K. A. Monk et al. / Bioorg. Med. Chem. 14 (2006) 3231–3244
3239
equivalent in 20 mL of dichloromethane) was trans-
ferred to the round-bottomed flask using a cannula.
The reaction mixture was allowed to warm from 0 ꢁC
to room temperature. The reaction was monitored by
TLC and cautiously quenched with 5 mL of water (after
approximately 5–8 h). The products were isolated by
extraction with dichloromethane and purified with flash
chromatography using gradient elution.
(d, 1H, J = 12.0, vinyl CH), 6.83 (s, 1H, ArH), 6.61 (d,
1H, J = 12.0, vinyl CH), 6.31 (s, 2H, ArH), 6.08 (s,
1H, ArH), 3.99 (s, 3H, OCH3), 3.81 (s, 3H, OCH3),
3.64 (s, 6H, OCH3). 13C NMR (CDCl3, 75 MHz): d
152.8, 150.2, 145.4, 140.2, 137.6, 131.4, 130.6, 129.6,
126.6, 117.1, 107.3, 106.5, 60.9, 56.5, 55.9. Anal. Calcd
for C18H19NO7: C, 59.83; H, 5.30; N, 3.88. Found: C,
59.97; H, 5.20; N, 3.91.
3.2.12. (Z)-2-(20-Nitro-30-tert-butyldimethylsilyloxy-40-
methoxyphenyl)-1-(3,4,5-trimethoxyphenyl)ethene (23a).
Yield (47%) of a yellow liquid. Rf (25% EtOAc/hex-
3.2.17. (E)-2-(30-Hydroxy-40-methoxy-60-nitrophenyl)-1-
(3,4,5-trimethoxyphenyl)ethene (25b)ꢀ. Yield (33%) of a
yellow solid. Rf (25% EtOAc/hexanes) = 0.16. 1H
NMR (CDCl3, 300 MHz): d 7.64 (s, 1H, ArH), 7.62
(d, 1H, J = 15.9, vinyl CH), 7.22 (s, 1H, ArH), 6.90 (d,
1H, J = 15.9, vinyl CH), 6.75 (s, 2H, ArH), 6.15 (s,
1H, ArH), 3.99 (s, 3H, OCH3), 3.91 (s, 6H, OCH3),
3.88 (s, 3H, OCH3). 13C NMR (CDCl3, 75 MHz): d
153.5, 150.3, 145.6, 140.0, 138.6, 132.8, 132.5, 129.3,
123.8, 113.1, 107.8, 104.1, 61.0, 56.5, 56.2.
1
anes) = 0.41. H NMR (CDCl3, 300 MHz): d 6.77 (s,
2H, ArH), 6.61 (d, 1H, J = 12.0, vinyl CH), 6.41 (s,
2H, ArH), 6.38 (d, 1H, J = 12.0, vinyl CH), 3.82 (s,
3H, OCH3), 3.81 (s, 3H, OCH3), 3.67 (s, 6H, OCH3),
0.94 (s, 9H, t-Bu CH3), 0.19 (s, 6H, CH3). 13C NMR
(CDCl3, 75 MHz): d 152.8, 149.9, 144.3, 137.4, 137.2,
133.6, 131.6, 122.8, 122.6, 122.1, 112.4, 106.1, 60.9,
55.8, 55.6, 25.6, 18.5, ꢁ4.3.
3.2.18. (Z)-2-(20-Nitro-30-methoxy-40-tert-butyldimethyl-
silyloxyphenyl)-1-(3,4,5-trimethoxyphenyl)ethene (39a).
Yield (21%) of a yellow oil. Rf (25% EtOAc/hex-
3.2.13. (E)-2-(20-Nitro-30-tert-butyldimethylsilyloxy-40-
methoxyphenyl)-1-(3,4,5-trimethoxyphenyl)ethene (23b).
Yield (25%) of a yellow solid. Rf (25% EtOAc/hex-
1
anes) = 0.53. H NMR (CDCl3, 300 MHz): d 6.88 (d,
1
anes) = 0.29. H NMR (CDCl3, 300 MHz): d 7.23 (d,
1H, J = 8.5, ArH), 6.81 (d, 1H, J = 8.5, ArH), 6.63 (d,
1H, J = 12.0, vinyl CH), 6.40 (s, 2H, ArH), 6.37 (d, 1H,
J = 12.0, vinyl CH), 3.90 (s, 3H, OCH3), 3.82, (s, 3H,
OCH3), 3.68 (s, 6H, OCH3), 1.01 (s, 9H, t-Bu CH3),
0.20 (s, 6H, CH3). 13C NMR (CDCl3, 75 MHz): d 152.9,
148.7, 146.4, 143.1, 137.6, 133.9, 131.3, 125.4, 123.8,
122.7, 122.1, 106.1, 61.9, 60.9, 55.8, 25.5, 18.2, ꢁ4.6.
1H, J = 8.4, ArH), 6.94 (d, 1H, J = 15.9, vinyl CH),
6.93 (d, 1H, J = 8.7, ArH), 6.73 (d, 1H, J = 15.9, vinyl
CH), 6.66 (s, 2H, ArH), 3.89 (s, 6H, OCH3), 3.87 (s,
3H, OCH3), 3.86 (s, 3H, OCH3), 0.95 (s, 9H, t-Bu
CH3), 0.21 (s, 6H, CH3). 13C NMR (CDCl3, 75 MHz):
d 153.4, 150.0, 143.6, 138.4, 137.1, 132.3, 131.7, 122.6,
120.2, 118.1, 112.8, 103.8, 61.0, 56.1, 55.6, 25.6, 18.5,
ꢁ4.2.
