Structural modification of steroids through functionalised organolithium compounds

Tetrahedron Asymmetry

Volumn 11, Issue 10, 2000, Pages 2063-2066

  Falvello, Larry R ^a   Foubelo, Francisco ^b   Soler, Tatiana ^b   Yus, Miguel ^b  

^a Instituto de Nanociencia y Materiales de Aragón   (Spain)

^b UNIVERSITY OF ALICANTE   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

CHOLESTANE DERIVATIVE; EPOXYSTEROID; ESTRONE DERIVATIVE; LITHIUM; ORGANOLITHIUM COMPOUND; STEROID; UNCLASSIFIED DRUG; WATER;

ARTICLE; CATALYSIS; CHEMICAL MODIFICATION; CONTROLLED STUDY; DRUG PURITY; DRUG STRUCTURE; DRUG SYNTHESIS; ENANTIOMER; HYDROLYSIS; NUCLEAR MAGNETIC RESONANCE; PRIORITY JOURNAL; STEREOCHEMISTRY; TECHNIQUE; TEMPERATURE; X RAY CRYSTALLOGRAPHY;

EID: 0034595691     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(00)00175-0     Document Type: Article

References (26)

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5. For reviews, see: (a) Yus, M. Chem. Soc. Rev. 1996, 155-161. (b) Ramón, D. J.; Yus, M. Eur. J. Org. Chem. 2000, 225-237.
6. For a previous contribution on this topic from our laboratory, see: Lorenzo, E.; Alonso, F.; Yus, M. Tetrahedron Lett. 2000, 41, 1661-1665.
7. For a polymer supported arene-catalysed version of this reaction, see: (a) Gómez, C.; Ruiz, S.; Yus, M. Tetrahedron Lett. 1998, 39, 1397-1400. (b) Gómez, C.; Ruiz, S.; Yus, M. Tetrahedron 1999, 55, 7017-7026.
8. For a polymer supported arene-catalysed version of this reaction, see: (a) Gómez, C.; Ruiz, S.; Yus, M. Tetrahedron Lett. 1998, 39, 1397-1400. (b) Gómez, C.; Ruiz, S.; Yus, M. Tetrahedron 1999, 55, 7017-7026.
9. For reviews, see: (a) Nájera, C.; Yus, M. Trends Org. Chem. 1991, 1, 155-181. (b) Nájera, C.; Yus, M. Recent Res. Devel. Org. Chem. 1997, 1, 67-96.
10. For reviews, see: (a) Nájera, C.; Yus, M. Trends Org. Chem. 1991, 1, 155-181. (b) Nájera, C.; Yus, M. Recent Res. Devel. Org. Chem. 1997, 1, 67-96.
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12. For a stoichiometric version of this process, see: (a) Bartmann, E. Angew. Chem., Int. Ed. Engl. 1986, 25, 653-654. (b) Barluenga, J.; Fernández-Simón, J. L.; Concellón, J. M.; Yus, M. J. Chem. Soc., Chem. Commun. 1987, 915-916. (c) Barluenga, J.; Fernández-Simón, J. L.; Concellón, J. M.; Yus, M. J. Chem. Soc., Perkin Trans. 1 1988, 3339-3343. (d) Dorigo, A. E.; Houk, K. N.; Cohen, T. J. Am. Chem. Soc. 1989, 111, 8976-8978. (e) Cohen, T.; Jeong, I.-H.; Mudryk, B.; Bhupathy, M.; Awad, M. M. A. J. Org. Chem. 1990, 55, 1528-1536. (f) Conrow, R. E. Tetrahedron Lett. 1993, 34, 5553-5554.
13. For a stoichiometric version of this process, see: (a) Bartmann, E. Angew. Chem., Int. Ed. Engl. 1986, 25, 653-654. (b) Barluenga, J.; Fernández-Simón, J. L.; Concellón, J. M.; Yus, M. J. Chem. Soc., Chem. Commun. 1987, 915-916. (c) Barluenga, J.; Fernández-Simón, J. L.; Concellón, J. M.; Yus, M. J. Chem. Soc., Perkin Trans. 1 1988, 3339-3343. (d) Dorigo, A. E.; Houk, K. N.; Cohen, T. J. Am. Chem. Soc. 1989, 111, 8976-8978. (e) Cohen, T.; Jeong, I.-H.; Mudryk, B.; Bhupathy, M.; Awad, M. M. A. J. Org. Chem. 1990, 55, 1528-1536. (f) Conrow, R. E. Tetrahedron Lett. 1993, 34, 5553-5554.
14. For a stoichiometric version of this process, see: (a) Bartmann, E. Angew. Chem., Int. Ed. Engl. 1986, 25, 653-654. (b) Barluenga, J.; Fernández-Simón, J. L.; Concellón, J. M.; Yus, M. J. Chem. Soc., Chem. Commun. 1987, 915-916. (c) Barluenga, J.; Fernández-Simón, J. L.; Concellón, J. M.; Yus, M. J. Chem. Soc., Perkin Trans. 1 1988, 3339-3343. (d) Dorigo, A. E.; Houk, K. N.; Cohen, T. J. Am. Chem. Soc. 1989, 111, 8976-8978. (e) Cohen, T.; Jeong, I.-H.; Mudryk, B.; Bhupathy, M.; Awad, M. M. A. J. Org. Chem. 1990, 55, 1528-1536. (f) Conrow, R. E. Tetrahedron Lett. 1993, 34, 5553-5554.
