H. Asghedom et al. / Tetrahedron Letters 43 (2002) 3989–3991
3991
analyzed by GC MS or purified by chromatography for
analysis by spectroscopic methods.
C-4a)], [147.4, 148.2, 152.7, 153.1 (C-3%, C-4%, C-6, C-7)],
+
169.5 (CꢀO); HRMS [M ] calcd for C H N O :
24
28
2
11
5
20.1693; found: 520.1732 (7.5 ppm deviation).
25
7: [h] −64.4 (c 2.2, acetone); IR 3013, 1743, 1519, 1330,
D
−
1 1
Acknowledgements
880 cm ; H NMR (CDCl
3
) l 7.65 (1H, s), 7.59 (1H, s),
.96 (1H, s), 6.85 (1H, d, J=3.75 Hz, H-4), 6.77 (1H, s),
.11 (1H, dd, J=8.85, 5.24 Hz, H-3), 3.97 (6H, s, -OCH3),
), 3.92 (3H, s, -OCH ), 3.85 (1H, t,
6
4
We thank the Nebraska Center for Mass Spectrometry
at the University of Nebraska for running the high
resolution mass spectra for compounds 6, 7, 8, and 12.
3.92 (3H, s, -OCH
3
3
J=8.83 Hz, H-3), 3.74 (1H, t, J=7.61 Hz, H-1), 3.68 (1H,
t, J=8.15 Hz, H-1), 3.28 (1H, dd, J=13.45, 4.63 Hz, H-9),
3.08 (1H, dd, J=13.48, 10.57 Hz, H-9), 2.94–2.99 (1H, m,
H-3a), 2.71–2.77 (1H, m, H-9a), 2.18 (3H, s, OCOCH );
3
13
References
C NMR (CDCl
) l 21.2 (CH of acetoxy), 30.6 (C-9),
3 3
4
3.2 (C-9a), 45.4 (C-3a), 56.27 (-OCH ), 56.37 (-OCH ),
3
3
1
. (a) Wilson, L.; Friedkin, M. Biochemistry 1967, 6, 3126;
b) Loike, J. D.; Brewer, C. F.; Sternlicht, H.; Gensler, W.
J.; Horwitz, S. B. Cancer Res. 1978, 38, 2688; (c) Brewer,
C. F.; Loike, J. D.; Horwitz, S. B.; Sternlicht, H.; Gensler,
W. J. J. Med. Chem. 1979, 22, 215; (d) Zavala, F.; Gue-
nard, D.; Robin, J. P.; Brown, E. J. Med. Chem. 1980, 23,
56.43 (-OCH ), 56.46 (-OCH ), 68.2 (C-3), 69.6 (C-4), 72.1
(C-1), [108. 51, 108.54, 113.4 (C-2%, C-5%, C-5, C-8)],
[130.66, 130.70 (C-8a, C-1%)], [140.1, 141.1 (C-4a, C-6%)],
3 3
(
[147.5, 148.4, 153.2, 153.6 (C-3%, C-4%, C-6, C-7)], 169.5
+
(CꢀO); HRMS [M ] calcd for C24
H N O11: 520.1693;
26 2
found: 520.1716 (4.4 ppm deviation).
8: [h] −27.4 (c 11.5, acetone); H NMR l 7.41 (s, 1H,
25
1
5
46.
. Tomioka, K.; Ishiguro, T.; Koga, K. Chem. Pharm. Bull.
985, 33, 4333.
D
2
H-5), 6.44 (d, 1H, H-2%), 6.65–6.66 (overlapping peaks,
H-5%, H-6%), 6.39 (s, 1H, H-2), 5.35 (d, 1H, H-7%), 4.00 (dd,
1
3
4
5
6
. Ho, T. L. Synthesis 1973, 347.
J=6.8, 9.1 Hz, 1H, H-9%), 3.94 (s, 3H, OCH
overlaps with OCH peak, H-9), 3.92 (s, 3H, OCH
(s, 3H, OCH ), 3.87 (s, 3H, OCH ), 3.75 (overlaps with
OCH , 1H, H-9%), 3.58 (dd, J=4.6, 9.1 Hz, 1H, H-9), 3.06
(dd, J=6, 13.1 Hz, 1H, H-7), 2.66 (dd, J=9.3, 13.1 Hz,
), 3.93 (1H,
3
. Ruck, K.; Kunz, H. J. Prakt. Chem. 1994, 336, 470.
