Oxidation Reactions in 9a-Halosteroids by Jones Reagent
DOI:
https://doi.org/10.29356/jmcs.v51i4.1288Keywords:
Oxidation, androstane, anabolic activity, stereochemistryAbstract
Abstract. Current investigations guided to searching androstane derivatives with potential anabolic activity, weakly androgenic one directed us to synthesize 3b,11b-dihydroxy-9a-halo-5a-androstane-17-ones (4a-c). These compounds were oxidized by Jones’ Reagentat 0°C obtaining a selective oxidation of the equatorial 3b-hydroxyl group. This behaviour could be explained by the high steric hindrance at the 11b-position, increased by the strong inductive effect of the halogen atom at C-9a over the electronic density of the H-11a.
Resumen. Investigaciones recientes dirigidas a encontrar derivados androstánicos con potencial actividad anabólica y débil carácterandrogénico nos llevó a sintetizar 3b,11b-dihidroxi-9a-halo-5aandrostan-17-onas (4a-c). Estos compuestos fueron oxidados con el reactivo de Jones a 0°C obteniendo una oxidación selectiva del grupo ecuatorial 3b-hidroxilo. Este comportamiento puede ser explicado por el elevado impedimento estérico en la posición 11b, incrementado por el fuerte efecto inductivo en el C-9a sobre la densidad electrónica de H-11a.
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9. Fuente, A.; Reyes, M.; Álvarez, Y. M.; Ruiz, J. A.; Vélez, H.; Viñas-Bravo, O.; Montiel-Smith, S.; Meza-Reyes, S.; Sandoval- Ramírez, J. Magn. Reson. Chem. 2005, 43, 676-678.
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16. Novoa de Armas, H.; Peeters, O. M.; Blaton, N. M.; De Ranter, C. J.; Ruiz, J. A.; Reyes, M.; Álvarez, Y. M. Acta Cryst. 2001, E57, 39-40.
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21. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A.; Vreven, Jr. T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.;
Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox,
D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Revision D.01, Gaussian, Inc., Pittsburgh, PA 2003.
22. Frisch, A.; Dennington II, R. D.; Keith, T. A.; Nielsen, A. B.; Holder, A. J. Gaussview, Reference, Gaussian, Inc., Pittsburgh, PA 1997-2003. http://www.gaussian.com/gv_plat.htm.
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