A Mild One-Pot Method for Conversion
of Various Steroidal Secondary Alcohols into the Corresponding
Olefins

Raju Ranjith Kumar; Shrutisagar Dattatraya Haveli; Henri B. Kagan

doi:10.1055/s-0030-1260803

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synlett 2011(12): 1709-1712
DOI: 10.1055/s-0030-1260803

LETTER

A Mild One-Pot Method for Conversion of Various Steroidal Secondary Alcohols into the Corresponding Olefins

Raju Ranjith Kumar, Shrutisagar Dattatraya Haveli, Henri B. Kagan*
Laboratoire de Catalyse Moléculaire, Institut de Chimie Moléculaire et des Matériaux d’Orsay (UMR CNRS 8182), Bâtiment 420, Université Paris-Sud, 91405 Orsay, France
Fax: +33(1)69154680; e-Mail: henri.kagan@u-psud.fr;

Further Information

Publication History

Received 7 April 2011
Publication Date:
21 June 2011 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

The addition of Tf₂O to some hydroxy steroids in the presence of excess base directly leads to steroidal olefins. This methodology is useful for the one-pot synthesis of Δ^²- or Δ^³-steroids under mild conditions from the corresponding alcohols.

Key words

alcohols - biliary acid, elimination - steroids - triflic anhydride

References and Notes

1 Baulieu EE. Biol. Cell. 1991, 71: 3

Crossref Google Scholar
2a Kandutsch AA. Chen HW. Heiniger HJ. Science 1978, 201: 498

Google Scholar
2b Smith JG. Synthesis 1984, 629

Google Scholar
2c Misharin AY. Mehtiev AR. Morozevich GE. Tkachev YV. Timofeev VP. Bioorg. Med. Chem. 2008, 16: 1460

Google Scholar
3a Wharton PS. Dunny S. Krebs LS. J. Org. Chem. 1964, 29: 958

Google Scholar
3b Fieser LF. Dominguez XA. J. Am. Chem. Soc. 1953, 75: 1704

Google Scholar
3c Roy J. DeRoy P. Poirier D. J. Comb. Chem. 2007, 9: 347

Google Scholar
4 Santos GAG. Murray AP. Pujol CA. Damonte EB. Maier MS. Steroids 2003, 68: 125

Crossref Google Scholar
5 Henningsen MC. Jeropoulos S. Smith EH. J.Org. Chem. 1989, 54: 3015

Crossref Google Scholar
6 Freaure-Tromeur M. Zard SZ. Tetrahedron Lett. 1999, 40: 1305

Crossref Google Scholar
7 D’Onofrio F. Scettri A. Synthesis 1985, 1159

Article in Thieme Connect Google Scholar
8 Crabbe P. Leon C. J. Org. Chem. 1970, 35: 2594

Crossref Google Scholar
9 Cruz Silva MM. Riva S. Sá e Melo ML. Tetrahedron 2005, 61: 3065

Crossref Google Scholar
10 Shimizu et al. have studied the leaving group ability of some steroidal sulfonates in substitution reactions. During the triflation reaction of several secondary alcohols they noticed formation of an alkene instead of the expected triflate. See: Shimizu T. Ohzeki T. Hiramoto K. Nakatha T. Synthesis 1999, 1373

Article in Thieme Connect Google Scholar
11 Edwards JA. Holton PG. Orr JC. Ibanez LC. Necoechea E. de la Roz A. Segovia E. Urquiza R. Bowers A. J. Med. Chem. 1963, 6: 174

Crossref Google Scholar
12 Neti S. Vijayavitthal TM. Vurimindi H. Jaydeepkumar L. Asian. J. Chem. 2009, 21: 4399

Google Scholar
13 Xiong Q. Wilson WK. Pang J. Lipids 2007, 42: 87

Crossref Google Scholar
14 Romeo A. Villotti R. Ann. Chim. (Rome) 1957, 47: 684

Google Scholar
15 Miura T. Takagi H. Harita K. Kimura M. Chem. Pharm. Bull. 1979, 27: 452

Crossref Google Scholar
16 Iida T. Momose T. Chang FC. Goto J. Nambara T. Chem. Pharm. Bull. 1989, 37: 3323

Crossref Google Scholar
17 Hodosan F. Jude I. Serban N. Bull. Soc. Chim. Fr. 1964, 10: 2691

Google Scholar

18

The Tf₂O/DMAP protocol was applied to primary alcohols (aliphatic alcohols, bisacetonide of glucopyranose), which were transformed into the corresponding triflates devoid of elimination products. Triflates were also produced from some secondary alcohols in carbohydrate family (as bisacetonide of galactopyranose). Terpenoid secondary alcohols provided elimination products.