B. Schmidt et al.
General procedure for the Pd-catalyzed [2+2+1] cyclization: Compound
4 (0.5 mmol) and Pd(OAc)2 (0.6 mg, 0.5 mol%) or Pd(CF3CO2)2 (0.8 mg,
found: C 85.2, H 5.0; IR (KBr disk): n˜ =3053 (m), 1740 (s), 1662 (s),
C
N
1440 (s), 1267 (s), 1082 cmÀ1 (m).
0.5 mol%) were added to a solution of 5 (1.0 mmol) in methanol (5 mL).
The solution was stirred at ambient temperature for the time indicated in
Table 2. The resulting precipitate was dissolved with dichloromethane
and filtered over silica and Celite. The solvent was removed and the resi-
due was purified by column chromatography on silica (hexane/MTBE 5:1
as the eluent, unless specified otherwise).
8-Oxo-1,2,3,4-tetra(4’-methoxyphenyl)spiroACTHNUTRGNE[UNG 4.5]deca-1,3,6,9-tetraene
(6ab): Obtained from 4a (104 mg, 0.5 mmol) and 5b (238 mg, 1.0 mmol)
as an orange solid (222 mg, 78%). M.p. 1108C; 1H NMR (300 MHz,
CDCl3): d=6.98 (d, J=8.9 Hz, 4H), 6.81 (d, J=8.8 Hz, 4H), 6.77 (d, J=
10.0 Hz, 2H), 6.65 (d, J=8.8 Hz, 4H), 6.64 (d, J=8.9 Hz, 4H), 6.42 (d,
J=10.0 Hz, 2H), 3.75 (s, 6H), 3.73 ppm (s, 6H); 13C NMR (75 MHz,
CDCl3): d=186.5 (0), 158.7 (0), 158.7 (0), 149.1 (1), 146.7 (0), 139.3 (0),
131.6 (1), 131.4 (1), 130.6 (1), 127.5 (0), 127.4 (0), 113.5 (1), 113.5 (1),
66.2(0), 55.2 ppm (3); MS (EI): m/z (%): 246 (27), 540 (27), 568 (42)
[M]+; HRMS (EI): m/z: calcd for C38H32O5: 568.2244; found: 568.2224
[M]+; elemental analysis (%) calcd for C38H32O5: C 80.2, H 5.6; found: C
79.9, H 5.5; IR (KBr disk): n˜ =2835 (m), 1656 (s), 1601 (s), 1502 (s), 1286
(s), 1246 (s), 1175 cmÀ1 (s).
8-Oxo-1,2,3,4-tetraphenyl-spiroACTHUNRTGNEUNG[4.5]deca-1,3,6,9-tetraene (6aa): Obtained
from 4a (104 mg, 0.5 mmol) and 5a (178 mg, 1.0 mmol) as a colorless
solid (202 mg, 90%). M.p. 2438C; 1H NMR (300 MHz, CDCl3): d=7.22–
7.02 (m, 16H), 7.00–6.88 (m, 4H), 6.83 (d, J=9.2 Hz, 2H), 6.45 ppm (d,
J=9.2 Hz, 2H); 13C NMR (75 MHz, CDCl3): d=186.2 (0), 148.0 (1),
147.8 (0), 141.5 (0), 134.9 (0), 134.7 (0), 132.0 (1), 130.1 (1), 129.5 (1),
128.1 (1), 128.1 (1), 127.6 (1), 127.4 (1), 66.4 ppm (0); MS (ESI): m/z
(%): 313 (45), 341 (73), 449 (100) [M+H]+; HRMS (ESI): m/z: calcd for
C34H24O: 449.1905; found: 449.1925 [M+H]+; elemental analysis calcd
(%) for C34H24O: C 91.0, H 5.4; found: C 90.8, H 5.4; IR (KBr disk): n˜ =
3058 (m), 1657 (s), 1617 (m), 1598 (m), 1440 (s), 1276 cmÀ1 (m).
