Download PDF
Synlett 2011(12): 1660-1667  
DOI: 10.1055/s-0030-1260813
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Asymmetric Organocatalyzed Direct Aldol Additions of Enolizable Aldehydes

Ulf Scheffler, Rainer Mahrwald*
Department of Chemistry, Humboldt University of Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany
Fax: +49(30)20935553; e-Mail: rainer.mahrwald@rz.hu-berlin.de;
Further Information

Publication History

Received 8 March 2011
Publication Date:
05 July 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

The enantioselective direct cross-aldol addition between enolizable aldehydes is of great importance because this transformation provides access to configurationally defined β-hydroxyaldehydes. These products in turn are valuable building blocks in total syntheses of natural polyketide structures. This account gives an overview of advances made in this field of organocatalysis.

1 Introduction

2 Direct Aldol Additions of Enolizable Aldehydes Catalyzed by Proline, Proline Derivatives, and Imidazolidinone

2.1 Direct Aldol Additions Catalyzed by Proline and Proline Derivatives

2.2 Direct Aldol Additions Catalyzed by Imidazolidinone

3 Direct Aldol Additions of Enolizable Aldehydes Catalyzed by Histidine

4 Conclusion

Key words

aldol reactions - enolizable aldehydes - asymmetric ­catalysis - organocatalysis - stereoselectivity

