Synthesis 2005(10): 1713-1717  
DOI: 10.1055/s-2004-834869
PSP
© Georg Thieme Verlag Stuttgart · New York

A Convenient Way for the Conversion of Carboxylic Esters into 2-Substituted Allyl Halides

Oleg G. Kulinkovich*, Yurii Y. Kozyrkov, Andrei V. Bekish, Evgenii A. Matiushenkov, Ivan L. Lysenko
Department of Organic Chemistry, Belarusian State University, Skoriny av. 4, 220050 Minsk, Belarus
Fax: +375(172)265609; e-Mail: [email protected];
Further Information

Publication History

Received 1 June 2004
Publication Date:
03 November 2004 (online)

Abstract

The preparation of functionalized 2-substituted allyl bromides and chlorides from carboxylic esters is reported. The carboxylic esters were transformed first to 1-substituted cyclopropanols by treating with ethylmagnesium bromide in the presence of titanium alkoxide. Mesylation of the cyclopropanols followed by halide displacement of the sulfonate group to halogen, accompanied by cyclopropyl-allyl rearrangement, affords the required allyl bromides and chlorides.

    References

  • 1a Comprehensive Organic Functional Group Transformations   Katritzky AR. Meth-Cohn O. Rees CW. Elsevier; Oxford: 1995. 
  • 1b Satchell DPN. Satchell RS. In The Chemistry of Carboxylic Acids and Esters   Patai S. Wiley; New York: 1969.  p.375 
  • 1c Dieter RK. Tetrahedron  1999,  55:  4177 
  • 2a Kulinkovich OG. Sviridov SV. Vasilevskii DA. Pritytskaya TS. Zh. Org. Khim.  1989,  25:  2244 ; J. Org. Chem. USSR (Engl. Transl.) 1989, 25, 2027
  • 2b Kulinkovich OG. Sviridov SV. Vasilevskii DA. Savchenko AI. Pritytskaya TS. Zh. Org. Khim.  1991,  27:  294 ; J. Org. Chem. USSR (Engl. Transl.) 1991, 27, 250
  • 2c Kulinkovich OG. Sviridov SV. Vasilevskii DA. Synthesis  1991,  234 
  • 2d Kulinkovich OG. de Meijere A. Chem. Rev.  2000,  100:  2789 
  • 3a Kulinkovich OG. Chem. Rev.  2003,  103:  2597 
  • 3b Gibson DH. De Puy CH. Chem. Rev.  1974,  74:  605 
  • 4 Kozyrkov YY. Kulinkovich OG. Synlett  2002,  443 
  • For recent applications of 2-substituted allyl halides in the syntheses of biologically active natural products, see:
  • 5a Harada T. Takahashi T. Takahashi S. Tetrahedron Lett.  1992,  33:  369 
  • 5b Wovkulich PM. Shankaran K. Kiegiel J. Uskokoviæ MR. J. Org. Chem.  1993,  58:  832 
  • 5c Fürstner A. Weintritt H. J. Am. Chem. Soc.  1997,  119:  2944 
  • 5d Wiliams DR. Clark MP. Berliner MA. Tetrahedron Lett.  1999,  40:  2287 
  • 5e Hughes RS. Dvorak CA. Meyers AI. J. Org. Chem.  2001,  66:  6936 
  • 5f Bekish AV. Prokhorevich KN. Kulinkovich OG. Tetrahedron Lett.  2004,  45:  5253 
  • 6 Raiman MV. Il’ina NA. Kulinkovich OG. Synlett  1999,  1053 
  • 7a De Puy CH. Schnack LG. Hausser JW. J. Am. Chem. Soc.  1966,  88:  3343 
  • 7b Schöllkopf U. Angew. Chem., Int. Ed. Engl.  1968,  7:  588 ; Angew. Chem. 1968, 80, 601
  • 7c Friedrich EC. In The Chemistry of the Cyclopropyl Group   Rappoport Z. Wiley; Chichester: 1987.  p.633 
  • 7d Boche G. Walborsky HM. Cyclopropane Derived Reactive Intermediates   Patai S. Rappoport Z. Wiley; Chichester: 1990.  p.117 
  • 7e Jendralla H. In Houben-Weyl   4th ed., Vol. E17:  de Meijere A. Thieme; Stuttgart: 1996.  p.2313 
  • 8 Lysenko IL. Kulinkovich OG. Zh. Org. Khim.  2004,  in press 
  • 9a Xiong ZM. Yang J. Li YL. Tetrahedron: Asymmetry  1966,  9:  2607 
  • 9b Bulliard M. Balme G. Gore J. Tetrahedron Lett.  1989,  30:  5767 
  • 9c Arora S. Binger P. Köster R. Synthesis  1973,  146 
  • 9d Yamanaka M. Nishida A. Nakagawa M. Tetrahedron Lett.  2002,  43:  2403 
  • 9e Moreno-Dorado FJ. Guerra FM. Manzano FL. Aladro FJ. Jorge ZD. Massanet GM. Tetrahedron Lett.  2003,  44:  6691 ; and references cited herein
  • 10a Hawthorne MF. J. Am. Chem. Soc.  1960,  82:  1886 
  • 10b Marshall JA. Andersen NH. Hochstetler AR. J. Org. Chem.  1967,  32:  113 
  • 10c Corey JP. Helquist P. Tetrahedron Lett.  1975,  4167 
  • 10d Baker R. Winton PM. Tetrahedron Lett.  1980,  21:  1175 
  • 10e Trost B. Curran D. Tetrahedron Lett.  1981,  22:  5023 
  • 10f Rastetter WH. Adams J. Tetrahedron Lett.  1982,  23:  1319 
  • 10g Overman LE. Lesuisse D. Tetrahedron Lett.  1985,  26:  4167 
  • 11 Stoller A. Moiskowski C. Sepulchre C. Belamy F. Tetrahedron Lett.  1990,  31:  361 
  • 12 Sviridov SV. Vasilevskii DA. Kulinkovich OG. Zh. Org. Khim.  1991,  27:  1431 ; J. Org. Chem. USSR (Engl. Transl.) 1991, 27, 1251
  • 13 Lysenko IL. Bekish AV. Kulinkovich OG. Zh. Org. Khim.  2002,  38:  918 ; Russ. J. Org. Chem. (Engl. Transl.) 2002, 38, 875
  • For other methods of preparation of compound 1, see:
  • 14a Applequist DE. Fanta GF. Henrikson BW. J. Am. Chem. Soc.  1960,  82:  2368 
  • 14b See also: Fuchs J. Szeimies G. Chem. Ber.  1992,  125:  2517