8-Oxo-1,2,3,4-tetra(4’-chlorophenyl)spiroACHTNUGTRNEUNG[4.5]deca-1,3,6,9-tetraene (6ae):
Obtained from 4a (104 mg, 0.5 mmol) and 5e (247 mg, 1.0 mmol) as a
colorless solid (105 mg, 36%). M.p. >3108C; 1H NMR (300 MHz,
CDCl3): d=7.14 (d, J=8.5 Hz, 4H), 7.11 (d, J=8.6 Hz, 4H), 6.95 (d, J=
8.6 Hz, 4H), 6.79 (d, J=8.5 Hz, 4H), 6.70 (d, J=10.1 Hz, 2H), 6.45 ppm
(d, J=10.0 Hz, 2H); 13C NMR (75 MHz, CDCl3): d=185.4 (0), 146.5 (1),
146.4 (1), 141.4 (0), 134.1 (0), 134.0 (0), 132.5 (1), 132.4 (0), 131.2 (1),
130.5 (1), 128.7 (1), 128.7 (1), 66.0 ppm (0); MS (EI): m/z (%): 83 (100),
339 (20), 558 (26), 586 (17) [M]+; HRMS (EI): m/z: calcd for
C34H20OCl4: 584.0268; found: 584.0273 [M]+; elemental analysis (%)
calcd for C34H20OCl4: C 69.6, H 3.4; found: C 69.4, H 3.2; IR (KBr disk):
n˜ =1659 (s), 1618 (w), 1482 (s), 1393 (m), 1086 (s), 1010 cmÀ1 (s).
7-Nitro-8-oxo-1,2,3,4-tetraphenyl-spiro
G
(6ba):
Obtained from 4b (127 mg, 0.5 mmol) and 5a (178 mg, 1.0 mmol) as a
yellow solid (202 mg, 82%). M.p. 2098C; 1H NMR (300 MHz, CDCl3):
d=7.60 (d, J=2.6 Hz, 1H), 7.21–7.07 (m, 12H), 7.06–6.96 (m, 4H), 6.94–
6.83 (m, 5H), 6.50 ppm (d, J=9.8 Hz, 1H); 13C NMR (75 MHz, CDCl3):
d=175.0 (0), 149.7 (0), 149.4 (0), 147.1 (1), 146.1 (1), 140.0 (0), 133.9 (0),
133.4 (0), 131.9 (1), 129.9 (1), 129.3 (1), 128.5 (1), 128.3 (1), 128.1 (1),
127.9 (1), 66.0 ppm (0); MS (EI): m/z (%): 341 (23), 448 (17), 493 (100)
[M]+; HRMS (EI): m/z: calcd for C34H23NO3: 493.1672; found: 493.1662
[M]+; elemental analysis calcd (%) for C34H23NO3: C 82.7, H 4.7, N 2.8;
found: C 82.4, H 4.4, N 2.9; IR (KBr disk): n˜ =3050 (m), 1675 (s), 1529
(s), 1486 (s), 1440 (s), 1350 cmÀ1 (m).
8-Oxo-1,2,3,4-tetra(4’-methylphenyl)spiroACHTNUGTRNEUNG[4.5]deca-1,3,6,9-tetraene (6af):
Obtained from 4a (104 mg, 0.5 mmol) and 5 f (206 mg, 1.0 mmol) as a
colorless solid (171 mg, 68%). M.p. 2368C; 1H NMR (300 MHz, CDCl3):
d=7.04–6.89 (m, 12H), 6.83 (d, J=8.5 Hz, 6H), 6.46 (d, J=9.9 Hz, 2H),
2.29 (s, 6H), 2.27 ppm (s, 6H); 13C NMR (75 MHz, CDCl3): d=186.5 (0),
148.7 (1), 147.4 (0), 140.3 (0), 137.0 (0), 136.7 (0), 132.0 (0), 131.9 (0),
131.6 (1), 129.9 (1), 129.2 (1), 128.7 (1), 128.6 (1), 66.3 (0), 21.3 (3),
21.2 ppm (3); MS (EI): m/z (%): 385 (13), 476 (89), 504 (100) [M]+;
HRMS (EI): m/z: calcd for C38H32O: 504.2448; found: 504.2482 [M]+; el-
emental analysis calcd (%) for C38H32O: C 90.4, H 6.4; found: C 90.6, H
6.2; IR (KBr disk): n˜ =3075 (m), 2917 (m), 1655 (s), 1502 (s), 1389 (m),
1017 cmÀ1 (m).
