The first synthesis of an A-ring fused steroidal isothiazole
A simple and efficient route to A-ring fused steroidal isothiazoles was developed. The key step involves C-S bond formation via substitution of a vinyl triflate at C-3. © 1994.
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| Autor principal: | |
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| Otros Autores: | , |
| Formato: | Capítulo de libro |
| Lenguaje: | Inglés |
| Publicado: |
1994
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| Acceso en línea: | Registro en Scopus DOI Handle Registro en la Biblioteca Digital |
| Aporte de: | Registro referencial: Solicitar el recurso aquí |
| Sumario: | A simple and efficient route to A-ring fused steroidal isothiazoles was developed. The key step involves C-S bond formation via substitution of a vinyl triflate at C-3. © 1994. |
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| Bibliografía: | Alivizatos, On, (1993) Anti Cancer Drugs, 4, p. 301 Murakoshi, Inada, Tagawa, Makino, Suzuki, Mieda, Honma, Yamanaka, (1992) Acta Pathologica Japonica, 42, p. 151 Ichikawa, Akimoto, Shimazaki, (1993) Endocrine Journal, 40, p. 425 Juniewicz, Hoekstra, Lemp, Barbolt, Devin, Gauthier, Frenette, Tremblay, (1993) Endocrinology, 133, p. 904 Stinson, Prostate drug Proscar cleared for marketing (1992) Chemical & Engineering News, 29, p. 7 Snyder, Winneker, Batzold, (1989) J. Steroid Biochem., 33, p. 1127 Mallamo, Pilling, Wetzel, Kowalczyk, Bell, Kullnig, Batzold, Winneker, (1992) J. Med. Chem., 35, p. 1663 Kumar, Daum, Bell, Alexander, Christiansen, Ackerman, Krolski, Wagner, (1991) Tetrahedron, 47, p. 5099 Kumar, Bell, (1992) Heterocycles, 34, p. 1289 Suschitzky, Scriven, (1992) Progress in Heterocyclic Chemistry, 4. , Pergamon Press Suschitzky, Scriven, (1993) Progress in Heterocyclic Chemistry, 5. , Pergamon Press Schulze, Mütze, Selke, Kempe, (1993) Tetrahedron Lett., 34, p. 1909 Mander, Sethi, (1983) Tetrahedron Lett., 24, p. 5425 Ziegler, Stirchak, Wester, (1986) Tetrahedron Lett., 27, p. 1229 Childs, Weber, (1976) J. Org. Chem., 41, p. 3486 Stang, Hanck, Subramanian, Perfluoroalkanesulfonic Esters: Methods of Preparation and Applications in Organic Chemistry (1982) Synthesis, p. 85 Lee, Snyder, (1990) J. Org. Chem., 55, p. 4995 McMurry, Scott, (1980) Tetrahedron Lett., 21, p. 4313 Brückner, Scheuplein, Suffert, (1991) Tetrahedron Lett., 32, p. 1449 Beard, Baum, Grakauskas, (1973) J. Org. Chem., 38, p. 3673. , Tetrahydrofuran must not be employed as a solvent in this reaction because it reacts with trifluoromethanesulfonic anhydride, or leads to polymerization Smith, Trott, (1956) C.A., 50, p. 13982. , U.S. Patent 2732398 (1956) A solution of 2-carboxymethyl-3-trifluoromethansulfonyloxy-5α-cholest-2-eno (IV) (1.44 g, 2.51 mmol) in ethanethiol (40 ml) was added to a suspension of sodium thioethoxide (9.74 g, 116 mmol) in ethanethiol (34.5 ml). The reaction mixture was kept at room temperature for 15 hs. After dilution with ethyl acetate, the mixture was washed with 1N NaOH and water. The dried (MgSO4) extract was evaporated and the residue was purified by flash chromatography to give pure thioenolether V (1.16 g, 95%); Cha, Kwon, (1987) J. Org. Chem., 52, p. 5486 Mancuso, Huang, Swern, (1978) J. Org. Chem., 43, p. 2480 Kimura, Fujita, Ando, Sonochemical activation of manganese dioxide. (1988) Chemistry Letters, p. 1387 McKinnon, Lee, Fused heterocycles fromo-acylbenzenethiol derivatives (1988) Canadian Journal of Chemistry, 66, p. 1405 Compound I was characterized: m.p.: 109.5–110°C (from methanol); [α]D: +61.0° (c=1.3, CHCl3); 1H-NMR (200 MHz, CDCl3) δ 0.69(3H,s,18-Me); 0.74(3H,s,19-Me); 0.87(6H,d,J=6.6 Hz, 26-Me y 27-Me); 0.92 (3H,d,J=6.4 Hz, 21-Me) ; 2.22 (1H,d,J=15.8 Hz, 1α-H); 2.44 (1H,ddd,J=17.6,11.1,2.0 Hz,4β-H); 2.78(1H,d,J=15.7 Hz,1β-H); 2.83(1H,dd,J=17.7,4.5 Hz,4α-H); 8,16(1H,s,2′-H); 13C-NMR (50 MHz, CDCl3) δ 11.6(C-19); 12.0(C-18); 18.7(C-21); 21.1(C-11); 22.5(C-26); 22.8(C-27); 23.8(C-23); 24.2(C-15); 27.8(C-4); 28.0(C-25); 28.2(C-16); 28.8(C-6); 31.6(C-7); 35.6(C-8); 35.8(C-10 y C-20); 36.2(C-22); 37.1(C-1); 39.5(C-24); 39.9(C-12); 42.4(C-13); 42.5(C-5); 53.7(C-9); 56.3(C-14 y C-17); 133.2(C-2); 157.3(C-3); 157.8(C-2′) |
| ISSN: | 00404039 |
| DOI: | 10.1016/S0040-4039(00)73456-3 |