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Abstract:

Bis(tributyltin)oxide (BBTO) has been utilized for the first time for the deprotection of steroid esters. The best results were obtained for 3β-esters, in particular the selective hydrolysis of the 3β-acetyl group in 3β,6α-diacetoxy-5α-pregnan-20-one to give 6α-acetoxy-3β-hydroxy-5α-pregnan-20-one. © 1995.

Registro:

Documento: Artículo
Título:Mild deprotection of steroid esters by Bis(tributyltin)oxide
Autor:Pérez, M.G.; Maier, M.S.
Filiación:Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pab. 2, Ciudad Universitaria, 1428 Buenos Aires, Argentina
Palabras clave:6alpha acetoxy 3beta hydroxy 5alpha pregnan 20 one; estrogen; gestagen; unclassified drug; article; hydrolysis; reaction analysis; steroidogenesis
Año:1995
Volumen:36
Número:19
Página de inicio:3311
Página de fin:3314
DOI: http://dx.doi.org/10.1016/0040-4039(95)00616-K
Título revista:Tetrahedron Letters
Título revista abreviado:Tetrahedron Lett.
ISSN:00404039
CODEN:TELEA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00404039_v36_n19_p3311_Perez

Referencias:

  • Greene, Wuts, (1991) Protective Groups in Organic Synthesis, pp. 10-142. , Wiley Interscience, New York
  • Therisod, Klibanov, (1987) J. Am. Chem. Soc., 109, pp. 3977-3981
  • Njar, Caspi, (1987) Tetrahedron Lett., 28, pp. 6549-6552
  • Salomon, Matta, Mascaretti, (1993) Tetrahedron, 49, pp. 3691-3748. , and references cited therein
  • Honda, Komori, (1986) Tetrahedron Lett., 27, pp. 3369-3372. , Compound 3a was prepared from pregnenolone acetate and 4-methyl-2-trimethylsilyloxy-1-pentene by means of the Mukaiyama's cross-aldol reaction as described in:, 1H NMR (CDCl3, 200 MHz) δ 0.86 (3H, s, H-18), 0.91 (3H, d, J 6.5 Hz, H-26), 0.92 (3H, d, J 6.5 Hz, H-27), 1.02 (3 H, s, H-19), 1.32 (3H, s, H-21), 2.03 (3H, s, CH3COO), 2.28 (2H, d, J 6.7 Hz, H-24), 2.54 (2H, d, J 6.5 Hz, H-22), 4.60 (1H, bs, H-3), 5.38 (1H, bs, H-6)
  • Vedejs, Erdman, Powell, (1993) J. Org. Chem., 58, pp. 2840-2845
  • Schwenk, Riegel, Moffett, Stahl, (1943) J. Am. Chem. Soc., 65, pp. 549-551. , Compound 5a was obtained by treatment of pregnenolone with succinic anhydride in pyridine and further methylation with diazomethane as described in:, 1H NMR (CDCl3, 200 MHz) δ 0.63 (3H, s, H-18), 1.02 (3H, s, H-19), 2.13 (3H, s, H-21), 2.62 (4H, s, CH3OCOCH2CH2COO), 3.70 (3H, s, CH3COO), 4.62 (1H, m, H-3), 5.38 (1H, bs, H-6)
  • Compound 6a was obtained by acetylation (Ac2O/Py, r.t., 18h) of 11a-hydroxyprogesterone. 1H NMR (CDCl3, 200 MHz) δ 0.75 (3H, s, H-18), 1.28 (3H, s, H-19), 2.05 (3H, s, CH3COO), 2.12 (3H, s, H-21), 5.30 (1H, m, H-11b), 5.77 (1H, s,H-4); Salomon, C.J.E.; Matta, G.; Mascaretti, O.A. J. Org. Chem. (in press); Kirk, Toms, Douglas, White, Smith, Latif, Hubbard, A survey of the high-field 1H NMR spectra of the steroid hormones, their hydroxylated derivatives, and related compounds (1990) Journal of the Chemical Society, Perkin Transactions 2, pp. 1567-1594
  • 1H NMR (CDCl3, 200 MHz) δ 0.61 (3H, s, H-18), 0.87 (3H, s, H-19), 2.03 (3H, s, CH3COO), 2.11 (3H, s, H-21), 3.55 (1H, m, H-3), 4.68 (1H, td, J 4.3 and J 10.8 Hz, H-6). 13C NMR (CDCl3, 50.1 MHz) δ 209.2 (C-20), 170.7 (CH3COO), 170.5 (CH3COO), 72.2 (C-6), 70.9 (C-3), 63.6 (C-17), 56.3 (C-14), 53.6 (C-9), 48.7 (C-5), 44.1 (C-13), 38.8 (C-12), 37.6 (C-7), 37.2 (C-1), 36.5 (C-10), 34.0 (C-8), 32.2 (C-4), 31.1 (C-2 and C-21), 24.3 (C-15), 22.8 (C-16), 21.1 (C-11 and CH3COO), 13.6 (C-19), 13.3 (C-18); Roccatagliata, Maier, Seldes, Iorizzi, Minale, (1994) J. Nat. Prod., 57, pp. 747-754
  • Nakamura, Yamada, Fujimoto, Kakinuma, Ikekawa, (1988) Chem. Pharm. Bull., 36, pp. 2808-2812
  • Honda, Igarashi, Komori, Biologically active glycosides from asteroidea, XXI. Structure of pectinioside C: Determination of the stereochemistry of the C-17 side chain of the steroidal aglycone (1990) Liebigs Annalen der Chemie, pp. 547-553

Citas:

---------- APA ----------
Pérez, M.G. & Maier, M.S. (1995) . Mild deprotection of steroid esters by Bis(tributyltin)oxide. Tetrahedron Letters, 36(19), 3311-3314.
http://dx.doi.org/10.1016/0040-4039(95)00616-K
---------- CHICAGO ----------
Pérez, M.G., Maier, M.S. "Mild deprotection of steroid esters by Bis(tributyltin)oxide" . Tetrahedron Letters 36, no. 19 (1995) : 3311-3314.
http://dx.doi.org/10.1016/0040-4039(95)00616-K
---------- MLA ----------
Pérez, M.G., Maier, M.S. "Mild deprotection of steroid esters by Bis(tributyltin)oxide" . Tetrahedron Letters, vol. 36, no. 19, 1995, pp. 3311-3314.
http://dx.doi.org/10.1016/0040-4039(95)00616-K
---------- VANCOUVER ----------
Pérez, M.G., Maier, M.S. Mild deprotection of steroid esters by Bis(tributyltin)oxide. Tetrahedron Lett. 1995;36(19):3311-3314.
http://dx.doi.org/10.1016/0040-4039(95)00616-K