7-Bromo-8-oxo-1,2,3,4-tetraphenyl-spiroACTHUNTGRNEUNG[4.5]deca-1,3,6,9-tetraene (6ca):
Obtained from 4c (144 mg, 0.5 mmol) and 5a (178 mg, 1.0 mmol) as a
colorless solid (216 mg, 82%). M.p. 2438C; 1H NMR (300 MHz, CDCl3):
d=7.27 (d, J=2.6 Hz, 1H), 7.21–7.00 (m, 16H), 6.93–6.87 (m, 4H), 6.85
(dd, J=9.7, 2.6 Hz, 1H), 6.50 ppm (d, J=9.7 Hz, 1H); 13C NMR
(75 MHz, CDCl3): d=178.9 (0), 148.1 (0), 148.0 (1), 147.7 (1), 140.2 (0),
134.4 (0), 134.1 (0), 130.5 (1), 129.9 (1), 129.3 (1), 128.2 (1), 128.0 (1),
127.8 (1), 127.5 (1), 126.5 (0), 69.0 ppm (0); MS (EI): m/z (%): 419 (54),
447 (18), 526 (100) [M]+; HRMS (EI): m/z: calcd for C34H23OBr:
526.0927; found: 526.0940 [M]+; elemental analysis calcd (%) for
C34H23OBr: C 77.4, H 4.4; found: C 77.1, H 4.1; IR (KBr disk): n˜ =3051
(m), 1657 (s), 1588 (m), 1485 (m), 1439 (s), 1330 cmÀ1 (m).
8-Oxo-1,3-di(4’-methoxyphenyl)-2,4-diphenyl-spiroACHTNUTRGNE[NUG 4.5]deca-1,3,6,9-tet-
raene and two regioisomers (6ag): Obtained from 4a (104 mg, 0.5 mmol)
and 5g (208 mg, 1.0 mmol) as an inseparable mixture of regioisomers in
1:2:1 ratio; yellow solid (190 mg, 74%). MS (EI): m/z (%): 83 (100), 135
(25), 480 (9), 508 (8) [M]+; HRMS (EI): m/z: calcd for C36H28O3:
508.2038; found: 508.2022 [M]+; elemental analysis calcd (%) for
C36H28O3: C 85.0, H 5.5; found: C 85.3, H 5.4.
8-Oxo-1,2,3,4-tetraphenyl-spiroACTHNUTRGNEU[GN 4.5]deca-1,3,6,9-tetraene-7-carboxylic
acid (6da): Obtained from 4d (126 mg, 0.5 mmol) and 5a (178 mg,
1.0 mmol) as a yellow solid (177 mg, 72%). M.p. 210–2118C; column
chromatography was performed on silica with hexane/MTBE/acetic acid
40:8:1 as the eluent; 1H NMR (300 MHz, [D6]acetone): d=8.28 (d, J=
2.8 Hz, 1H), 7.43 (dd, J=2.8, 9.7 Hz, 1H), 7.26–7.01 (m, 20H), 6.62 ppm
(d, J=9.7 Hz, 1H); 13C NMR (75 MHz, [D6]acetone): d=188.8 (0), 163.6
(0), 161.9 (1), 152.5 (1), 150.9 (0), 140.0 (0), 135.5 (0), 134.9 (0), 131.5 (1),
130.7 (1), 130.4 (1), 129.7 (0), 128.9 (1), 128.7 (1), 128.6 (1), 128.4 (1),
68.5 ppm (0); MS (ESI): m/z (%): 461 (82), 475 (100), 493 (86) [M+H]+;
HRMS (ESI): m/z: calcd for C35H24O3Na: 515.1623; found: 515.1613
[M+Na]+; elemental analysis calcd (%) for C35H24O3: C 85.3, H 4.9;
found: C 85.1, H 4.6; IR (KBr disk): n˜ =3053 (m), 1744 (s), 1638 (s),
1598 (s), 1439 (s), 1401 cmÀ1 (s).
