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7.42 (d, J = 8.1 Hz, 2H), 7.36 (d, J = 1.7 Hz, 1H), 7.23
(d, J = 7.7 Hz, 2H), 7.13 (d, J = 8.6 Hz, 1H), 7.09 (d,
J = 8.1 Hz, 1H), 6.89–6.80 (m, 6H), 4.65 and 4.56 (s,
2H), 3.95 (s, 3H), 3.84 (s, 3H), 2.89–2.67 (m, 4H); MS
(FAB) 530 (M+).
4.1.44. 4-Methoxy-3-[4-(5-methoxy-2-{4-[(1,1,1-trip-
henylphosphino)methyl]phenyl}phenethyl)phenoxy]benzal-
dehyde bromide (17c). This compound was prepared
from 16c by means of a procedure similar to that used
1
for 17a. H NMR (500 MHz, CDCl3) d 9.78 (s, 1H),
7.78–7.72 (m, 9H), 7.63 (dd, J = 8.1, 1.7 Hz, 1H),
7.60–7.56 (m, 6H), 7.34 (d, J = 1.7 Hz, 1H), 7.11 (d,
J = 8.1 Hz, 3H), 7.03 (d, J = 7.7 Hz, 3H), 6.90 (d,
4.1.39. 3-[4-(5-Methoxy-2-{(2-methoxy-4-bromomethyl)
phenyl}phenethyl)phenoxy]benzaldehyde (16d). This com-
pound was prepared from 15d by means of a procedure
similar to that used for 16a. 1H NMR (500 MHz,
CDCl3) d 9.92 (s, 1H), 7.54 (d, J = 7.7 Hz, 1H), 7.45
(dd, J = 8.1, 7.7 Hz, 1H), 7.40–7.39 (m, 1H), 7.07 (dd,
J = 7.7 Hz, 1H), 7.03–6.98 (m, 3H), 6.91–6.79 (m, 7H),
4.63 and 4.54 (s, 2H), 3.81 (s, 3H), 3.76 (s, 3H), 2.66
(br s, 4H); MS (FAB) 530 (M+).
J = 8.6 Hz, 2H), 6.81–6.77 (m, 4H), 5.48 (d,
J
(31P–1H) = 14 Hz, 2H), 3.95 (s, 3H), 3.82 (s, 3H), 2.80–
2.67 (br m, 4H); MS (FAB) 713 (MꢀBr)+.
4.1.45. 3-[4-(5-Methoxy-2-{2-methoxy-4-[(1,1,1-trip-
henylphosphino)methyl]phenyl}phenethyl)phenoxy]benzal-
dehyde bromide (17d). This compound was prepared
from 16d by means of a procedure similar to that used
1
4.1.40. 4-Methoxy-3-[4-(2-{(4-bromomethyl)phenyl}phen-
ethyl)phenoxy]benzaldehyde (16e). This compound was
prepared from 15e by means of a procedure similar to that
used for 16a. 1H NMR (500 MHz, CDCl3) d 9.80 (s, 1H),
7.62 (dd, J = 8.1, 2.1 Hz, 1H), 7.44 (d, J = 8.1 Hz, 2H),
7.36 (d, J = 1.7 Hz, 1H), 7.32–7.24 (m, 5H), 7.20 (d,
J = 7.3 Hz, 1H), 7.09 (d, J = 8.1 Hz, 1H), 6.88–6.82 (m,
4H), 4.66 and 4.57 (s, 2H), 3.95 (s, 3H), 2.89–2.86 (m,
2H), 2.70–2.67 (m, 2H); MS (FAB) 500 (M+).
for 17a. H NMR (500 MHz, CDCl3) d 9.92 (s, 1H),
7.80–7.73 (m, 10H), 7.61–7.56 (m, 7H), 7.48 (d,
J = 7.7 Hz, 1H), 7.46 (d, J = 2.1 Hz, 1H), 7.03 (m,
1H), 6.99 (d, J = 8.1 Hz, 1H), 7.02 (s, 1H), 6.99 (d,
J = 8.6 Hz, 1H), 6.94 (d, J = 8.6 Hz, 1H), 6.86–6.77
(m, 4H), 6.60–6.57 (m, 1H), 5.49–5.43 (m, 2H), 3.81 (s,
3H), 3.45 (s, 3H), 2.70 (br s, 4H); MS (FAB) 713
(MꢀBr)+.
4.1.46. 4-Methoxy-3-[4-(2-{4-[(1,1,1-triphenylphosphino)
methyl]phenyl}phenethyl)phenoxy]benzaldehyde bromide
(17e). This compound was prepared from 16e by means
4.1.41. 3-[4-(2-{(2-Methoxy-4-bromomethyl)phenyl}phen-
ethyl)phenoxy]benzaldehyde (16f). This compound was
prepared from 15f by means of a procedure similar to
1
of a procedure similar to that used for 17a. H NMR
1
that used for 16a. H NMR (500 MHz, CDCl3) d 9.94
(500 MHz, CDCl3) d 9.76 (s, 1H), 7.78–7.70 (m, 10H),
7.62–7.57 (m, 8H), 7.32 (d, J = 2.1 Hz, 1H), 7.30–7.22
(m, 2H), 7.15–7.03 (m, 5H), 6.87 (d, J = 8.6 Hz, 2H),
6.78 (d, J = 8.6 Hz, 2H), 5.50 (d, J (31P–1H) = 14 Hz,
2H), 3.93 (s, 3H), 2.83–2.77 (m, 2H), 2.72–2.70 (m,
2H); MS (FAB) 683 (MꢀBr)+.
