C. Kalogiros, L.P. Hadjiarapoglou / Tetrahedron 67 (2011) 3216e3225
3223
cycloadduct 6cc (0.36 g, 90%) was isolated as a colorless oil; [found:
C, 77.51; H, 6.06. C25H24O4 requires C, 77.30; H, 6.23%]; Rf (20%
EtOAc/CH2Cl2) 0.58; nmax (liquid film) 3059, 2945, 1736, 1713, 1672,
2837, 1737, 1669, 1624, 1568, 1467, 1393, 1311, 1267, 1152, 1055,
978,748 cmꢁ1
;
dH (250 MHz, CDCl3) 7.53 (dd, J¼0.8, 1.7 Hz, 1H),
7.20e7.25 (m, 2H), 7.06e7.16 (m, 5H), 6.89 (d, J¼16.1 Hz, 1H),
6.52e6.58 (m, 1H), 6.46 (dd, J¼1.7, 3.6 Hz, 1H), 6.25 (d, J¼8.3 Hz,
1H), 3.67e3.73 (m, 1H), 3.27 (s, 3H), 3.24 (s, 3H), 3.05e3.11 (m, 1H),
2.59e2.69 (m, 1H), 1.59 (ddd, J¼3.3, 5.2, 13.9 Hz, 1H); dC (62.5 MHz,
CDCl3) 198.8, 176.8, 152.8, 146.5, 142.1, 134.9, 134.6, 131.8, 128.8,
127.4, 127.1, 126.5, 117.9, 112.2, 93.7, 59.4, 50.3, 49.6, 48.5, 37.9, 37.1.
1626, 1450, 1302, 1217, 1150, 1057, 982, 770 cmꢁ1
; dH (250 MHz,
CDCl3) 7.44e7.50 (m, 3H), 7.18e7.36 (m, 5H), 7.10e7.13 (m, 2H), 7.00
(d, J¼16.3 Hz, 1H), 6.73e6.79 (m, 1H), 6.40 (d, J¼16.3 Hz, 1H), 6.23
(d, J¼8.2 Hz, 1H), 3.42 (s, 3H), 3.37 (s, 3H), 3.29e3.32 (m, 2H),
2.63e2.7 (m, 1H),1.76 (ddd, J¼2.7, 6.7, 13.3 Hz, 1H); dC (62.5 MHz,
CDCl3) 199.1, 190.8, 143.3, 142.2, 137.3, 135.5, 132.4, 128.7, 128.6,
128.5, 128.3, 128.1, 127.1, 126.8, 93.9, 58.9, 50.3, 49.8, 45.5, 38.7, 32.1.
4.4.13. Methyl (2E)-3-(11,11-dimethoxy-10-oxo-1,4a,9,9a-tetrahy-
dro-4H-1,4-ethanofluoren-4-yl)acrylate (6be). By following the
above mentioned procedure, in which dimer 3b (0.25 g,
0.53 mmol) and indene 4e (0.58 g, 5.0 mmol) were heated at
230 ꢀC for 5.5 h, cycloadduct 6be (0.35 g, 92%) was isolated as
a colorless oil; [found: C, 70.95; H, 6.51. C21H22O5 requires C,
71.17; H, 6.26%]; Rf (20% EtOAc/CH2Cl2) 0.50; nmax (liquid film)
4.4.9. (E)-1-(3-(Furan-2-yl)-3-oxoprop-1-enyl)-3,3-dimethoxy-6-
phenylbicyclo[2.2.2]oct-7-en-2-one (6dc). By following the above
mentioned procedure, in which dimer 3d (0.28 g, 0.51 mmol) and
styrene 4c (0.52 g, 5.0 mmol) were heated at 230 ꢀC for 18 h,
cycloadduct 6dc (0.16 g, 41%) was isolated as a white solid; mp
61e63 ꢀC (EtOAc/pet. ether); [found: C, 73.09; H, 5.81. C23H22O5
requires C, 73.00; H, 5.86%]; Rf (20% EtOAc/CH2Cl2) 0.51; nmax (KBr)
2950, 1735, 1669, 1623, 1567, 1464, 1394, 1317, 1152, 1054, 767,
2952, 2841, 1728, 1659, 1441, 1313, 1177, 1060, 881, 839, 742 cmꢁ1
;
dH (250 MHz, CDCl3) 7.34 (d, J¼16.3 Hz, 1H), 6.96e7.10 (m, 4H),
6.28e6.34 (m, 1H), 5.85 (d, J¼16.3 Hz, 1H), 5.85 (br s, 1H), 3.75 (s,
3H), 3.66 (d, J¼8.8 Hz, 1H), 3.38 (s, 3H), 3.26 (s, 3H), 3.22e3.31 (m,
2H), 3.10 (dd, J¼10.2, 16.5 Hz, 1H), 2.69 (dd, J¼4.8, 16.5 Hz, 1H); dC
(62.5 MHz, CDCl3) 200.5, 165.9, 144.1, 144.0, 140.3, 132.7, 127.4,
127.0, 125.7, 125.6, 124.0, 123.3, 93.9, 58.8, 53.0, 51.5, 50.1, 49.5,
43.3, 37.1, 36.2.