3.2.19. (E)-2-(20-Nitro-30-methoxy-40-tert-butyldimethyl-
silyloxyphenyl)-1-(3,4,5-trimethoxyphenyl)ethene (39b).
Yield (30%) of a yellow solid. Rf (25% EtOAc/hex-
3.2.14. (Z)-2-(30-tert-Butyldimethylsilyloxy-40-methoxy-
50-nitrophenyl)-1- (3,4,5-trimethoxyphenyl)ethene (24a).
Yield (33%) of a yellow oil. Rf (25% EtOAc/hex-
1
anes) = 0.45. H NMR (CDCl3, 300 MHz): d 7.33 (d,
1H, J = 8.7, ArH), 6.96 (d, 1H, J = 16.2, vinyl CH),
6.96 (d, 1H, J = 8.7, ArH), 6.75 (d, 1H, J = 16.2, vinyl
CH), 6.66 (s, 2H, ArH), 3.91 (s, 3H, OCH3), 3.90 (s,
6H, OCH3), 3.87 (s, 3H, OCH3), 1.03 (s, 9H, t-Bu
CH3), 0.24 (s, 6H, CH3). 13C NMR (CDCl3, 75 MHz):
d 153.4, 148.8, 145.7, 143.0, 138.6, 132.3, 132.1, 123.3,
123.0, 121.1, 119.7, 103.9, 61.9, 60.9, 56.1, 25.6, 18.2,
ꢁ4.5.
1
anes) = 0.75. H NMR (CDCl3, 300 MHz): d 7.31 (d,
1H, J = 2.0, ArH), 6.93 (d, 1H, J = 2.0, ArH), 6.62 (d,
1H, J = 12.0, vinyl CH), 6.43 (s, 2H, ArH), 6.43 (d, 1H,
J = 12.0, vinyl CH), 3.90 (s, 3H, OCH3), 3.84 (s, 3H,
OCH3), 3.73 (s, 6H, OCH3), 0.94 (s, 9H, t-Bu CH3),
0.06 (s, 6H, CH3). 13C (CDCl3, 75 MHz): d 153.3,
150.2, 145.2, 143.8, 137.7, 133.2, 132.1, 131.8, 127.3,
125.1, 117.6, 105.8, 61.8, 60.9, 56.0, 25.5, 18.1, ꢁ4.8.
3.2.20. (Z)-2-(30-Methoxy-40-tert-butyldimethylsilyloxy-
50-nitrophenyl)-1-(3,4,5-trimethoxyphenyl)ethene (40a).
Yield (40%) of a yellow liquid. Rf (25% EtOAc/hex-
3.2.15. (E)-2-(30-tert-Butyldimethylsilyloxy-40-methoxy-
50-nitrophenyl)-1 -(3,4,5-trimethoxyphenyl)ethene (24b).
Yield (24%) of a yellow solid. Rf (25% EtOAc/hex-
1
anes) = 0.50. H NMR (CDCl3, 300 MHz): d 7.27 (d,
1
anes) = 0.58. H NMR (CDCl3, 300 MHz): d 7.54 (d,
1H, J = 1.9, ArH), 6.90 (d, 1H, J = 1.9, ArH), 6.58 (d,
1H, J = 12.1, vinyl CH), 6.51 (s, 2H, ArH), 6.43 (d, 1H,
J = 12.1, vinyl CH), 3.84 (s, 3H, OCH3), 3.73 (s, 6H,
OCH3), 3.59 (s, 3H, OCH3), 0.95 (s, 9H, t-Bu CH3),
0.16 (s, 6H, CH3). 13C NMR (CDCl3, 75 MHz): d 153.2,
151.0, 142.6, 138.4, 137.6, 132.0, 131.1, 129.6, 127.7,
117.0, 115.2, 105.9, 60.9, 56.0, 55.4, 25.6, 18.6, ꢁ4.2.
3.2.21. (E)-2-(30-Methoxy-40-tert-butyldimethylsilyloxy-
50-nitrophenyl)-1-(3,4,5-trimethoxyphenyl)ethene (40b).
Yield (33%) of a yellow solid. Rf (25% EtOAc/
1H, J = 2.2, ArH), 7.15 (d, 1H, J = 2.2, ArH), 6.96 (d,
1H, J = 16.2, vinyl CH), 6.86 (d, 1H, J = 16.2, vinyl
CH), 6.73 (s, 2H, ArH), 3.95 (s, 3H, OCH3), 3.93 (s,
6H, OCH3), 3.88 (s, 3H, OCH3), 1.05 (s, 9H, t-Bu
CH3), 0.26 (s, 6H, CH3). 13C (CDCl3, 75 MHz): d
153.5, 150.8, 145.5, 144.3, 138.5, 133.5, 132.1, 130.6,
125.4, 122.9, 114.9, 103.8, 61.8, 61.0, 56.2, 25.6, 18.3,
ꢁ4.5.
3.2.16. (Z)-2-(30-Hydroxy-40-methoxy-60-nitrophenyl)-1-
(3,4,5-trimethoxyphenyl)ethene (28). Yield (11%) of a
yellow solid. Rf (35% EtOAc/hexanes) = 0.21. 1H
NMR (CDCl3, 300 MHz): d 7.74 (s, 1H, ArH), 6.85
ꢀ
TBS-deprotection occurred in the reaction.