Synthesis 2005(18): 3179-3180  
DOI: 10.1055/s-2005-872177
PSP
© Georg Thieme Verlag Stuttgart · New York

Preparation of 3-Oxocyclohex-1-ene-1-carbonitrile

Fraser F. Fleming*, Zhiyu Zhang, Guoqing Wei
Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282, USA
Fax: +1(412)3965683; e-Mail: [email protected];
Further Information

Publication History

Received 3 May 2005
Publication Date:
17 August 2005 (online)

Abstract

Chromium trioxide oxidation of cyclohexenecarbonitrile efficiently provides analytically pure 3-oxocyclohex-1-ene-1-carbonitrile. The procedure is described in detail, providing a very reliable, one-step synthesis of a highly versatile oxonitrile.

    References

  • 1a Cantrell TS. Tetrahedron  1971,  27:  1227 
  • 1b Agosta WC. Lowrance WW. Tetrahedron Lett.  1969,  3053 
  • 2 Serebryakov EP. Kulomzina-Pletneva SD. Margaryan AK. Tetrahedron  1979,  35:  77 
  • 3 Yang WQ. Chen SZ. Huang L. Chin. Chem. Lett.  1998,  9:  233 ; Chem. Abstr.  1999,  131:  736759 
  • 4 Fleming FF. Zhang Z. Wang Q. Steward OW. Angew. Chem. Int. Ed.  2004,  43:  1126 
  • 5 Fleming FF. Wang Q. Steward OW. J. Org. Chem.  2003,  68:  4235 
  • 6 Fleming FF. Zhang Z. Wei G. Steward OW. Org. Lett.  2005,  7:  447 
  • 7a Wang Y. Doering WVE. Staples RJ. J. Chem. Crystallogr.  1999,  29:  977 
  • 7b Cronyn MW. Goodrich JE. J. Am. Chem. Soc.  1952,  74:  3331 
  • 8 Agosta WC. Lowrance WW. J. Org. Chem.  1970,  35:  3851 
  • 10 Nakai T. Tomooka K. In Encyclopedia of Reagents for Organic Synthesis   Vol. 3:  Paquette LA. Wiley; Chichester: 1995.  p.1779 
  • 11 Nicolaou KC. Gray DLF. Montagnon T. Harrison ST. Angew. Chem. Int. Ed.  2002,  41:  996 
  • 12 Zimmerman HE. Pasteris RJ. J. Org. Chem.  1980,  45:  4864 
  • 13a Johnson JN. In Encyclopedia of Reagents for Organic Synthesis   Vol. 2:  Paquette LA. Wiley; Chichester: 1995.  p.1275-1277  
  • 13b Lee TV. In Comprehensive Organic Synthesis   Vol. 7:  Fleming I. Trost BM. Pergamon; Oxford: 1991.  p.291-303  
  • 13c Salmond WG. Barta MA. Havens JL. J. Org. Chem.  1978,  43:  2057 
  • 14 Mousseron M. Jacquier R. Fontaine A. Zagdoun R. Bull. Soc. Chim. Fr.  1954,  1247 
  • 15 Kurihara T. Miki M. Yoneda R. Harusawa S. Chem. Pharm. Bull.  1986,  34:  2747 
  • 16 Attempts to optimize the selenium dioxide oxidation of 1 afforded low yields of 2 despite excellent results with related unsaturated esters: Bestmann HJ. Schobert R. Angew. Chem., Int. Ed. Engl.  1985,  24:  791 
  • 17 Yu J.-Q. Wu H.-C. Corey EJ. Org. Lett.  2005,  7:  1415 
  • 18a Attempted oxidation with hydrogen peroxide and chromium hexacarbonyl is ineffective: Pearson AJ. Chen Y.-S. Han GR. Hsu S.-Y. Ray T. J. Chem. Soc., Perkin Trans. 1  1985,  267 
  • 18b

    The lack of oxidation may be due to competitive metal ligation of the nitrile as occurs with dirhodium(II) caprolactamate: Doyle M. P. personal communication.

  • 18c For a related oxidation see: Catino AJ. Forslund RE. Doyle MP. J. Am. Chem. Soc.  2004,  126:  13622 
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19

Assaying several different solvent mixtures identified CH2Cl2-hexanes (1.5:1) as optimal, although a stepped EtOAc-hexanes gradient (3:17, 1:4, 1:3) permitted isolation of 2.30 g of 2 in 64% yield.