Synthesis of pentacyclic steroids via tandem Stille coupling and Diels-Alder reactions

Journal of Organic Chemistry

Volumn 62, Issue 5, 1997, Pages 1326-1332

  Skoda Földes, Rita ^a   Jeges, György ^a   Kollár, László ^a   Horváth, Judit ^b   Tuba, Zoltán ^b  

^a UNIVERSITY OF PANNONIA   (Hungary)

^b GEDEON RICHTER LTD   (Hungary)

Author keywords

[No Author keywords available]

Indexed keywords

ANDROSTANE DERIVATIVE; STEROID;

ARTICLE; CHIRALITY; DRUG SYNTHESIS; GAS CHROMATOGRAPHY; IN VITRO STUDY; MASS SPECTROMETRY; METHODOLOGY; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030996240     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9615256     Document Type: Article

References (26)

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6. (b) Skoda-Földes, R.; Csákai, Z.; Kollár, L.; Horváth, J.; Tuba, Z. Steroids 1995, 60, 786.
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15. 4 in 4.5 h under the same conditions.
16. 1H-NMR δ 5.54 (brs, 1H), 5.15 (m, 1H), 4.02-4.24 (m, 4H), 3.28 (m, 1H), 3.00 (dd, J = 5.2 Hz, 12.5 Hz), 2.90 (m, 1H), 2.58 (m, 1H), 2.39 (m, 2H), 2.32 (m, 1H), 2.29 (m, 1H), 1.10-2.00 (m, 15H), 1.23 (t, J = 7.1 Hz, 3H), 1.20 (t, J = 7.1 Hz, 3H), 0.90 (s, 3H), 0.82 (s, 3H).
17. 1H-NMR δ 5.28 (m, 1H); MS m/e 410 (18), 367 (55), 91 (93), 67 (82), 55 (100).
18. 1H-NMR: δ 5.28 (m, 1H), 4.72-4.84 (m, 2H).
19. The five isomers were detected by GC-MS and gave almost identical mass spectra: (5a) MS m/e 370 (17), 355 (25), 93 (100), 67 71, 55 (83); (5b) MS m/e 355 (24), 217 (24), 145 (33), 121 (31), 91 (79), 67 (89), 55 (100); (5c) MS m/e 370 (3), 355 (89), 311 (55), 145 (30), 131 (33), 91 (68), 67 (77), 55 (100); (5d) MS m/e 370 (7), 355 (100), 145 (33), 131 (38), 91 (64), 67 (69), 55 (85); (6e) MS m/e 370 (1), 355 (100), 145 (31), 131 (29), 91 (59), 67 (60), 55 (81).
20. Heck, R. F. Palladium Reagents in Organic Synthesis; Academic Press: New York, 1985; pp 214-222.
21. For the spectral data of the main component (18) see Experimental Section. The minor, isomeric product was detected by GCMS: MS m/e 428 (1), 413 (100), 396 (28), 381 (36), 369 (50), 353 (77), 91 (72), 55 (65).
22. This compound was detected by GC-MS: MS m/e 342 (12), 327 (25), 178 (38), 91 (61), 67 (78), 55 (100).
23. Six-membered alicyclic rings can be aromatized e.g. in the presence of hydrogenation catalysts like platinum, palladium, and nickel. For a review, see: Rylander, P. N. Organic Synthesis with Noble Metal Catalysts; Academic Press: New York, 1973; pp 1-59.
24. Dehydrogenation of alkanes and alkenes via oxidative addition can take place in the presence of transition metal complexes. See: Crabtree, R. H.; Habib, A. Oxydation by Chemical Methods. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1993; Vol. 7, pp 4-7.
25. Coulson, D. R. Inorg. Synth. 1970, 13, 121.
26. Ukai, T.; Kawazura, H.; Ishii, Y. J. Organomet. Chem. 1974, 65, 253-266.