(s, 1H), 7.56 (d, J = 7.7 Hz, 1H), 7.47 (dd, J = 8.1,
7.7 Hz, 1H), 7.39 (s, 1H), 7.31–7.23 (m, 3H), 7.17 (d,
J = 7.7 Hz, 1H), 7.09 (d, J = 7.3 Hz, 1H), 7.06–7.01
(m, 2H), 6.88 (d, J = 4.7 Hz, 2H), 6.90–6.85 (m, 3H),
4.66 and 4.57 (s, 2H), 3.78 (s, 3H), 2.78–2.64 (m, 4H);
MS (FAB) 500 (M+).
4.1.47. 3-[4-(2-{2-Methoxy-4-[(1,1,1-triphenylphosphino)
methyl]phenyl}phenethyl)phenoxy]benzaldehyde bromide
(17f). This compound was prepared from 16f by means
4.1.42. 4-Methoxy-3-[4-(5-methoxy-2-{2-methoxy-4-[(1,1,
1-triphenylphosphino)methyl]phenyl}phenethyl)phenoxy]
benzaldehyde bromide (17a). A mixture of 16a (876 mg,
1.56 mmol), triphenylphosphine (540 mg, 2.06 mmol),
and 15 mL of toluene was stirred for 19 h at 110 °C.
The mixture was filtered to afford 1.05 g (81%) of the ti-
1
of a procedure similar to that used for 17a. H NMR
(500 MHz, CDCl3) d 9.90 (s, 1H), 7.78–7.71 (m, 10H),
7.62–7.55 (m, 8H), 7.46 (dd, J = 8.1, 7.7 Hz, 1H),
7.38–7.36 (m, 1H), 7.05–7.03 (m, 3H), 6.91 (d,
J = 8.5 Hz, 2H), 6.84–6.82 (m, 4H), 6.61–6.58 (m, 1H),
5.50–5.46 (m, 2H), 3.44 (s, 3H), 2.76–2.63 (m, 4H);
MS (FAB) 683 (M+).
1
tle compound as a white solid. H NMR (500 MHz,
CDCl3) d 7.77 (s, 1H), 7.77–7.73 (m, 9H), 7.63–7.57
(m, 7H), 7.32 (d, J = 1.7 Hz, 1H), 7.10 (d, J = 8.6 Hz,
1H), 6.99 (d, J = 8.1 Hz, 1H), 6.92–6.90 (m, 3H), 6.84–
6.76 (m, 5H), 6.58 (d, J = 8.1 Hz, 1H), 5.42–5.37 (m,
2H), 3.95 (s, 3H), 3.81 (s, 3H), 3.43 (s, 3H), 2.69 (br s,
4H); MS (FAB) 743 (M+).
4.1.48. Trimethyl ether of (E/Z)-dehydroriccardin C
(18a). To a suspension of sodium methoxide (15.5 mg,
0.287 mmol) and 100 mL of dehydrated dichlorometh-
ane was added dropwise a solution of 17a (98.0 mg,
0.119 mmol) in 100 mL of dehydrated dichloromethane.
The mixture was refluxed for 30 h, filtered, and concen-
trated. The residue was purified by silica gel column
chromatography (eluent; n-hexane/ethyl acetate = 3:1,
v/v) to afford 44.3 mg (80%) of the title compound as
4.1.43. 4-Methoxy-3-[4-(2-{2-methoxy-4-[(1,1,1-trip-
henylphosphino)methyl]phenyl}phenethyl)phenoxy]benzal-
dehyde bromide (17b). This compound was prepared
from 16b by means of a procedure similar to that used
1
for 17a. H NMR (500 MHz, CDCl3) d 9.76 (s, 1H),
7.79–7.73 (m, 10H), 7.63–7.57 (m, 7H), 7.32 (d,
J = 1.7 Hz, 1H), 7.29–7.21 (m, 2H), 7.10 (d,
J = 8.1 Hz, 1H), 7.06 (d, J = 7.3 Hz, 1H), 6.97 (s, 1H),
6.90 (d, J = 8.6 Hz, 2H), 6.84 (d, J = 7.3 Hz, 1H), 6.80
(d, J = 8.1 Hz, 2H), 6.60 (d, J = 7.7 Hz, 1H), 5.48–5.40
(m, 2H), 3.95 (s, 3H), 3.44 (s, 3H), 2.70 (br m, 4H);
MS (FAB) 713 (MꢀBr)+.
1
a white solid. H NMR (500 MHz, CDCl3) d 7.37 (d,
J = 8.1 Hz, 1H), 7.07 (d, J = 8.6 Hz, 1H), 7.02–6.61
(m, 10H), 6.36 (d, J = 3.9 Hz, 1H), 6.17 (d, J = 6.2 Hz,
1H), 5.04 (s, 1H), 3.98 and 3.95 (s, 3H), 3.88 and 3.87
(s, 3H), 3.71 and 3.66 (s, 3H), 3.16–2.57 (m, 4H); MS
(FAB) 464 (M+).