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Synthesis 2011(23): 3899-3907  
DOI: 10.1055/s-0031-1289294
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Michael Addition of Various Nitrogen and Oxygen Nucleophiles to 1,1-Diethoxybut-3-yn-2-one

Myagmarsuren Sengee, Leiv K. Sydnes*
Department of Chemistry, University of Bergen, Allégt. 41, 5007 Bergen, Norway
Fax: +4755589490; e-Mail: leiv.sydnes@kj.uib.no;
Further Information

Publication History

Received 9 August 2011
Publication Date:
17 October 2011 (online)

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Abstract

1,1-Diethoxybut-3-yn-2-one, a conjugated terminal acetylenic ketone, reacts with nitrogen and oxygen nucleophiles and gives Michael adducts, in most cases in good to excellent yield. In almost every case the predominant reaction is monoaddition, which leads to formation of the corresponding β-substituted α,β-unsaturated ketones in a stereospecific fashion. The stereochemistry depends on the nature of the nucleophile, the general pattern being that ammonia and primary amines give Z-alkenones, whereas secondary amines and alcohols afford E-alkenones. Triethylamine does not furnish a Michael addition product, but catalyzes a trimerization that leads to formation of a 6H-1,3-dioxine derivative. When bis-nucleophiles, for instance hydrazine and hydroxylamine, are used, the Michael-addition products are unstable and undergo secondary reactions to form heterocyclic compounds, which are isolated in excellent yields.

Key words

acetylenic ketones - Michael additions - vinyl ketones - cyclotrimerization - acetals

    References

  • 1a Perlmutter P. Conjugate Addition Reactions in Organic Synthesis   Pergamon; Oxford: 1992. 
    Google Scholar
  • 1b Bergmann ED. Ginsburg D. Pappo R. Org. React.  1959,  10:  182 
    Google Scholar
  • 1c Rossiter BE. Swingle NM. Chem. Rev.  1992,  92:  771 
    Google Scholar
  • 2 Bol’shedvorskaya RL. Vereshchagin LI. Russ. Chem. Rev.  1973,  42:  225 
    Google Scholar
  • 3a Posner GH. Org. React.  1972,  19:  1 
    Google Scholar
  • 3b Kozlowski JA. In Comprehensive Organic Synthesis   Vol. 4:  Trost BM. Fleming I. Pergamon; Oxford: 1991.  Chap. 1.4.
    Google Scholar
  • 3c Tomioka K. Synthesis  1990,  541 
    Google Scholar
  • 3d Sydnes LK. Holmelid B. Sengee M. Hanstein M. J. Org. Chem.  2009,  74:  3430 
    Google Scholar
  • 4a Gaunt MJ. Sneddon HF. Hewitt PR. Orsini P. Hook DF. Ley SV. Org. Biomol. Chem.  2003,  1:  15 
    Google Scholar
  • 4b Sneddon HF. Gaunt MJ. Ley SV. Org. Lett.  2003,  5:  1147 
    Google Scholar
  • 5a Sydnes LK. Holmelid B. Kvernenes OH. Sandberg M. Hodne M. Bakstad E. Tetrahedron  2007,  63:  4144 
    Google Scholar
  • 5b Holmelid B. Kvernenes OH. Hodne M. Sydnes LK. ARKIVOC  2008,  (vi):  26 
    Google Scholar
  • 6a Sydnes LK. Holmelid B. Kvernenes OH. Valdersnes S. Hodne M. Boman K. ARKIVOC  2008,  (xiv):  242 
    Google Scholar
  • 6b Sydnes LK. Kvernenes OH. Valdersnes S. Pure Appl. Chem.  2005,  77:  119 
    Google Scholar
  • 6c Sengee M. Sydnes LK. Pure Appl. Chem.  2011,  83:  587 
    Google Scholar
  • 7 Chapman AV. Cook MJ. Katrizky AR. Abraham MH. Danil de Namor AF. Dumont L. Reisse J. Tetrahedron  1978,  34:  1571 
    Google Scholar
  • 8 Umeda Y. Moriguchi M. Kuroda H. Nakamura T. Fujii A. Iinuma H. Takeuchi T. Umezawa H. J. Antibiot.  1987,  40:  1303 
    Google Scholar