G. Neef et al. / Tetrahedron Letters 42 (2001) 1011–1015
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13. Wipf, P.; Jeger, P.; Kim, Y. Bioorg. Med. Chem. Lett. 1998,
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14. (a) Goldenstein, K.; Fendert, T.; Proksch, P.; Winterfeldt,
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15. Selected physicochemical and spectroscopic data: 5, mp
191–193°C (ethyl acetate), [h]D +46.5 (CHCl3, c=0.505);
1H NMR (CDCl3, 400 MHz):16 l=1.55 ppm (dd, J=11
and 14 Hz, 1H, H-5); 1.68 (s, 3H, 4-C[ꢀC]-CH3); 1.78 (ddd,
J=6, 10, 15 Hz, 1H, H-3); 1.95 (s, 3H, 5%-CH3); 2.03–2.12
(m, 1H, H-3); 2.53 (dd, J=8 and 14 Hz, 1H, H-5); 2.09–2.11
(m, 1H, H-4); 3.44 (dd, J=3 and 5 Hz, 1H, H-5%%); 3.48 (dd,
J=3 and 5 Hz, 1H, H-7%%); 3.77 (t, J=5 Hz, 1H, H-1%%); 3.93
(s, 3H, COOCH3); 4.07 (t, J=5 Hz, 1H, H-3%%); 4.18 (dd,
J=6 and 7 Hz, 1H, H-2); 4.45–4.58 (AB-system, 2H,
O-CH2-Ph); 4.69 (s, 1H, C=CH[‘Z’]); 4.78 (s, 1H,
CꢀCH[‘E’]); 7.34 (d, J=8 Hz, 2H, aryl-H); 8.03 (d, J=
8 Hz, 2H, aryl-H). 6, mp 192–194°C (MeCN–H2O),
[h]D +205.5 (CHCl3, c=0.523); 1H NMR (CDCl3, 400
MHz):16 l=1.68 ppm (ddd, J=5, 12.5, 15 Hz, 1H, H-3);
1.77 (s, 3H, 2-C[ꢀC]-CH3); 1.84 (t, J=12.5 Hz, 1H, H-5);
2.00 (s, 3H, 11-CH3); 2.33 (d, J=13 Hz, 8-OH); 2.35–2.45
(m, 2H, H-3 and H-5); 2.45–2.57 (m, 1H, H-4); 2.84–2.90
(m, 2H, H-7); 4.12 (dt, J=13 and 7.5 Hz, 1H, H-8); 4.78
(s, 1H, C=CH); 4.83 (d, J=2 Hz, 1H, C=CH); 5.12 (d;
J=5 Hz, 1H, H-3a); 5.78 (s, 1H, 5-OH). 8, mp 176–179°C
(hexane–ethyl acetate), [h]D +109.0 (CHCl3, c=0.5); 1H
NMR (CDCl3, 400 MHz):16 l=1.48 ppm (ddd, J=6, 11,
14 Hz, 1H, H-3); 1.69 (t, J=14 Hz, 1H, H-1); 1.73 (s, 3H,
2-C[=C]-CH3); 1.98 (s, 3H, 11-CH3); 2.08 (ddd, J=2, 5,
14 Hz, 1H, H-3); 2.23 (ddd, J=2, 4, 14 Hz, 1H, H-1);
2.35–2.44 (m, 1H, H-2); 3.53 (dd, J=1 Hz and 4 Hz, 1H,
H-7); 3.65–3.68 (m, 1H, H-6); 3.80–3.82 (m, 1H, H-5); 3.92
(s, 3H, COOCH3); 4.07 (t, J=2 Hz, 1H, H-4a); 4.38 (d, J=6
Hz, 1H, H-3a); 4.57 (d, J=13 Hz, 1H, O-CH2-Ph); 4.73
(s, 1H, C=CH [Z]); 4.74 (d, J=13 Hz, 1H, O-CH2-Ph);
4.80 (s, 1H, C=CH [E]); 7.44 (d, J=8 Hz, 2H, aryl-H);
8.01 (d, J=8 Hz, 2H, aryl-H). 9, mp 172-173 (hexane–ethyl
acetate), [h]D −154.7 (CHCl3, c=0.506); 1H NMR (CDCl3,
400 MHz):16 l=1.64 ppm (s, 6H, [H3C]2C=C); 2.04 (s, 3H,
