Mechanistic studies of the rearrangements of steroidal 16,17-ketols and syntheses of 20→16-cis-γ-carbolactones
Utilization of 17-keto-androstanes as starting materials for the synthesis of α- or β-oriented steroidal 20→16-γ-carbolactones has been explored following two different strategies. A highly efficient, stereospecific protocol has been developed for the β-oriented cis-γ-lactone. A different approach,...
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| Publicado: |
1999
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| Acceso en línea: | Registro en Scopus DOI Handle Registro en la Biblioteca Digital |
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| LEADER | 05885caa a22008537a 4500 | ||
|---|---|---|---|
| 001 | PAPER-2653 | ||
| 003 | AR-BaUEN | ||
| 005 | 20230518203207.0 | ||
| 008 | 190411s1999 xx ||||fo|||| 00| 0 eng|d | ||
| 024 | 7 | |2 scopus |a 2-s2.0-0033135903 | |
| 024 | 7 | |2 cas |a Androstanols; Lactones; Spironolactone, 52-01-7 | |
| 040 | |a Scopus |b spa |c AR-BaUEN |d AR-BaUEN | ||
| 030 | |a BMECE | ||
| 100 | 1 | |a Bruttomesso, A.C. | |
| 245 | 1 | 0 | |a Mechanistic studies of the rearrangements of steroidal 16,17-ketols and syntheses of 20→16-cis-γ-carbolactones |
| 260 | |c 1999 | ||
| 270 | 1 | 0 | |m Gros, E.G.; Departamento Quimica Organica, Fac. Ciencias Exactas/Naturales, Universidad de Buenos Aires, Pabellon 2, Buenos Aires 1428, Argentina; email: gros@quimor.qo.fcen.uba.ar |
| 506 | |2 openaire |e Política editorial | ||
| 504 | |a Heftmann, E., Schwimmer, S., (1972) Phytochem., 11, p. 2783 | ||
| 504 | |a Ripperger, H., Schreiber, K., (1981) The Alkaloids, 19, p. 81. , Academic Press: New York | ||
| 504 | |a Mazur, Y., Danieli, N., Sondheimer, F., (1960) J. Am. Chem. Soc., 82, p. 5889 | ||
| 504 | |a Fieser, L.F., Fieser, M., (1959) Steroids, pp. 810-846. , Reinhold: New York | ||
| 504 | |a Barton, D.H.R., Beckwith, A.L., Goosen, A., (1965) J. Chem. Soc., p. 181 | ||
| 504 | |a González, A.G., Francisco, C.G., Barreira, R.F., López, E.S.A., (1971) Quím., 67, p. 433. , Vespertilin (Ib) | ||
| 504 | |a Chackravarty, A.K., Das, B., Pakrashi, S.C., (1982) Phytochem., 21, p. 2083. , Solanolide (Ic) | ||
| 504 | |a Doller, D., Gros, E.G., (1990) Synth. Commun., 20, p. 3115 | ||
| 504 | |a Pelc, B., (1973) Steroids, p. 92. , Johns, W. F.; Ed.; Butterworths University Park Press: London | ||
| 504 | |a Mazur, Y., Danieli, N., Sondheimer, F., (1960) J. Am. Chem. Soc., 82, p. 5889 | ||
| 504 | |a NMR analysis of the reaction product showed attack from the β-face. Reference 9 reported the opposite stereochemistry for the attack by the Reformatsky reagent; Ola, K., Hara, S., (1978) J. Org. Chem., 43, p. 4408 | ||
| 504 | |a Doller, D., Gros, E.G., (1988) Magnetic Resonance in Chemistry, 26, p. 529 | ||
| 504 | |a Doller, D., Gros, E.G., (1989) Helvetica Chimica Acta, 31, p. 353 | ||
| 504 | |a Abraham, R.J., Loftus, P., (1981) Proton and Carbon-13 NMR Spectroscopy, p. 72. , Heyden and Son: Philadelphia | ||
| 504 | |a Numazawa, M., Nagaoka, M., Mutsumi, A., (1987) Chem. Pharm. Bull., 35, p. 4763 | ||
| 504 | |a Molecular mechanics calculations (MM2) were carried out using Chem3D Pro version 4.0 (1997), Cambridge Soft Corporation, Cambridge, MA; Bruttomesso, A.C., Doller, D., Gros, E.G., (1998) Synth. Commun., 28, p. 4043 | ||
