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Synlett 2012(2): 314-316  
DOI: 10.1055/s-0031-1290113
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Enantioselective Protonation in the Sulfa-Michael Addition Using Chiral Squaramides as Hydrogen-Bonding Organocatalysts

Le Dai, Hongjun Yang, Jingze Niu, Fener Chen*
Fudan-DSM Joint Lab for Synthetic Method and Chiral Technology, Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433, P. R. of China
Fax: +86(21)65643811; e-Mail: rfchen@fudan.edu.cn;
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Publication History

Received 26 September 2011
Publication Date:
13 December 2011 (online)

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Abstract

An enantioselective protonation of transient enolate generated in sulfa-Michael addition was investigated. Various α-substituted acrylic derivatives and thiols were examined as substrates. α-Benzyl acrylimide gave the best results in terms of chemical yield and enantioselectivity (up to 93% yield and 92% ee)

Key words

asymmetric protonation - enantioselective catalysis - squaramide - hydrogen bonding

    References

  • For reviews of asymmetric protonations:
  • 1a Duhamel L. Duhamel P. Plaquevent JC. Tetrahedron: Asymmetry  2004,  15:  3653 
    Search in Google Scholar
  • 1b Yanagisawa A. Ishihara K. Yamamoto H. Synlett  1997,  411 
  • 1c Mohr JT. Hong AY. Stoltz BM. Nat. Chem.  2009,  1:  359 
    Search in Google Scholar
  • 2a Morita M. Drouin L. Motoki R. Kimura Y. Fujimori I. Kanai M. Shibasaki M. J. Am. Chem. Soc.  2009,  131:  3858 
    Search in Google Scholar
  • 2b Cheon CH. Yamamoto H. J. Am. Chem. Soc.  2008,  130:  9246 
    Search in Google Scholar
  • 2c Poisson T. Dalla V. Marsais F. Dupas G. Oudeyer S. Levacher V. Angew. Chem. Int. Ed.  2007,  119:  7220 
    Search in Google Scholar
  • 2d Yanagisawa A. Touge T. Arai T. Angew. Chem. Int. Ed.  2005,  44:  1546 
    Search in Google Scholar
  • 2e Sugiura M. Nakai T. Angew. Chem. Int. Ed.  1997,  36:  2366 
    Search in Google Scholar
  • 2f Mitsuhashi K. Ito R. Arai T. Yanagisawa A. Org. Lett.  2006,  8:  1721 
    Search in Google Scholar
  • 2g Poisson T. Oudeyer S. Dalla V. Marsais F. Levacher V. Synlett  2008,  2447 
  • 3a Poisson T. Yamashita Y. Kobayashi S. J. Am. Chem. Soc.  2010,  132:  7890 
    Search in Google Scholar
  • 3b Sibi MP. Coulomb J. Stanley LM. Angew. Chem. Int. Ed.  2008,  47:  9913 
    Search in Google Scholar
  • 3c Frost CG. Stephen D. Lambshead K. Raithby PR. Warren JE. Gleave R. Org. Lett.  2007,  9:  2119 
    Search in Google Scholar
  • 3d Sibi MP. Tatamidani H. Patil K. Org. Lett.  2005,  7:  2571 
    Search in Google Scholar
  • 3e Hamashima Y. Tamura T. Suzuki S. Sodeoka M. Synlett  2009,  1631 
  • 3f Phua PH. Mathew SP. White AJP. de Vries JG. Blackmond DG. Hii KKM. Chem. Eur. J.  2007,  13:  4602 
    Search in Google Scholar
  • 4 Leow D. Lin S. Chittimalla SK. Fu X. Tan CH. Angew. Chem. Int. Ed.  2008,  47:  5641 
    Search in Google Scholar
  • Selected reviews of bifunctional organocatalysis:
  • 5a Connon SJ. Chem. Commun.  2008,  2499 
  • 5b Dalko PI. Moisan L. Angew. Chem. Int. Ed.  2004,  43:  5138 
    Search in Google Scholar
  • 5c Pihko PM. Angew. Chem. Int. Ed.  2004,  43:  2062 
    Search in Google Scholar
  • 5d Seayad J. List B. Org. Biomol. Chem.  2005,  3:  719 
    Search in Google Scholar
  • Selected reviews of squaramide catalysis:
  • 5e Alemán J. Parra A. Jiang H. Jørgensen KA. Chem. Eur. J.  2011,  17:  6890 
    Search in Google Scholar
  • 5f Storer RI. Aciro C. Jones LH. Chem. Soc. Rev.  2011,  40:  2330 
    Search in Google Scholar
  • 6 Berkessel A. Gröger H. Asymmetric Organocatalysis: From Biomimetic Concepts to Applications in Asymmetric Synthesis   Wiley-VCH; Weinheim: 2004. 
  • 7a Li BJ. Jiang L. Liu M. Chen YC. Ding LS. Wu Y. Synlett  2005,  603 
  • 7b Emori E. Arai T. Sasai H. Shibasaki M. J. Am. Chem. Soc.  1998,  120:  4043 
    Search in Google Scholar
  • For selected chiral squaramide catalysts promoted asymmetric organic reactions, see:
  • 8a Dai L. Wang SX. Chen FE. Adv. Synth. Catal.  2010,  352:  2137 
    Search in Google Scholar
  • 8b Dai L. Yang HJ. Chen FE. Eur. J. Org. Chem.  2011,  26:  5071 
    Search in Google Scholar
  • 8c Zhu Y. Malerich JP. Rawal VH. Angew. Chem. Int. Ed.  2010,  49:  153 
    Search in Google Scholar
  • 8d Konishi H. Lam TY. Malerich JP. Rawal VH. Org. Lett.  2010,  12:  2028 
    Search in Google Scholar
  • 8e Qian Y. Ma G. Lv A. Zhu H.-L. Zhao J. Rawal VH. Chem. Commun.  2010,  46:  3004 
    Search in Google Scholar
  • 8f Xu D.-Q. Wang Y.-F. Zhang W. Luo S.-P. Zhong A.-G. Xia A.-B. Xu Z.-Y. Chem. Eur. J.  2010,  16:  4177 
    Search in Google Scholar
  • 8g Yang W. Du D.-M. Org. Lett.  2010,  12:  5450 
    Search in Google Scholar
  • 8h Lee JW. Ryu TH. Oh JS. Bae HY. Jang HB. Song CE. Chem. Commun.  2009,  7224 
  • 9 Evans DA. Mathre DJ. Scott WL. J. Org. Chem.  1985,  50:  1830 
    Search in Google Scholar