5%-CH3); 2.37–2.47 (m, 1H, H-3); 2.46 (d, J=16 Hz, 1H,
H-5); 2.52 (d, J=16 Hz, 1H, H-5); 2.85 (dd, J=17 Hz and
8 Hz, 1H, H-3); 2.38 (dd, J=3 Hz and 4 Hz, 1H, H-5¦);
3.49 (dd, J=3 Hz and 4 Hz, 1H, H-7¦); 3.60 (t, J=8 Hz,
1H, H-1¦); 3.86 (t, J=8 Hz, 1H, H-3¦); 3.92 (s, 3H,
COOCH3); 4.18 (t, J=8 Hz, 1H, H-2); 4.46 (d, J=12 Hz,
1H, O-CH2-Ph); 4.69 (d, J=12 Hz, 1H, O-CH2-Ph); 7.34
(d, J=8 Hz, 2H, aryl-H); 8.02 (d, J=8 Hz, 2H, aryl-H).
16. Atom numbering for compounds 5 and 6.
6. Mancini, I.; Guella, G.; Laboute, P.; Debitus, C.; Pietra,
F. J. Chem. Soc., Perkin Trans. 1 1993, 3121.
7. Neef, G.; Baesler, S.; Depke, G.; Vierhufe, H. Tetrahedron
Lett. 1999, 40, 7969.
8. Domagala, J. M.; Bach, R. D.; Wemple, J. J. Am. Chem.
Soc. 1976, 98, 1975.
9. Kac¸an, M.; Koyuncu, D.; McKillop, A. J. Chem. Soc.,
Perkin Trans. 1 1993, 1771.
10. Crystal data for 5:15 C25H27NO7, M=453.48, orthorhom-
bic, space group P2(1)2(1)2(1), crystal size 0.7×0.25×0.1
mm3, unit cell dimensions a=9.606(2), b=10.482(2), c=
3
,
,
22.943(3) A, h=90, i=90, k=90°, V=2310.1(7) A , Z=4,
D=1.304 Mg/m3, absorption coefficient 0.095 mm−1, T=
,
273(2) K, wavelength u=0.71073 A, 3352 reflections col-
lected, 3146 independent reflections [R(int)=0.0128], R
indices (all data) R1=0.0505, wR2=0.1210. The crystallo-
graphic data for 5 have been deposited at the CCDC, 12
Union Road, Cambridge CB2 1EZ, UK and copies can be
obtained on request, free of charge, by quoting the
publication citation and the deposition number CCDC
152704.
11. (a) Loupy, A.; Petit, A.; Hamelin, J.; Texier-Boullet, F.;
Jacquault, P.; Mathe´, D. Synthesis 1998, 1213; (b) The
equipment used was a Synthewave 402, ProLabo. After 5
min of irradiation (300 W) the internal temperature of the
probe had reached 162°C.
12. Crystal data for 6·0.5H2O:15 C16H19NO5, M=305.54,
orthorhombic, space group P2(1)2(1)2(1), crystal size 0.7×
0.5×0.2 mm3, unit cell dimensions a=6.732(1), b=
,
10.576(2), c=21.90(4) A, h=90, i=90, k=90°, V=
3
3
,
1559.3(5) A , Z=4, D=1.335 Mg/m , absorption coeffi-
cient 0.101 mm−1, T=173(2) K, wavelength u=0.71073 A,
,
2939 reflections collected, 2512 independent reflections
[R(int)=0.0204], R indices (all data) R1=0.0309, wR2=
0.0734. The crystallographic data for 6 have been deposited
at the CCDC under deposition number CCDC 152705.
.