J.F.S. Carvalho et al. / Tetrahedron 66 (2010) 2455–2462
2461
J¼3.3, 1.8 Hz, 16-H); 13C NMR (75 MHz, DMSO-d6)
d ppm 15.8, 16.0,
3. Wielkoszynski, T.; Gawron, K.; Strzelczyk, J.; Bodzek, P.; Zalewska-Ziob, M.;
Trapp, G.; Srebniak, M.; Wiczkowski, A. BioEssays 2006, 28, 387–398.
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20.4 (CH2), 27.0, 28.3, 31.0 (CH2), 31.8 (CH2), 31.8 (CH2), 34.3 (CH2),
34.6 (CH2), 38.0 (C-10), 40.8 (CH2), 44.9, 45.8 (C-13), 55.7, 65.6, 74.0,
74.4, 145.3 (C-16), 154.4 (C-17), 196.2 (C-20); MS m/z (%): 349.4 (15)
[MþH]þ, 302.9 (96), 239.0 (54), 216.9 (42), 156.0 (45), 102.2 (100).
`
7. Joffre, C.; Leclere, L.; Buteau, B.; Martine, L.; Cabaret, S.; Malvitte, L.; Acar, N.;
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Mp 244–246 ꢀC (AcOEt/EtOH, thermal decomposition); lit.,64 232–
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20
235 ꢀC; [
a]
þ20 (c 0.25); IR (film) 3384, 2938, 2867, 1695, 1157,
D
1086, 1042, 1018, 961, 875 cmꢁ1
ppm 0.62 (3H, s, 18-CH3), 0.70 (1H, t, J¼38.5, 38.5 Hz), 1.17 (3H, s,
19-CH3), 2.10 (3H, s, 21-CH3), 2.53 (1H, d, J¼6.3 Hz,17 -H), 2.92 (1H,
s, OH), 3.28 (1H, d, J¼4.3 Hz, OH), 3.54 (1H, m, 6 -H), 3.66 (1H, d,
J¼4.1 Hz, OH), 3.73 (1H, d, J¼4.8 Hz, OH), 4.03 (1H, m, 3 -H), 4.68
(1H, m, 16 ppm 0.51 (3H, s, 18-
-H); 1H NMR (400 MHz, DMSO-d6)
CH3), 1.01 (3H, s, 19-CH3), 2.07 (3H, s, 21-CH3), 2.43 (1H, d, J¼6.3 Hz,
17 -H), 3.31 (1H, m, 6 -H), 3.69 (1H, s, OH), 3.80 (1H, m, 3 -H), 4.18
;
1H NMR (400 MHz, acetone-d6)
d
a
a
a
b
d
a
a
a
(1H, d, J¼4.2 Hz, OH), 4.42 (1H, d, J¼4.3 Hz, OH), 4.50 (1H, t,
J¼6.3 Hz, 16
b
-H); 4.63 (1H, d, J¼5.0 Hz, OH); 13C NMR (101 MHz,
DMSO-d6)
d
ppm 14.3, 16.1, 20.3 (CH2), 29.5, 31.0 (CH2), 31.7, 31.8
(CH2), 34.3 (CH2), 35.6 (CH2), 37.8 (C-10), 38.5 (CH2), 40.8 (CH2),
44.5, 44.6 (C-13), 53.4, 65.6, 70.4, 73.2, 73.9, 74.2 (C-5), 208.1
(C]O); MS m/z (%): 365.5 (4) [MꢁH]þ, 293.5 (4), 265.8 (10), 165.2
(100), 121.2 (13), 111.2 (13); HRMS (ESI), positive mode, m/z
[MþNa]þ calcd for C21H34NaO5: 389.2298, found: 389.2305.
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4.3.8. 16
a,17a-Epoxy-20-oxo-3b,5a,6b-trihydroxypregnan-21-yl
acetate (20). Flash chromatography (chloroform/ethanol 10:1 to
20
5:1) afforded a pure white solid. Mp 214–216 ꢀC (EtOH); [
(c 0.28); IR (film) 3399, 2940, 2867,1745,1719,1381,1231,1152,1053,
1007, 959, 874, 832 cmꢁ1; 1H NMR (400 MHz, DMSO-d6)
ppm 0.98
(3H, s, 18-CH3), 1.03 (3H, s, 19-CH3), 2.07 (3H, s, CH3COO), 3.31 (1H,
m, 6 -H), 3.69 (1H, s, OH), 3.79 (1H, m, 3 -H), 4.04 (1H, s, 16 -H),
a]
þ28.6
D
d
a
a
b
4.17 (1H, d, J¼5.7 Hz, OH), 4.46 (d, J¼4.1 Hz, OH), 4.64 and 4.76 (each
1H, 2 d, J¼17.4 Hz, 21-Ha and 21-Hb); 13C NMR (101 MHz, DMSO-d6)
34. Ibrahim-Ouali, M. Steroids 2007, 72, 475–508.
35. Salvador, J. A. R.; Silvestre, S. M.; Moreira, V. M. Curr. Org. Chem. 2008, 12,
492–522.
d
ppm 14.9, 16.0, 20.0 (CH2), 20.2, 27.0 (CH2), 27.4, 30.9 (CH2), 31.3
(CH2), 31.8 (CH2), 34.0 (CH2), 37.9 (C-10), 40.7 (CH2), 42.0 (C-13),
44.0, 44.9, 60.9, 65.5 (CH2), 65.6, 69.6 (C), 73.9, 74.3 (C), 169.6
(CH3COO), 199.3 (C]O); MS m/z (%): 421.6 (6) [MꢁH]þ, 388.9 (8),
353.7 (7), 339.4 (6), 325.8 (7), 311.9 (7), 307.7 (7), 293.6 (47), 265.9
(97), 149.5 (100), 146.8 (12); HRMS (ESI), positive mode, m/z
[MþNa]þ calcd for C23H34NaO7: 445.2197, found: 445.2196.
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Acknowledgements
43. Carvalho, J. F. S.; Silva, M. M. C.; Sa´ e Melo, M. L. Tetrahedron 2009, 65,
2773–2781.
44. Brougham, P.; Cooper, M. S.; Cummerson, D. A.; Heaney, H.; Thompson, N.
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ˆ
We thank Fundaça˜o para a Ciencia e Tecnologia (FCT), Portugal,
through FEDER/POCI 2010 for financial support. We acknowledge
the ‘Laboratorio de Espectrometria de Massa do Centro de Estudos
´
45. Heaney, H. Aldrichim Acta 1993, 26, 35–45.
46. Hua, R. Curr. Org. Synth. 2008, 5, 1–27.
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Tetrahedron Lett. 1999, 40, 285–286.
ˆ
Farmaceuticos da Universidade de Coimbra’, Portugal, for providing
data from the LC-MSn (QIT-MS), integrated in the Portuguese Na-
tional Mass Spectrometry Network (RNEM). J.F.S.C. also thanks
Fundaça˜o para a Cieˆncia e Tecnologia (FCT), Portugal, for a grant
´
48. Repichet, S.; Zwick, A.; Vendier, L.; Le Roux, C.; Dubac, J. Tetrahedron Lett. 2002,
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(SFRH/BD/18263/2004). Thanks are due to Fatima Nunes, from the
Mass Spectrometry Lab, University of Coimbra (LEM at CEF-UC).
51. Kamal, A.; Ahmed, S. K.; Sandbhor, M.; Ahmed Khan, M. N.; Arifuddin, M. Chem.
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Supplementary data
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Supplementary data associated with this article can be found, in
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