| 504 | |a Numazawa, M., Osawa, Y., (1980) J. Am. Chem. Soc., 102, p. 5402 | ||
| 504 | |a Collins, C.J., Easthman, J.F., (1966) The Chemistry of the Carbonyl Compounds, p. 761. , Patai, S.; Ed.; John Wiley: New York Chapter 15 | ||
| 520 | 3 | |a Utilization of 17-keto-androstanes as starting materials for the synthesis of α- or β-oriented steroidal 20→16-γ-carbolactones has been explored following two different strategies. A highly efficient, stereospecific protocol has been developed for the β-oriented cis-γ-lactone. A different approach, involving prior attachment of a 3-carbon side chain on C-17 of a 17-oxo-16β-acetoxy-androstane led to the epimeric, α-oriented lactone. The mechanism of the rearrangement of epimeric 16β- or 16α-hydroxy-17-keto-androstanes to 17β-hydroxy-16-keto-androstanes was studied by 13C NMR spectroscopy. The former occurs through a 1,2-sigmatropic H-shift, while the latter is likely to take place by simple enolization-reprotonation. Copyright (C) 1999 Elsevier Science Ltd. |l eng | |
| 536 | |a Detalles de la financiación: Consejo Nacional de Investigaciones Científicas y Técnicas | ||
| 536 | |a Detalles de la financiación: Consejo Nacional de Investigaciones Científicas y Técnicas | ||
| 536 | |a Detalles de la financiación: We thank Universidad de Buenos Aires and Consejo Nacional de Investigaciones Cientı́ficas y Técnicas (CONICET, Argentina) for partial financial support. | ||
| 593 | |a Depto. de Quim. Orgánica, Fac. de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 2, 1428 Buenos Aires, Argentina | ||
| 593 | |a 3-Dimensional Pharmaceuticals, 665 Stockton Drive, Exton, PA 19341, United States | ||
| 690 | 1 | 0 | |a BIOSYNTHESIS |
| 690 | 1 | 0 | |a NATURAL PRODUCTS |
| 690 | 1 | 0 | |a NMR |
| 690 | 1 | 0 | |a STEREOSPECIFICITY |
| 690 | 1 | 0 | |a STEROIDS AND STEROLS |
| 690 | 1 | 0 | |a CARBONYL DERIVATIVE |
| 690 | 1 | 0 | |a HYDROXYL GROUP |
| 690 | 1 | 0 | |a KETOL |
| 690 | 1 | 0 | |a LACTONE DERIVATIVE |
| 690 | 1 | 0 | |a STEROID |
| 690 | 1 | 0 | |a TOMATINE |
| 690 | 1 | 0 | |a ARTICLE |
| 690 | 1 | 0 | |a CARBON NUCLEAR MAGNETIC RESONANCE |
| 690 | 1 | 0 | |a REACTION ANALYSIS |
| 690 | 1 | 0 | |a SYNTHESIS |
| 690 | 1 | 0 | |a ANDROSTANOLS |
| 690 | 1 | 0 | |a LACTONES |
| 690 | 1 | 0 | |a MAGNETIC RESONANCE SPECTROSCOPY |
| 690 | 1 | 0 | |a MODELS, CHEMICAL |
| 690 | 1 | 0 | |a MODELS, MOLECULAR |
| 690 | 1 | 0 | |a SPIRONOLACTONE |
| 700 | 1 | |a Doller, D. | |
| 700 | 1 | |a Gros, E.G. | |
| 773 | 0 | |d 1999 |g v. 7 |h pp. 943-947 |k n. 5 |p Bioorg. Med. Chem. |x 09680896 |w (AR-BaUEN)CENRE-3989 |t Bioorganic and Medicinal Chemistry | |
| 856 | 4 | 1 | |u https://www.scopus.com/inward/record.uri?eid=2-s2.0-0033135903&doi=10.1016%2fS0968-0896%2899%2900042-5&partnerID=40&md5=4f868ac95e39b230f0d26580e03a5149 |y Registro en Scopus |
| 856 | 4 | 0 | |u https://doi.org/10.1016/S0968-0896(99)00042-5 |y DOI |
| 856 | 4 | 0 | |u https://hdl.handle.net/20.500.12110/paper_09680896_v7_n5_p943_Bruttomesso |y Handle |
| 856 | 4 | 0 | |u https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_09680896_v7_n5_p943_Bruttomesso |y Registro en la Biblioteca Digital |
| 961 | |a paper_09680896_v7_n5_p943_Bruttomesso |b paper |c PE | ||
| 962 | |a info:eu-repo/semantics/article |a info:ar-repo/semantics/artículo |b info:eu-repo/semantics/publishedVersion | ||
| 963 | |a VARI | ||
| 999 | |c 63606 | ||