Journal of Asian Natural Products Research
531
room temperature. After 4 h, appropriate
NaBH4 was added to the solution at 08C,
and after an additional 4 h, 5% HCl was
added to the mixture to adjust pH value to
7. The mixture was poured into a large
amount of water, and the precipitate was
filtered to get the product (Scheme1).
3.81 (6H, br s, 40, 500-OCH3), 4.21–4.32
(2H, m, H-11), 4.56 (1H, d, J ¼ 4.2 Hz, H-
4), 4.70 (1H, d, J ¼ 5.1 Hz, H-1), 5.24
(2H, s, CH2-1000), 5.87 (1H, s, H-13), 5.93
(1H, s, H-13), 6.37 (2H, s, H-20, 60), 6.53
(1H, s, H-5), 6.65 (1H, s, H-8), 6.88 (1H,
dd, J ¼ 2.4, 8.9 Hz, H-600), 7.06 (2H,
J ¼ 8.2 Hz, H-3000, 5000), 7.19 (1H, d,
J ¼ 8.9 Hz, H-700), 7.32 (2H, d,
J ¼ 8.2 Hz, H-2000,6000), 7.40 (1H, s, H-200),
7.74 (1H, d, J ¼ 2.4 Hz, H-400), 8.52 (1H, s,
H-1000); 13C NMR (300 MHz, CDCl3): d
175.6 (C-12), 152.5 (C-30, 50), 147.6 (C-7),
147.1 (C-6), 136.1 (C-1’), 133.3 (C-40),
131.8 (C-10), 133.2 (C-9), 104.3 (C-5),
110.8 (C-8), 108.5 (C-20, 60), 104.3 (C-13),
68.4 (C-11), 60.7 (C-4), 55.7 (C-40-OCH3),
56.3 (C-30, 50-OCH3), 50.3 (C-indol-
OCH3), 44.2 (C-1), 41.7 (C-2), 38.0
(C-3), 131.6 (C-200), 114.0 (C-300), 125.8
(C-400), 154.5 (C-500), 126.8 (C-700), 110.8
(C-600), 131.6 (C-800), 130.3 (C-900), 55.7
(100-CH2), 155.5 (CvN), 126.8 (C-2000,6000),
125.8 (C-3000,5000), 113.2 (C-4000), 133.4
(C-1000), 34.5 (4000-CH), 31.2 (C-(CH3)3);
HR-ESI-MS: m/z 717.3196 [M þ H]þ
(calcd for C43H45N2O8, 717.3176).
3.2.1 Compound 8: N0-4b-imino-[1-(2-
fluoro)-benzyl-5-methoxyl-1H-indol-3-
methylene]-4-deoxypodophyllotoxin
20
White powder; ½aꢀD 2 26.1 (c ¼ 0.52,
1
CH2Cl2); H NMR (300 MHz, CDCl3): d
3.01–3.20 (1H, m, H-3), 3.77 (6H, s, 30, 50-
OCH3), 3.81 (6H, s, 40, 500-OCH3), 3.83
(1H, d, J ¼ 4.8 Hz, H-2), 4.23–4.29 (2H,
m, H-11), 4.56 (1H, d, J ¼ 4.2 Hz, H-4),
4.70 (1H, d, J ¼ 4.8 Hz, H-1), 5.32 (2H, s,
CH2-1000), 5.87 (2H, s, H-13), 6.37 (2H, s,
H-20, 60), 6.53 (1H, s, H-5), 6.65 (1H, s, H-
8), 6.80–6.90 (2H, m, H-3000, 6000), 6.93–
7.05 (2H, m, H-4000,5000), 7.06–7.28 (2H, m,
H-600, 700), 7.74 (1H, d, J ¼ 2.4 Hz, H-200),
8.53 (1H, s, H-1000); 13C NMR (300 MHz,
CDCl3): d 174.6 (C-12), 160.6 (C-2000),
158.2 (CvN), 153.4 (C-500), 151.5 (C-30,
50), 146.7 (C-7), 146.1 (C-6), 135.1 (C-1’),
135.1 (C-40), 132.4 (C-10), 132.3 (C-800),
131.2 (C-900), 131.3 (C-200), 130.0 (C-5000),
128.1 (C-9), 125.6 (C-6000), 123.6(C-400),
123.5 (C-1000), 122.5 (C-4000), 122.4 (C-600),
114.5 (C-3000), 113.3 (C-300), 112.3 (C-700),
111.2 (C-8), 109.5 (C-5), 107.5 (C-20, 60),
100.5 (C-13), 67.5 (C-CH2), 67. 4 (C-11),
59.7 (C-4), 55.3 (C-30, 50-OCH3), 54.7 (C-
500-OCH3), 54.5 (C-40-OCH3), 43.2 (C-1),
43.3 (C-2), 37.0 (C-3); HR-ESI-MS: m/
3.2.3 Compound 10: N’-4b-imino(1-
benzyl-5-methoxyl-1H-indol-3-
methylene)-4-deoxypodophyllotoxin
20
White powder; ½aꢀD 2 35.9 (c ¼ 0.56,
1
CH2Cl2); H NMR (300 MHz, CDCl3): d
3.09–3.12 (2H, m, H-2, 3), 3.77 (6H, s, H-
30, 50-OCH3), 3.81 (6H, s, H-40, 500-OCH3),
4.22–4.32 (2H, m, H-11), 4.55 (1H, d,
J ¼ 3.9 Hz, H-4), 4.69 (1H, d, J ¼ 4.8 Hz,
H-1), 5.41 (2H, s, CH2-1000), 6.01 (1H, s, C-
13), 5.94 (1H, s, C-13), 6.37 (2H, s, H-20,
60), 6.65 (1H, s, H-5), 6.53 (1H, s, H-8),
6.87 (1H, d, J ¼ 2.1 Hz, H-600), 7.06 (2H,
J ¼ 6.6 Hz, H-3000, 5000), 7.74 (1H, d,
J ¼ 2.1 Hz, H-700), 7.31 (2H, d,
J ¼ 6.6 Hz, H-2000, 6000), 7.39 (1H, s, H-
400), 7.16 (1H, s, H-200), 8.53 (1H, s, H-1000);
13C NMR (300 MHz, CDCl3): d 175.6 (C-
12), 152.6 (C-30, 50), 147.7 (C-7), 136.1
(C-10), 136.3 (C-40), 128.9 (C-9), 132.5 (C-
z
C39H36FN2O8, 679.2456).
679.2468 [M þ H]þ (calcd for
3.2.2 Compound 9: N’-4b-imino[1-(4-t-
butyl)-benzyl-5-methoxyl-1H-indol-3-
methylene]-4-deoxypodophyllotoxin
20
White powder; ½aꢀD 2 65.8 (c ¼ 0.49,
1
CH2Cl2); H NMR (300 MHz, CDCl3): d
1.29 (9H, s, 4000-CH(CH3)3), 3.09–3.12
(2H, m, H-2, 3), 3.77 (6H, s, 30, 50-OCH3),