Mechanistic insights and new products of the reaction of steroid sapogenins with NaNO2 and BF3·Et2O in acetic acid

Steroids

Volumn 73, Issue 6, 2008, Pages 657-668

  López, Yliana ^a   Ruíz Pérez, Karen M ^b   Yépez, Rebeca ^a   Santillan, Rosa ^a   Flores Alamo, Marcos ^b   Iglesias Arteaga, Martín A ^b  

^a DEPARTAMENTO DE FÍSICA   (Mexico)

^b UNIVERSIDAD NACIONAL AUTÓNOMA DE MÉXICO   (Mexico)

Author keywords

23 Nitroenaminosapogenins 5 acetoxy 6 nitroiminosteroids; 23 Nitrominosapogenins; 23 Oxosapogenins; NMR; X ray diffraction

Indexed keywords

ACETIC ACID; BORON TRIFLUORIDE; ETHER; SAPOGENIN; SODIUM NITRITE; STEROID SAPOGENIN DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; COLUMN CHROMATOGRAPHY; NUCLEAR MAGNETIC RESONANCE; X RAY DIFFRACTION;

EID: 41749120743     PISSN: 0039128X     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.steroids.2008.02.003     Document Type: Article

References (33)

1. Barton D.H.R., Sammes P.G., Taylor M.V., and Werstiuk E. Transformation of the steroidal sapogenin side chain. Part 1. Reactions of 9(11)-dehydrohecogenin acetate with nitrous acid and with paraformaldehyde. J Chem Soc (C) (1970) 1977-1981
2. Gonzalez A.G., Freire R., García-Estrada M.G., Salazar J.A., and Suarez E. Reaction of spirostan sapogenins with nitrous acid 23-Nitrimines as intermediates in the formation of 23-ketospirostan sapogenins. Ann Quim 67 (1971) 903-905
3. For review see. Gryszkiewicz-Wojtkielewicz A., Jastrzêbska I., Morzycki J.W., and Romanowska D.B. Approaches towards the synthesis of cephalostatins, ritterazines and saponins from Ornithogalum saundersiae-new natural products with cytostatic activity. Curr Org Chem 7 (2003) 1257-1277
4. Betancor C., Freire R., Perez-Martin I., Prange T., and Suarez E. Hydrogen atom transfer methodology for the synthesis of C-22, C-23, and C-25 stereoisomers of cephalostatin north 1 side chain from spirostan sapogenins. Tetrahedron 61 (2005) 2803-2814
5. Betancor C., Freire R., Perez-Martin I., Prange T., and Suarez E. A convenient synthesis of C-22 and C-25 stereoisomers of cephalostatin north 1 side chain from spirostan sapogenins. Org Lett 4 (2002) 1295-1297
6. Iglesias-Arteaga M.A., Leliebre Lara V., Pérez Martínez C.S., and Coll Manchado F. Synthesis of spirobrassinosteroids analogues of 6-desoxocastasterone. Quim Nova 20 4 (1997) 361-364 (Chem Abstr 1997;27:95449)
7. Iglesias-Arteaga M.A., Pérez Gil R., Pérez Martínez C.S., and Coll Manchado F. Spirostanic analogues of teasterone: synthesis, characterization and biological activity of laxogenin (23S)-hydroxylaxogenin and 23-ketolaxogenin (23-oxolaxogenin). J Chem Soc Perkin Trans I 3 (2001) 26-66
8. Iglesias-Arteaga M.A., Pérez Martínez C.S., and Coll Manchado F. Spirostanic analogues of castasterone. Steroids 67 (2002) 159-163
9. Iglesias-Arteaga M.A., Pérez Gil R., Leliebre Lara V., Pérez Martínez C.S., and Coll Manchado F. Synthesis of (25R)-2α,3α-epoxy-5α- spirostan-6, 23-dione. Synth Commun 28 (1998) 4387-4392
10. Iglesias-Arteaga M.A., Gil R.P., Martínez C.S.P., and Manchado F.C. Synthetic steroidal sapogenins Part III. 23-Ketohecogenin and 23-ketoisochiapagenin. Synth Commun 30 (2000) 163-170
11. Iglesias Arteaga M.A., Pérez Martínez C.S., and Coll Manchado F. Synthesis of (25R)-2α,3α-Epoxy-5α-Spirostan-12,23-dione. Synth Commun 29 (1999) 1811-1818
