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Synlett 2010(18): 2717-2720  
DOI: 10.1055/s-0030-1258813
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

TBAF-Promoted Dehydrobrominations of Vicinal Dibromides Having an Adjacent O-Functional Group

Noriki Kutsumura*, Keisuke Kubokawa, Takao Saito*
Department of Chemistry, Faculty of Science, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
Fax: +81(3)52614631; e-Mail: nkutsu@rs.kagu.tus.ac.jp; e-Mail: tsaito@rs.kagu.tus.ac.jp;
Further Information

Publication History

Received 23 August 2010
Publication Date:
08 October 2010 (online)

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Abstract

Regioselective HBr elimination of vicinal dibromides having an adjacent oxygen functional group to give the corresponding 2-bromoalk-1-enes was controlled using 1.1 equivalents of TBAF. Two-step elimination to give the corresponding alkynes was controlled using 5.0 equivalents of TBAF. High yield and high selectivity require the presence of an oxygen functional group at the neighboring position of the elimination site.

Key words

elimination - 2-bromoalk-1-enes - alkynes - TBAF - vicinal dibromides

    References and Notes

  • 1a Paqutte LA. Hofferberth JE. J. Org. Chem.  2003,  68:  2266 
    Google Scholar
  • 1b Poss CS. Rychnovsky SD. Schreiber SL.
    J. Am. Chem. Soc.  1993,  115:  3360 
    Google Scholar
  • 2 Yokota M. Toyota M. Ihara M. Chem. Commun.  2003,  422 
    CrossrefGoogle Scholar
  • 3a Novikov YY. Sampson P. J. Org. Chem.  2005,  70:  10247 
    Google Scholar
  • 3b Vanbrunt MP. Ambenge RO. Weinreb SM. J. Org. Chem.  2003,  68:  3323 
    Google Scholar
  • 4a Suzuki H. Sakai N. Iwahara R. Fujiwara T. Satoh M. Kakehi A. Konakahara T. J. Org. Chem.  2007,  72:  5878 
    Google Scholar
  • 4b Miyamoto H. Okawa Y. Nakazaki A. Kobayashi S. Tetrahedron Lett.  2007,  48:  1805 
    Google Scholar
  • 4c Ohno H. Yamamoto M. Iuchi M. Tanaka T. Angew. Chem. Int. Ed.  2005,  44:  5103 
    Google Scholar
  • 5a Prusov E. Röhm H. Maier ME. Org. Lett.  2006,  8:  1025 
    Google Scholar
  • 5b Daniel PT. Koert U. Schuppan J. Angew. Chem. Int. Ed.  2006,  45:  872 
    Google Scholar
  • 5c Denmark SE. Yang SM. J. Am. Chem. Soc.  2004,  126:  12432 
    Google Scholar
  • 5d Fujii K. Maki K. Kanai M. Shibasaki M. Org. Lett.  2003,  5:  733 
    Google Scholar
  • 5e Chavez DE. Jacobsen EN. Angew. Chem. Int. Ed.  2001,  40:  3667 
    Google Scholar
  • 5f Duffault JM. Einhorn J. Alexakis A. Tetrahedron Lett.  1991,  32:  3701 
    Google Scholar
  • 6a Sugiyama H. Yokokawa F. Shioiri T. Org. Lett.  2000,  2:  2149 
    Google Scholar
  • 6b Kamiya N. Chikami Y. Ishii Y. Synlett  1990,  675 
    Google Scholar
  • 7a Narayan RS. Borhan B. J. Org. Chem.  2006,  71:  1416 
    Google Scholar
  • 7b Usugi S. Yorimitsu H. Shinokubo H. Oshima K. Bull. Chem. Soc. Jpn.  2002,  75:  2687 
    Google Scholar
  • 8a Izzo I. De Caro S. De Riccardis F. Spinella A. Tetrahedron Lett.  2000,  41:  3975 
    Google Scholar
  • 8b Sonogashira K. Tohda Y. Hagihara N. Tetrahedron Lett.  1975,  16:  4467 
    Google Scholar
  • 8c Ireland RE. Wipf P. J. Org. Chem.  1990,  55:  1425 
    Google Scholar
  • 9a Ohgiya T. Nakamura K. Nishiyama S. Bull. Chem. Soc. Jpn.  2005,  78:  1549 
    Google Scholar
  • 9b Ohgiya T. Nishiyama S. Chem. Lett.  2004,  33:  1084 
    Google Scholar
  • 9c Ohgiya T. Nishiyama S. Heterocycles  2004,  63:  2349 
    Google Scholar
  • 9d Ohgiya T. Nishiyama S. Tetrahedron Lett.  2004,  45:  8273 
    Google Scholar
  • 9e Yokoyama T. Kutsumura N. Ohgiya T. Nishiyama S. Bull. Chem. Soc. Jpn.  2007,  80:  578 
    Google Scholar
  • 9f Kutsumura N. Yokoyama T. Ohgiya T. Nishiyama S. Tetrahedron Lett.  2006,  47:  4133 
    Google Scholar
  • For reviews on the elimination reactions of 1,2-dibromoalkanes, see:
  • 9g Ohgiya T. Kutsumura N. Nishiyama S. Synlett  2008,  3091 
    Google Scholar
  • 9h Ohgiya T. Kutsumura N. Nishiyama S. J. Synth. Org. Chem. Jpn.  2008,  66:  139 
    Google Scholar
  • 10 Kutsumura N. Niwa K. Saito T. Org. Lett.  2010,  12:  3316 
    CrossrefGoogle Scholar
  • 11a Andrei D. Wnuk SF. Org. Lett.  2006,  8:  5093 
    Google Scholar
  • 11b Nakata M. Enari H. Kinoshita M. Bull. Chem. Soc. Jpn.  1982,  55:  3283 
    Google Scholar
  • 12a Okutani M. Mori Y. J. Org. Chem.  2009,  74:  442 
    Google Scholar
  • 12b Okutani M. Mori Y. Tetrahedron Lett.  2007,  48:  6856 
    Google Scholar
  • 14a Feng L. Kumar D. Birney DM. Kerwin SM. Org. Lett.  2004,  6:  2059 
    Google Scholar
  • 14b Matloubi Moghaddam F. Emami R. Synth. Commun.  1997,  27:  4073 
    Google Scholar
  • 15a Fürstner A. De Souza D. Parra-Rapado L. Jensen JT. Angew. Chem. Int. Ed.  2003,  42:  5358 
    Google Scholar
  • 15b Kim D. Lee J. Shim PJ. Lim JI. Doi T. Kim S. J. Org. Chem.  2002,  67:  772 
    Google Scholar
  • 15c Yoshimitsu T. Ogasawara K. J. Chem. Soc., Chem. Commun.  1994,  2197 
    Google Scholar
  • 15d Keusenkothen PF. Smith MB. J. Chem. Soc., Perkin Trans. 1  1994,  2485 
    Google Scholar
13

General Procedures for the Syntheses of 2-Bromoalk-1-ene 1 and Alkyne 2
A mixture of 1,2-dibromoalkane 3 (1.0 equiv) and TBAF (1 M in THF solution, 1.1 equiv or 5.0 equiv) in DMF (0.1 M) was stirred at 60 ˚C. The reaction was quenched with sat. aq NH4Cl, and the reaction mixture was extracted with EtOAc, concentrated in vacuo, and purified by silica gel column chromatography to afford 1 or 2.