. James, B. M.; Noel, V. R. Aust. J. Chem. 1975, 28, 831.
. Pai, S. G.; Bajpai, A. R.; Deshpande, A. B.; Samant, S. D.
Synth. Commun. 1997, 27, 2267.
3
), 3.90
3
3
3
3
1
3
7
8
9
. Barbiero, G.; Kim, W.-G.; Hau, A. S. Tetrahedron Lett.
1H, H-7), 2.34–2.4 (m, 2H, H-8, H-8%); C NMR l 21.2
(CH ), 37.7 (C-7), 41.2 (C-8), 49.3 (C-8%), 56.0 (OCH ),
56.1 (OCH ), 56.2 (OCH ), 56.3 (OCH ), 70.7 (C-9%), 72.8
1
994, 35, 5833.
3
3
. Bandaranayake, W.; Singhe, M.; Riggs, N. V. Aust. J.
3
3
3
Chem. 1981, 34, 115.
(C-9), 77.1 (C-7%), 107.9 (C-5), 108.3 (C-2%), 110.4 (C-5%),
114.2 (C-2), 119.2 (C-6%), 130.0 (C-1), 132.0 (C-1%), 140.0
. Spectral and analytical data. Selected spectral data for
2
5
6
: [h] −181 (c 2.3, acetone); IR 3018, 1741, 1334, 867
(C-6), [147.2, 152.6, C-3, C-4], [148.5, 148.7, C-3%, C-4%],
D
−
1
1
+
cm ; H NMR (CDCl ) l 7.43 (1H, s), 7.38 (1H, s), 6.53
169.9 (CꢀO); HRMS [M ] calcd for C24
H
29NO
9
: 475.1842;
3
(
1H, s), 6.55 (1H, s, H-8), 6.36 (1H, d, J=8.02 Hz, H-4),
.02 (1H, dd, J=8.79, 6.66 Hz, H-1), 3.93–3.99 (1H, m,
H-3), 3.93 (3H, s, -OCH ) 3.91 (3H, s, -OCH ), 3.90 (3H,
found: 475.18355 (−1.8 ppm deviation).
12: H NMR l 7.54 (s, 1H), 7.24 (dd, J=2.21, 6.8 Hz,
2H), 6.84 (dd, J=2.12, 6.66 Hz, 2H), 6.65 (s, 1H), 5.73 (t,
1
4
3
,
3
s, -OCH ), 3.83 (1H, dd, J=10.28, 4.63 Hz, H-3), 3.80
J=7.0 Hz, 1H), 3.91 (s, 3H, OCH
3.76 (s, 3H, OCH ), 2.91 (t, J=7.8 Hz, 2H), 2.02 (s, 3H),
1.80–1.94 (m, 2H), 1.56–1.70 (m, 2H); C NMR l 21.1
(CH ), 26.5 (CH ), 33.1 (CH ), 35.6 (CH ), 55.0 (CH ),
56.1 (CH ), 75.1 (CH), 108.2 (CH), 113.1 (CH), 113.7
3
), 3.88 (s, 3H, OCH ),
3
3
(
(
3H, s, -OCH ), 3.61 (1H, dd, J=8.86, 5.01 Hz, H-1), 3.04
1H, dd, J=13.33, 8.47 Hz, H-9), 2.95 (1H, dd, J=13.34,
3
3
13
6
.16 Hz, H-9), 2.51–2.60 (2H, m, H-3a, H-9a), 1.99 (3H, s,
3
2
2
2
3
13
OCOCH3); C NMR (CDCl ) l 20.7 (CH of acetoxy),
3
3
3
3
6.7 (C-9), 41.3 (C-9a), 49.2 (C-3a), 56.0 (-OCH ), 56.1
(CH), 127.8 (CH), 130.1 (CH), 132.2 (C), 132.4 (C), 140.9
(C), 147.1 (C), 152.9 (C), 170.2 (CꢀO)); HRMS [M ] calcd
3
+
(
(
-OCH ), 56.2 (-OCH ), 56.3 (-OCH ), 70.1 (C-3), 70.7
C-4), 73.7 (C-1), [107.5, 108.0, 108.1 (C-2%, C-5%, C-5)],
13.8 (C-8), [129.7, 129.8 (C-1%, C-8a)], [140.9, 141.0 (C-6%,
3
3
3
for C21
tion).
H25NO : 403.1631; found: 403.1637 (1.4 ppm devia-
7
1