15. For a stoichiometric version of this process, see: (a) Bartmann, E. Angew. Chem., Int. Ed. Engl. 1986, 25, 653-654. (b) Barluenga, J.; Fernández-Simón, J. L.; Concellón, J. M.; Yus, M. J. Chem. Soc., Chem. Commun. 1987, 915-916. (c) Barluenga, J.; Fernández-Simón, J. L.; Concellón, J. M.; Yus, M. J. Chem. Soc., Perkin Trans. 1 1988, 3339-3343. (d) Dorigo, A. E.; Houk, K. N.; Cohen, T. J. Am. Chem. Soc. 1989, 111, 8976-8978. (e) Cohen, T.; Jeong, I.-H.; Mudryk, B.; Bhupathy, M.; Awad, M. M. A. J. Org. Chem. 1990, 55, 1528-1536. (f) Conrow, R. E. Tetrahedron Lett. 1993, 34, 5553-5554.
16. For a stoichiometric version of this process, see: (a) Bartmann, E. Angew. Chem., Int. Ed. Engl. 1986, 25, 653-654. (b) Barluenga, J.; Fernández-Simón, J. L.; Concellón, J. M.; Yus, M. J. Chem. Soc., Chem. Commun. 1987, 915-916. (c) Barluenga, J.; Fernández-Simón, J. L.; Concellón, J. M.; Yus, M. J. Chem. Soc., Perkin Trans. 1 1988, 3339-3343. (d) Dorigo, A. E.; Houk, K. N.; Cohen, T. J. Am. Chem. Soc. 1989, 111, 8976-8978. (e) Cohen, T.; Jeong, I.-H.; Mudryk, B.; Bhupathy, M.; Awad, M. M. A. J. Org. Chem. 1990, 55, 1528-1536. (f) Conrow, R. E. Tetrahedron Lett. 1993, 34, 5553-5554.
17. For a stoichiometric version of this process, see: (a) Bartmann, E. Angew. Chem., Int. Ed. Engl. 1986, 25, 653-654. (b) Barluenga, J.; Fernández-Simón, J. L.; Concellón, J. M.; Yus, M. J. Chem. Soc., Chem. Commun. 1987, 915-916. (c) Barluenga, J.; Fernández-Simón, J. L.; Concellón, J. M.; Yus, M. J. Chem. Soc., Perkin Trans. 1 1988, 3339-3343. (d) Dorigo, A. E.; Houk, K. N.; Cohen, T. J. Am. Chem. Soc. 1989, 111, 8976-8978. (e) Cohen, T.; Jeong, I.-H.; Mudryk, B.; Bhupathy, M.; Awad, M. M. A. J. Org. Chem. 1990, 55, 1528-1536. (f) Conrow, R. E. Tetrahedron Lett. 1993, 34, 5553-5554.
18. (a) Bachki, A.; Foubelo, F.; Yus, M. Tetrahedron: Asymmetry 1995, 6, 1907-1910.
19. (b) Bachki, A.; Foubelo, F.; Yus, M. Tetrahedron: Asymmetry 1996, 7, 2997-3008.
20. (c) Soler, T.; Bachki, A.; Falvello, L. R.; Foubelo, F.; Yus, M. Tetrahedron: Asymmetry 1998, 9, 3939-3943.
21. (d) Soler, T.; Bachki, A.; Falvello, L. R.; Foubelo, F.; Yus, M. Tetrahedron: Asymmetry 2000, 11, 493-518.
22. Seebach, D.; Hungerbühler, E. In Modern Synthetic Methods; Scheffold, R., Ed.; Salle and Sauerländer Verlag: Aarau, 1980; p. 91.
23. tOH reflux, 20 h in 82% overall yield.
24. 13d Those hydrogen atoms whose positions could be confidently predicted were given calculated coordinates and refined as riding atoms. Methyl hydrogen atoms and one of the hydroxy hydrogen atoms were located in local slant Fourier calculations, and refined as riding atoms; for each of the methyl groups a variable torsion angle about the adjoining C-C bond was refined. For one of the hydroxy groups, the hydrogen atom was located in a difference Fourier map and refined freely, with its own isotropic displacement parameter. All other hydrogen atoms were assigned isotropic displacement parameters equal to 1.2 times the equivalent isotropic displacement parameters of their respective parent atoms. One ether oxygen atom was found to be disordered over two positions, whose occupancies were fixed in a 2:1 ratio after initial refinement of variable occupancies had converged to this value. The final, convergent refinement involved 274 parameters, giving wR2=0.1513 and quality-of-fit=1.067 for all data and R1=0.0540 for 2516 Fo>4σ(Fo). The absolute structure was set on the basis of the previously established stereochemistries of four chiral centres in the molecule. (b) Data were processed on an AlphaStation 200 4/166 (OpenVMS/Alpha V6.2), using the program XCAD4B (K. Harms, University of Marburg, 1996) and the commercial package SHELXTL-PLUS Release 5.05/V © 1996 Siemens Analytical X-Ray Instruments, Inc., Madison, WI. (c) SHELXS-97: Fortran program for crystal structure solution, © 1997 G. M. Sheldrick. (d) SHELXL-97: Fortran program for crystal structure refinement, © 1997, G. M. Sheldrick.
25. Following the same procedure as for compound 1, cholestanone was epoxidised to give compound 4 in 85% yield.
26. 3 position: 147-149°C); see: Li, T.-S.; Li, A.-X. J. Chem. Soc., Perkin Trans. 1 1998, 1913-1917.