706 cmꢁ1
;
dH (250 MHz, CDCl3) 7.51 (dd, J¼0.8, 1.7 Hz, 1H),
7.05e7.20 (m, 6H), 6.91 (d, J¼3.6 Hz, 1H), 6.70e6.76 (m, 1H), 6.44
(dd, J¼1.7, 3.6 Hz, 1H), 6.33 (d, J¼16.2 Hz, 1H), 6.19 (d, J¼8.2 Hz, 1H),
3.40 (s, 3H), 3.35 (s, 3H), 3.26e3.37 (m, 2H), 2.60e2.70 (m, 1H), 1.73
(ddd, J¼2.8, 6.6, 13.3 Hz, 1H); dC (62.5 MHz, CDCl3) 199.2, 177.3,
152.8, 146.6, 142.7, 142.1, 135.5,128.7, 128.3, 127.4, 127.3, 127.2, 118.0,
112.2, 94.1, 59.0, 50.5, 49.9, 45.7, 38.9, 32.0.
4.4.14. 11,11-Dimethoxy-4-[(1E)-3-oxo-3-phenylprop-1-en-1-yl]-
4,4a,9,9a-tetrahydro-1H-1,4-ethanofluoren-10-one (6ce). By follow-
ing the above mentioned procedure, in which dimer 3c (0.29 g,
0.51 mmol) and indene 4e (0.58 g, 5.0 mmol) were heated at 230 ꢀC
for 5 h, cycloadduct 6ce (0.40 g, 98%) was isolated as a colorless oil;
[found: C, 78.15; H, 6.21. C26H24O4 (400.47): C, 77.98%]; H, 6.04; Rf
(20% EtOAc/CH2Cl2) 0.54; nmax (liquid film) 3062, 2949, 2837, 1735,
4.4.10. (E)-Methyl 3-(3,3-dimethoxy-2-oxo-6-(phenylthio)bicyclo
[2.2.2]oct-7-en-1-yl)prop-2-enoate (6bd). By following the above
mentioned procedure, in which dimer 3b (0.24 g, 0.5 mmol) and
phenylthioethylene (4d) (0.68 g, 5.0 mmol) were heated at 230 ꢀC
for 15 h, cycloadduct 6bd (0.35 g, 95%) was isolated as a colorless
oil; [found: C, 64.50; H, 6.11. C20H22O5S requires C, 64.15; H,
5.92%]; Rf (20% EtOAc/CH2Cl2) 0.61; nmax (liquid film) 3061, 2949,
2839, 1724, 1655, 1634, 1583, 1475, 1439, 1315, 1274, 1192, 1152,
1673, 1624, 1448, 1303, 1221, 1148, 1058, 987, 763, 732 cmꢁ1
; dH
(250 MHz, CDCl3) 7.97 (d, J¼7.1 Hz, 2H), 7.41e7.57 (m, 4H),
6.93e7.11 (m, 5H), 6.36e6.42 (m, 1H), 6.05 (d, J¼8.4 Hz, 1H), 3.75 (d,
J¼8.8 Hz, 1H), 3.44 (s, 3H), 3.33 (s, 3H), 3.26e3.39 (m, 2H), 3.15 (dd,
J¼10.2, 16.6 Hz, 1H), 2.74 (dd, J¼4.7, 16.6 Hz, 1H); dC (62.5 MHz,
CDCl3) 200.6, 189.5, 144.0, 143.8, 140.4, 137.3, 132.8, 132.7, 128.5,
128.3, 127.8, 127.5, 127.4, 125.9, 125.7, 124.0, 94.0, 59.2, 53.3, 50.2,
49.6, 43.3, 37.2, 36.2.
1059, 980 cmꢁ1
; dH (250 MHz, CDCl3) 7.14e7.27 (m, 5H), 6.91 (d,
J¼16.2 Hz, 1H), 6.50e6.56 (m, 1H), 6.15 (d, J¼8.2 Hz, 1H), 5.99 (d,
J¼16.2 Hz, 1H), 3.64e3.73 (m, 1H), 3.61 (s, 3H), 3.27 (s, 3H), 3.23
(s, 3H), 3.06e3.08 (m, 1H), 2.58e2.68 (m, 1H), 1.49e1.48 (m, 1H);
dC (62.5 MHz, CDCl3) 198.7, 165.6, 142.7, 134.9, 134.6, 131.7, 128.7,
126.9, 125.9, 123.6, 93.6, 59.1, 51.3, 50.2, 49.5, 47.9, 37.8, 31.4.