8-Oxo-1,2,3,4-tetra(2’-naphthyl)spiroACTHNUGRTNEUNG[4.5]deca-1,3,6,9-tetraene (6al): Ob-
tained from 4a (104 mg, 0.5 mmol) and 5l (278 mg, 1.0 mmol) as a color-
less solid (202 mg, 62%). M.p. 2318C; 1H NMR (300 MHz, CDCl3): d=
7.80–7.27 (m, 24H), 7.12 (dd, J=5.9, 1.7 Hz, 2H), 7.08 (dd, J=5.8,
1.7 Hz, 2H), 7.04 (d, J=10.0 Hz, 2H), 6.53 ppm (d, J=10.0 Hz, 2H);
13C NMR (75 MHz, CDCl3): d=186.1 (0), 148.2 (1), 148.0 (0), 141.8 (0),
133.1 (0), 132.5 (0), 132.5 (0), 132.3 (0), 132.2 (0), 132.1 (1), 129.6 (1),
128.3 (1), 128.2 (1), 127.8 (1), 127.7 (1), 127.7 (1), 127.6 (1), 127.6 (1),
126.3 (1), 126.2 (1), 126.2 (1), 126.0 (1), 66.8 ppm (0); MS (EI): m/z (%):
155 (96), 221 (100), 281 (61), 648 (3) [M]+; HRMS (EI): m/z: calcd for
C50H32O: 648.2453; found: 648.2488 [M]+; elemental analysis calcd (%)
for C50H32O: C 92.5, H 5.0; found: C 91.9, H 4.7; IR (KBr disk): n˜ =3054
(m), 1654 (s), 1624 (s), 1597 (s), 1506 (m), 1219 cmÀ1 (m).
Methyl-8-oxo-1,2,3,4-phenyl-spiroACTHNUTRGNEU[GN 4.5]deca-1,3,6,9-tetraene-7-carboxylate
(6ea). Obtained from 4e (0.5 mg, 133 mmol) and 5a (178 mg, 1.0 mmol)
as a colorless solid (175 mg, 69%). M.p. 1268C; 1H NMR (300 MHz,
CDCl3): d=7.61 (d, J=2.8 Hz, 1H), 7.24–7.05 (m, 12H), 7.05–6.98 (m,
4H), 6.90 (dd, J=8.0, 1.5 Hz, 4H), 6.80 (dd, J=9.9, 2.9 Hz, 1H), 6.45 (d,
J=9.8 Hz, 1H), 3.82 ppm (s, 3H); 13C NMR (75 MHz, CDCl3): d=181.7
(0), 164.6 (0), 155.0 (1), 148.5 (0), 145.7 (1), 141.0 (0), 134.4 (0), 134.0 (0),
133.4 (0), 132.7 (1), 129.9 (1), 129.4 (1), 128.2 (1), 128.0 (1), 127.8 (1),
127.5 (1), 66.1 (0), 52.5 ppm (3); MS (EI): m/z (%): 441 (19), 478 (15),
506 (10) [M]+; HRMS (EI): m/z: calcd for C36H26O3: 506.1882; found:
506.1896 [M]+; elemental analysis calcd (%) for C36H26O3: C 85.3, H 5.2;
6,10-Dimethyl-8-oxo-1,2,3,4-tetraphenyl-spiroACTHNUTRGENUG[N 4.5]deca-1,3,6,9-tetraene
(6ga): Obtained from 4g (118 mg, 0.5 mmol) and 5a (178 mg, 1.0 mmol)
as a colorless solid (141 mg, 60%). M.p. 2348C; 1H NMR (300 MHz,
CDCl3): d=7.24–7.05 (m, 12H), 7.04–6.88 (m, 8H), 6.35 (s, 2H),
1.96 ppm (s, 6H); 13C NMR (75 MHz, CDCl3): d=186.9 (0), 157.0 (0),
149.5 (0), 143.5 (0), 135.3 (0), 134.2 (0), 131.1 (1), 130.1 (1), 129.0 (1),
128.5 (1), 128.4 (1), 127.9 (1), 127.7 (1), 71.5 (0), 18.8 ppm (3); MS (EI):
m/z (%): 207 (33), 448 (15), 476 (100) [M]+; HRMS (EI): m/z: calcd for
C36H28O: 476.2135; found: 476.2158; elemental analysis calcd (%) for
7038
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 7032 – 7040