    References

  • 1 List B. Lerner RA. Barbas CF. J. Am. Chem. Soc.  2000,  122:  2395 
    CrossrefGoogle Scholar
  • 2a Li J. Fu N. Li X. Luo S. Cheng J.-P. J. Org. Chem.  2010,  75:  4501 
    Google Scholar
  • 2b Hajra S. Giri AK. Hazra S. J. Org. Chem.  2009,  74:  7978 
    Google Scholar
  • 2c Kano T. Yamaguchi Y. Maruoka K. Chem. Eur. J.  2009,  15:  6678 
    Google Scholar
  • 2d Siyutkin DE. Kucherenko AS. Zlotin SG. Tetrahedron  2009,  65:  1366 
    Google Scholar
  • 2e Xiong Y. Wang F. Dong S. Liu X. Feng X. Synlett  2008,  73 
    Google Scholar
  • 2f Zu L. Xie H. Li H. Wang J. Wang W. Org. Lett.  2008,  10:  1211 
    Google Scholar
  • 2g Kano T. Yamaguchi Y. Tanaka Y. Maruoka K. Angew. Chem. Int. Ed.  2007,  46:  1738 
    Google Scholar
  • 2h Hayashi Y. Aratake S. Itoh T. Okano T. Sumiya T. Shoji M. Chem. Commun. (Cambridge)  2007,  957 
    Google Scholar
  • with the exception of the reaction between dimethoxyacetaldehyde and hydrocinnamaldehyde
  • 2i Luo S. Li J. Xu H. Zhang L. Cheng J.-P. Org. Lett.  2007,  9:  3675 
    Google Scholar
  • 2j Mase N. Nakai Y. Ohara N. Yoda H. Takabe K. Tanaka F. Barbas CF. J. Am. Chem. Soc.  2006,  128:  734 
    Google Scholar
  • 2k Zhang F. Su N. Gong Y. Synlett  2006,  1703 
    Google Scholar
  • 2l Zhang S. Duan W. Wang W. Adv. Synth. Catal.  2006,  348:  1228 
    Google Scholar
  • 2m Hayashi Y. Urushima T. Shoji M. Uchimaru T. Shiina I. Adv. Synth. Catal.  2005,  347:  1595 
    Google Scholar
  • 2n Wang W. Li H. Wang J. Tetrahedron Lett.  2005,  46:  5077 
    Google Scholar
  • 3a Northrup AB. MacMillan DWC. J. Am. Chem. Soc.  2002,  124:  6798 
    Google Scholar
  • highlighted in
  • 3b Cauble DF. Krische MJ. Chemtracts  2002,  15:  380 
    Google Scholar
  • 3c Alcaide B. Almendros P. Angew. Chem. Int. Ed.  2003,  42:  858 
    Google Scholar
  • 3d Marigo M. Melchiorre P. ChemCatChem  2010,  2:  621 
    Google Scholar
  • 4a Northrup AB. Mangion IK. Hettche F. MacMillan DWC. Angew. Chem. Int. Ed.  2004,  43:  2152 
    Google Scholar
  • 4b Northrup AB. MacMillan DWC. Science (Washington, DC, U.S.)  2004,  305:  1752 
    Google Scholar
  • 5 Mangion IK. MacMillan DWC. J. Am. Chem. Soc.  2005,  127:  3696 
    CrossrefGoogle Scholar
  • 6 Pihko PM. Erkkilä A. Tetrahedron Lett.  2003,  44:  7607 
    CrossrefGoogle Scholar
  • 7 Smith AB. Tomioka T. Risatti CA. Sperry JB. Sfouggatakis C. Org. Lett.  2008,  10:  4359 
    CrossrefGoogle Scholar
  • 8 Storer RI. MacMillan DWC. Tetrahedron  2004,  60:  7705 
    CrossrefGoogle Scholar
  • 9 Chowdari NS. Ramachary DB. Cordova A. Barbas CF. Tetrahedron Lett.  2002,  43:  9591 
    CrossrefGoogle Scholar
  • 10 Cordova A. Tetrahedron Lett.  2004,  45:  3949 
    CrossrefGoogle Scholar
  • 11 Gijsen HJM. Wong C.-H. J. Am. Chem. Soc.  1995,  117:  7585 
    CrossrefGoogle Scholar
  • 12 Casas J. Engqvist M. Ibrahem I. Kaynak B. Cordova A. Angew. Chem. Int. Ed.  2005,  44:  1343 
    CrossrefPubMedGoogle Scholar
  • 13 Reyes E. Cordova A. Tetrahedron Lett.  2005,  46:  6605 
    CrossrefGoogle Scholar
  • 14a Cordova A. Engqvist M. Ibrahem I. Casas J. Sunden H. Chem. Commun. (Cambridge)  2005,  2047 
    Google Scholar
  • 14b Cordova A. Ibrahem I. Casas J. Sunden H. Engqvist M. Reyes E. Chem. Eur. J.  2005,  11:  4772 
    Google Scholar
  • 15 Zhao G.-L. Liao W.-W. Cordova A. Tetrahedron Lett.  2006,  47:  4929 
    CrossrefGoogle Scholar
  • 16a Kofoed J. Reymond J.-L. Darbre T. Org. Biomol. Chem.  2005,  3:  1850 
    Google Scholar
  • 16b Kofoed J. Machuqueiro M. Reymond J.-L. Darbre T. Chem. Commun. (Cambridge)  2004,  1540 
    Google Scholar
  • 17 Thayumanavan R. Tanaka F. Barbas CF. Org. Lett.  2004,  6:  3541 
    CrossrefPubMedGoogle Scholar
  • 18 Guillena G. Najera C. Ramon DJ. Tetrahedron: Asymmetry  2007,  18:  2249 
    CrossrefGoogle Scholar
  • 19 With the sole exception of cross-aldol additions involving isobutyraldehyde as the ene component and 4-nitrobenz-aldehyde as the carbonyl one, see: Mase N. Tanaka F. Barbas CF. Angew. Chem. Int. Ed.  2004,  43:  2420 
    CrossrefGoogle Scholar
  • 20 Hayashi Y. Aratake S. Okano T. Takahashi J. Sumiya T. Shoji M. Angew. Chem. Int. Ed.  2006,  45:  5527 
    CrossrefPubMedGoogle Scholar
  • 21 Mangion IK. Northrup AB. MacMillan DWC. Angew. Chem. Int. Ed.  2004,  43:  6722 
    CrossrefPubMedGoogle Scholar
  • 22 For chiral phosphine oxide catalysis, see: Kotani S. Shimoda Y. Sugiura M. Nakajima M. Tetrahedron Lett.  2009,  50:  4602 
    CrossrefGoogle Scholar
  • 24 Markert M. Mulzer M. Schetter B. Mahrwald R. J. Am. Chem. Soc.  2007,  129:  7258 
    CrossrefPubMedGoogle Scholar
  • 25a Markert M. Scheffler U. Mahrwald R. J. Am. Chem. Soc.  2009,  131:  16642 
    Google Scholar
  • highlighted in
  • 25b Zanda M. Synform  2010,  A16 ; DOI: 10.1055/s-0030-1259401
    Google Scholar
  • 25c Synfacts  2010,  101 
    Google Scholar
23

For primary amine catalysis, see: ref. 2a

26

Scheffler, U.; Mahrwald R. in preparation.