system was added 1-phenyl-1-propyne (0.090 mL, 0.720 mmol),
and the reaction was carried out at a specified temperature
and time as shown in Table 3. The reaction mixture was stirred
in the air for 15 min at ambient temperature, filtered through
Celite and silica gel, and eluted with dichloromethane. The
filtrate was concentrated, and the residue was separated on a
silica gel column using hexane-dichloromethane (2:1) as
eluent to afford the desired products. Spectral data for
compounds 17a and 17c are listed below, while the yields of
these products are shown in Table 3.
Compounds 13a -d and 14a -b were prepared by following
this procedure. Important spectral data of these compounds
follow.
5,6,7,8-Tet r a p h en yl-1,2,3,4,4a ,8a -h exa h yd r o-1-n a p h -
1
th a len on e (13a ). H NMR (300 MHz, CDCl3): δ 7.08 (m, 10
H, phenyl), 6.80 (m, 10 H, phenyl), 4.04 (d, J ) 6.0 Hz, 1 H,
CO-CH), 3.28 (d d d, J ) 6.0 Hz, J ) 3.3 Hz, J ) 3.3 Hz, 1
H), 2.41 (m, 1 H, CH2), 2.16 (m, 3 H, CH2), 1.88 (m, 1 H, CH2),
1.60 (m, 2 H, CH2). 13C{1H} NMR (75 MHz, CDCl3): δ 212.39
(s, CdO), 140.63 (s), 140.15 (s), 139.31 (s), 139.27 (s), 138.27
(s), 137.95 (s), 131.47 (s), 130.99 (d), 130.94 (d), 129.43 (d),
129.13 (d), 127.57 (d), 127.51 (d), 126.94 (d), 126.80 (d), 126.25
(d), 126.24 (d), 125.64 (d), 125.47 (d), 57.88 (d), 45.02 (d), 41.10
(t), 25.51 (t), 25.38 (t). IR (neat): 1706 cm-1. EI-MS m/z (rel
intensity): 452 (M+, 42.7), 424 (23.1), 395 (21.3), 317 (16.0).
HRMS: calcd for C34H28O 452.21141, found 452.2137.
Compounds 17b, 18b, and 19b were also prepared from the
reaction of ethyl acrylate (0.20 mL, 2.00 mmol) and diphen-
ylacetylene (0.0891 g, 0.5000 mmol) in the presence of Ni-
(PPh3)2Cl2 (or Ni(dppe)Cl2) (0.0500 mmol), Zn (0.1800 g, 2.750
mmol), and PPh3 (0.1574 g, 0.6000 mmol) in toluene (2.0 mL)
at 90 °C for 25 h by following a procedure similar to that
described above. Important spectral data of these products
follow.
4,4-Dim eth yl-5,6,7,8-tetr a p h en yl-1,2,3,4,4a ,8a -h exa h y-
1
d r o-1-n a p h th a len on e (13b). H NMR (300 MHz, CDCl3): δ
7.48-6.75 (m, 20 H, phenyl), 4.37 (d, J ) 6.4 Hz, 1 H), 3.08
(d, J ) 7.8 Hz, 1 H), 2.25 (m, 1 H), 1.95 (m, 1 H), 1.72 (s, 3 H,
CH3), 1.68-1.55 (m, 2 H), 0.64 (s, 3 H, CH3). 13C{1H} NMR
(75 MHz, CDCl3): δ 187.65 (s, CdO), 142.66 (s), 140.20 (s),
139.08 (s), 138.90 (s), 131.11 (d), 130.47 (s), 130.36 (d), 129.96
(d), 129.46 (d), 127.36 (d), 126.99 (d), 126.68 (d), 126.38 (d),
126.11 (d), 125.88 (d), 125.51 (d), 57.77 (d), 52.02 (d), 41.98
Eth yl (2E,4Z,6E)-4,6-Dim eth yl-5,7-d ip h en yl-2,4,6-h ep -
1
ta tr ien oa te (17a ). H NMR (400 MHz, CDCl3): δ 7.90 (d, J