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Synthesis 2006(13): 2143-2146  
DOI: 10.1055/s-2006-942409
PAPER
© Georg Thieme Verlag Stuttgart · New York

Efficient Synthesis of 2-Hydroxy-3,4-dienoates by Oxidation of Zirconium­allenyl Enolates with Dimethyldioxirane

Anja Hoffmann-Röder, Norbert Krause*
University of Dortmund, Organic Chemistry II, Otto-Hahn-Strasse 6, 44227 Dortmund, Germany
Fax: +49(231)7553884; e-Mail: norbert.krause@uni-dortmund.de;
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Publikationsverlauf

Received 1 May 2006
Publikationsdatum:
08. Juni 2006 (online)

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Abstract

The α-hydroxylation of zirconiumallenyl enolates, obtained from β-allenic esters by deprotonation with LDA or LiN(SiMe3)2 and transmetalation with Cp2ZrCl2, with dimethyldioxirane (DMDO) selectively affords 2-hydroxy-3,4-dienoates. The oxidation proceeds usually with high yield and substrate conversion and tolerates even sensitive or unreactive substrates.

Key words

allenes - chirality transfer - enolates - oxidation - zirconium

    References

  • 2 Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004. 
  • 3a Krause N. Hoffmann-Röder A. In Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.997-1039  
  • 3b Brummond KM. Chen H. In Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.1041-1089  
  • 4a Ma S. In Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.595-699  
  • 4b Hartung J. Kopf T. In Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.701-726  
  • 5a Ma S. Acc. Chem. Res.  2003,  36:  701 
    CrossrefSuche in Google Scholar
  • 5b Murakami M. Matsuda T. In Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.727-815  
    Crossref
  • 5c Tius MA. In Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.817-845  
    Crossref
  • 5d Mandai T. In Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.925-972  
    Crossref
  • 5e Wang KK. In Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.1091-1126  
    Crossref
  • 6 Hashmi ASK. In Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.877-923  
  • 7a Zimmer R. Dinesh CU. Nandanan E. Khan FA. Chem. Rev.  2000,  100:  3067 
    CrossrefPubMedSuche in Google Scholar
  • 7b Zimmer R. Reissig H.-U. In Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.847-876  
    CrossrefPubMed
  • 8a Marshall JA. Chem. Rev.  2000,  100:  3163 
    CrossrefPubMedSuche in Google Scholar
  • 8b Marshall JA. Gung BW. Grachan ML. In Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.493-592  
    CrossrefPubMed
  • 8c Dreller S. Dyrbusch M. Hoppe D. Synlett  1991,  397 
    CrossrefPubMed
  • 8d Schultz-Fademrecht C. Wibbeling B. Fröhlich R. Hoppe D. Org. Lett.  2001,  3:  1221 
    CrossrefPubMedSuche in Google Scholar
  • 8e Schultz-Fademrecht C. Tius MA. Grimme S. Wibbeling B. Hoppe D. Angew. Chem. Int. Ed.  2002,  41:  1532 ; Angew. Chem. 2002, 114, 1610
    CrossrefPubMedSuche in Google Scholar
  • 9a Krause N. Laux M. Hoffmann-Röder A. Tetrahedron Lett.  2000,  41:  9613 
    Thieme ConnectSuche in Google Scholar
  • 9b Krause N. Hoffmann-Röder A. Canisius J. Synthesis  2002,  1759 
    Thieme Connect
  • 10a Hoffmann-Röder A. Krause N. Org. Lett.  2001,  3:  2537 
    CrossrefSuche in Google Scholar
  • 10b Morita N. Krause N. Org. Lett.  2004,  6:  4121 
    CrossrefSuche in Google Scholar
  • 10c Morita N. Krause N. Angew. Chem. Int. Ed.  2006,  45:  1897 ; Angew. Chem. 2006, 118, 1930
    CrossrefSuche in Google Scholar
  • 11a Adam W. Hadjiarapoglou L. Top. Curr. Chem.  1993,  164:  45 
    CrossrefSuche in Google Scholar
  • 11b Adam W. Müller M. Prechtl F. J. Org. Chem.  1994,  59:  2358 
    CrossrefSuche in Google Scholar
  • 12The use of Davis’ oxaziridine12b as oxidizing agent instead of DMDO gave small amounts the desired allenes 2 which could not be separated from side products originating from the oxaziridine:
  • 12 " shownum = "0"> Davis FA. Sheppard AC. Tetrahedron  1989,  45:  5703 
    CrossrefSuche in Google Scholar
  • Substrates 1 are readily accessible by 1,6-cuprate addition to 2-en-4-ynoates, see:
  • 13a Krause N. Gerold A. Angew. Chem., Int. Ed. Engl.  1997,  36:  186 ; Angew. Chem. 1997, 109, 194
    CrossrefSuche in Google Scholar
  • 13b Krause N. Hoffmann-Röder A. In Modern Organocopper Chemistry   Krause N. Wiley-VCH; Weinheim: 2002.  p.145-166  
    Crossref
  • 15 Kofron WG. Baclawski LM. J. Org. Chem.  1976,  41:  1879 
    CrossrefSuche in Google Scholar
  • 16a Krause N. Chem. Ber.  1990,  123:  2173 
    CrossrefSuche in Google Scholar
  • 16b Arndt S. Handke G. Krause N. Chem. Ber.  1993,  126:  251 
    CrossrefSuche in Google Scholar
  • 16c Haubrich A. Van Klaveren M. Van Koten G. Handke G. Krause N. J. Org. Chem.  1993,  58:  5849 
    CrossrefSuche in Google Scholar
1

New address: A. Hoffmann-Röder, Institut für Organische Chemie, Universität Mainz, Duesbergweg 10-14, 55128 Mainz, Germany.

14

The corresponding reaction of allenic ester 1b with LiN(SiMe3)2, Cp2HfCl2 and DMDO furnished product 2b with complete conversion, but in only 38% yield.