12. Lopez Y., Santillan R., and Farfan N. New bisfuran derivative from sarsasapogenin. An X-ray and NMR analysis. Steroids 71 (2006) 12-17
13. Cyranski M.K., Frelek J., Jastrzebska I., and Morzycki J.W. Rearrangement of 23-oxospirostanes to the 22-oxo-23-spiroketal isomers promoted by Lewis acids. X-ray crystal structure of (23R,25S)-3β-acetoxy-16β,23:23,26-diepoxy-5β-cholestan-22 -one. Steroids 69 (2004) 395-400
14. Freeman J.P. The structure of pernitroso compounds of t-alkyl ketones. J Org Chem 26 (1961) 4190-4193
15. 13C NMR of synthetic steroid sapogenins. Part II. C-23 substituted derivatives of (25S)-spirostanes. ARKIVOC (2003) 163-171
16. Iglesias-Arteaga M.A., Sandoval-Ramírez J., Mata-Esma M.Y., Viñas-Bravo O., and Bernés S. Abnormal Beckmann rearrangement in 23-hydroxyiminodiosgenin acetate. Tetrahedron Lett 45 (2004) 4921-4926
17. AM1 and PM3 implemented in HyperChem v. 5.02 for Windows 95/NT. HyperCube, 1997.
18. Hu W.P., Wang J.J., and Tsai P.C. Novel examples of 3-Aza-Grob fragmentation. J Org Chem 65 (2000) 4208-4209
19. 2O-induced Beckmann rearrangement of 23-hydroxyiminosapogenins A shortcut to bisnorcholanic lactones. Tetrahedron Lett 47 (2006) 5351-5353
20. Iglesias-Arteaga M.A., Símuta-Lopez E.M., Xochihua-Moreno S., Viñas-Bravo O., Montiel-Smith S., Meza-Reyes S., et al. A convenient procedure for the synthesis of 3β-hydroxy-6-oxo-5α-steroids application to the synthesis of laxogenin. J Braz Chem Soc 16 (2005) 381-385
21. Allen F.H., Kennard O., Watson D.G., Brammer L., Orpen A.G., and Taylor R. Tables of bond lengths determined by X-ray and neutron diffraction Part 1. Bond lengths in organic compounds. J Chem Soc Perkin Trans 2 (1987) S1-S19
22. Orpen A.G., Brammer L., Allen F.H., Kennard O., Watson D.G., Taylor R., et al. Tables of bond lengths determined by X-ray and neutron diffraction. Part 2. Organometallic compounds and co-ordination complexes of the d- and f-block metals. J Chem Soc Dalton Trans (1989) S1-S83
23. Complete data for compound 9 have been deposited with the Cambridge Crystallographic Data Centre, CCDC, reference 658435.
24. Cremer D., and Pople J.A. General definition of ring puckering coordinates. J Am Chem Soc 97 (1975) 1354-1358
25. Duax W.L., Weeks C.M., and Rohrer D.C. Crystal structures of steroids. Topics in stereochemistry vol. 2 (1976), John Wiley, New York pp. 271-283
26. Altona C., Geise H.J., and Romers C. Conformation of non-aromatic ring Compounds-XXV. Tetrahedron 24 (1968) 13-32
27. Complete data for compound 10 have been deposited with the Cambridge Crystallographic Data Centre, CCDC, reference 658339.
28. Complete data for compound 12 have been deposited with the Cambridge Crystallographic Data Centre, CCDC, reference 658436.
29. Altomare A., Cascarano G., Giacovazzo C., and Guagliardi A. Completion and refinement of crystal structures with SIR92. J Appl Cryst 26 (1993) 343-350
30. Betteridge P.W., Carruthers J.R., Cooper R.I., Prout K., and Watkin D.J. CRYSTALS version 12: software for guided crystal structure analysis. J Appl Cryst 36 (2003) 1487-11487
31. Sheldrick G.M. SHELXL-97 a program for the refinement of crystal structure (1997), University of Göttingen, Germany
32. Iglesias-Arteaga M.A., Velázquez-Huerta G.A., Méndez-Stivalet J.M., Galano A., and Alvarez-Idaboy R. The Baeyer-Villiger reaction of 23-oxosapogenins. ARKIVOC VI (2005) 109-126
33. 3B. I. Derivados del Colestano. An Quim 68 (1972) 1145-1152