4.4.15. 4-[(1E)-3-(Furan-2-yl)-3-oxoprop-1-en-1-yl]-11,11-dime-
thoxy-4,4a,9,9a-tetrahydro-1H-1,4-ethanofluoren-10-one (6de). By
following the above mentioned procedure, in which dimer 3d
(0.28 g, 0.51 mmol) and indene 4e (0.58 g, 5.0 mmol) were heated
at 230 ꢀC for 17 h, cycloadduct 6de (0.34 g, 85%) was isolated as
a white solid; mp 78e80 ꢀC (Et2O/pet. ether); [found: C, 73.90; H,
5.74. C24H22O5 requires C, 73.83; H, 5.68%]; Rf (20% EtOAc/CH2Cl2)
0.54; nmax (KBr) 3139, 2954,1737,1668,1626,1565,1465,1395,1324,
4.4.11. (E)-3,3-Dimethoxy-1-(3-oxo-3-phenylprop-1-enyl)-6-(phe-
nylthio)bicyclo[2.2.2]oct-7-en-2-one (6cd). By following the above
mentioned procedure, in which dimer 3c (0.29 g, 0.51 mmol) and
phenylthioethylene (4d) (0.71 g, 5.22 mmol) were heated at 230 ꢀC
for 16 h, cycloadduct 6cd (0.43 g, ca. 100%) was isolated as a color-
less oil; [found: C, 71.12; H, 5.91. C25H24O4S requires C, 71.40; H,
5.75%]; Rf (20% EtOAc/CH2Cl2) 0.61; nmax (liquid film) 3030, 2946,
2836, 1738, 1671, 1625, 1475, 1446, 1332, 1300, 1217, 1149, 1061, 977,
1247, 1150, 1050, 986, 798, 755 cmꢁ1
; dH (250 MHz, CDCl3)
737 cmꢁ1
;
dH (250 MHz, CDCl3) 7.85 (dd, J¼1.5, 7.0 Hz, 2H),
7.57e7.58 (m, 1H), 7.49 (d, J¼16.2 Hz, 1H), 7.24 (d, J¼3.6 Hz, 1H),
6.90e7.12 (m, 4H), 6.84 (d, J¼16.2 Hz, 1H), 6.52 (ddd, J¼0.3, 1.7,
3.6 Hz, 1H), 6.34e6.40 (m, 1H), 6.03 (d, J¼8.5 Hz, 1H), 3.74e3.79 (m,
1H), 3.41 (s, 3H), 3.30 (s, 3H), 3.25e3.35 (m, 2H), 3.09e3.20 (m, 1H),
2.72 (dd, J¼4.7, 16.6 Hz, 1H); dC (62.5 MHz, CDCl3) 200.6, 177.0,
153.0,146.7,144.1,143.5,140.5,132.8,127.7,127.5,127.0,126.0,125.8,
124.1, 118.1, 112.4, 94.2, 59.3, 53.6, 50.3, 49.7, 43.5, 37.3, 36.3.
7.38e7.56 (m, 3H), 7.27e7.30 (m, 2H), 7.11e7.21 (m, 3H), 6.98 (s,
2H), 6.59e6.65 (m, 1H), 6.31 (d, J¼8.3 Hz, 1H), 3.75 (dd, J¼5.2,
9.2 Hz, 1H), 3.33 (s, 3H), 3.31 (s, 3H), 3.13e3.16 (m, 1H), 2.70 (ddd,
J¼2.7, 9.2, 13.8 Hz, 1H), 1.67 (ddd, J¼3.3, 5.2, 13.8 Hz, 1H); dC
(62.5 MHz, CDCl3) 199.0, 190.6, 143.1, 137.5, 135.0, 134.7, 132.5, 131.8,
128.9, 128.8, 128.7, 128.3, 127.2, 126.5, 93.8, 59.6, 50.4, 49.7, 48.4,
38.0, 31.8.
4.4.16. Methyl (2E)-3-(11,11-dimethoxy-12-oxo-10,10a-dihydro-7,10-
ethanofluornthen-7(6bH)-yl)acrylate (6bf). By following the above
mentioned procedure, in which dimer 3b (0.24 g, 0.5 mmol) and
acenaphthylene 4f (0.76 g, 5.0 mmol) were heated at 230 ꢀC for
15.5 h, cycloadduct 6bf (0.33 g, 85%) was isolated as a white solid;
mp 141e143 ꢀC (CHCl3 epet. ether); [found: C, 73.51; H, 5.80.
C24H22O5 requires C, 73.83; H, 5.68%]; Rf (20% EtOAc/CH2Cl2) 0.72;
nmax (KBr) 3037, 2952, 2836, 1725, 1656, 1599, 1440, 1291, 1232,
4.4.12. (E)-1-(3-(Furan-2-yl)-3-oxoprop-1-enyl)-3,3-dimethoxy-6-
(phenylthio)bicyclo[2.2.2]oct-7-en-2-one (6dd). By following the
above mentioned procedure, in which dimer 3d (0.28 g, 0.51 mmol)
and phenylthioethylene (4d) (0.68 g, 5.0 mmol) were heated at
230 ꢀC for 16 h, cycloadduct 6dd (0.33 g, 79%) was isolated as
a colorless oil; [found: C, 67.22; H, 5.35. C23H22O5S requires C, 67.30;
H, 5.40%]; Rf (20% EtOAc/CH2Cl2) 0.43; nmax (liquid film) 3060, 2945,