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Synlett 2005(5): 0732-0743  
DOI: 10.1055/s-2005-864794
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© Georg Thieme Verlag Stuttgart · New York

Design of Resolving Agents Based on Crystal Engineering

Kazushi Kinbara*
Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
Fax: +81(3)58417310; e-Mail: kinbara@macro.t.u-tokyo.ac.jp;
Further Information

Publication History

Received 8 July 2004
Publication Date:
09 March 2005 (online)

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Abstract

As a result of systematic studies on the optical resolution of racemates via crystallization, we have found that in many cases, common characteristic hydrogen-bond networks were formed in the less-soluble diastereomeric salts or conglomerates. Design of resolving/derivatizing agents could be achieved on the basis of the concept of crystal engineering, by which molecules were designed to achieve stable hydrogen-bond networks with target racemates.

  • 1 Introduction

  • 2 Design of Acidic Resolving Agents for Diastereomeric ­Resolution

  • 2.1 Systematic Study of the Resolution of 1-Arylethylamines with Mandelic Acid

  • 2.2 p-Substituted Mandelic Acids

  • 2.3 2-Naphthylglycolic Acid

  • 3 Design of Basic Resolving Agents for Diastereomeric ­Resolution

  • 3.1 Systematic Study of the Resolution of 2-Arylalkanoic Acids with 2-Amino-1,2-diphenylethanol

  • 3.2 cis-1-Aminoindan-2-ol

  • 3.3 trans-1-Aminoindan-2-ol, trans-Aminoindan-1-ol, and trans-Aminoindan-3-ol

  • 4 Design of Spontaneous Resolutions

  • 4.1 Salts of Achiral Carboxylic Acids with Racemic Primary Amines

  • 4.2 Salts of Racemic Acids with Racemic Primary Amines

  • 5 Summary

Key words

chiral resolution - chirality - enantiomeric resolution - supramolecular chemistry

    References

  • 1 Rouhi AM. Chem. Eng. News  2003,  81 (18):  44 
    Google Scholar
  • 2 Jacques JA. Collet A. Wilen SH. Enantiomers Racemates and Resolutions   Krieger Publishing Company; Malabar, Florida: 1994. 
    Google Scholar
  • 3a Pasteur L. C. R. Acad. Sci.  1853,  37:  162 
    Google Scholar
  • 3b Gernez M. Compt. Rend.  1866,  63:  843 
    Google Scholar
  • 4a Pasteur L. Ann. Chim. Phys.  1848,  24:  442 
    CrossrefGoogle Scholar
  • 4b Asai S. Ikegami S. Ind. Eng. Chem. Fundam.  1982,  21:  181 
    CrossrefGoogle Scholar
  • 5a Nohira H. Kai M. Nohira M. Nishikawa J. Hoshiko D. Saigo K. Chem. Lett.  1981,  951 
    Google Scholar
  • 5b Saigo K. Ogawa S. Kikuchi S. Kasahara A. Nohira H. Bull. Chem. Soc. Jpn.  1982,  55:  1188 
    Google Scholar
  • 6 Collet A. Jaques J. Bull. Soc. Chim. Fr.  1973,  3330 
    Google Scholar
  • 7 Marchand P. Lefebvre L. Querniard F. Cardinael P. Perez G. Counioux J.-J. Coquerel G. Tetrahedron: Asymmetry  2004,  15:  2455 
    CrossrefGoogle Scholar
  • 8a ten Hoeve W. Wynberg H. J. Org. Chem.  1985,  50:  4508 
    Google Scholar
  • 8b van der Haest AD. Wynberg H. Leusen FJJ. Bruggink A. Recl. Trav. Chim. Pays-Bas  1993,  112:  230 
    Google Scholar
  • 9a Newman P. Optical Resolution Procedures for Chemical Compounds   Vol 1:  Optical Resolution Information Center; New York: 1978. 
    Google Scholar
  • 9b Newman P. Optical Resolution Procedures for Chemical Compounds   Vol 2:  Optical Resolution Information Center; New York: 1981. 
    Google Scholar
  • 9c Newman P. Optical Resolution Procedures for Chemical Compounds   Vol 3:  Optical Resolution Information Center; New York: 1984. 
    Google Scholar
  • 10 Sakai K, Murakami N, Saigo K, and Nohira H. inventors; Jpn. Kokai Tokkyo Koho JP  06001757. 
  • 11 Kinbara K. Sakai K. Hashimoto Y. Nohira H. Saigo K. Tetrahedron: Asymmetry  1996,  7:  1539 
    CrossrefGoogle Scholar
  • 12 Kinbara K. Sakai K. Hashimoto Y. Nohira H. Saigo K. J. Chem. Soc., Perkin Trans. 2  1996,  2615 
    CrossrefGoogle Scholar
  • 13a Kinbara K. Hashimoto Y. Sukegawa M. Nohira H. Saigo K. J. Am. Chem. Soc.  1996,  118:  3441 
    CrossrefGoogle Scholar
  • 13b Kinbara K. Kai A. Maekawa Y. Hashimoto Y. Naruse S. Hasegawa M. Saigo K. J. Chem. Soc., Perkin Trans. 2  1996,  247 
    CrossrefGoogle Scholar
  • 14 Colon DF. Pickard ST. Smith HE. J. Org. Chem.  1991,  56:  2322 
    Google Scholar
  • 15 Hoover JRE. Dunn GL. Jakas LL. Taggart JJ. Guarini JR. Phillips L. J. Med. Chem.  1974,  17:  34 
    CrossrefGoogle Scholar
  • 16a Aston JG. Newkrik JD. Jenkins DM. Dorsky J. Org. Synth., Coll. Vol. III   John Wiley and Sons; New York: 1955.  p.538 
    Google Scholar
  • 16b Sugawara T. Toyota T. Sasakura K. Synth. Commun.  1979,  9:  583 
    Google Scholar
  • 17 Kinbara K. Harada Y. Saigo K. J. Chem. Soc., Perkin Trans. 2  2000,  1339 
    CrossrefGoogle Scholar
  • 18 Kinbara K. Kobayashi Y. Saigo K. J. Chem. Soc., Perkin Trans. 2  1998,  1767 
    CrossrefGoogle Scholar
  • 19 Kinbara K. Kobayashi Y. Saigo K. J. Chem. Soc., Perkin Trans. 2  2000,  111 
    CrossrefGoogle Scholar
  • 20 Ghosh AK. Fidanze S. Senanayake CH. Synthesis  1998,  937 
    Article in Thieme ConnectGoogle Scholar
  • 21 Kinbara K. Katsumata Y. Saigo K. Chirality  2003,  15:  564 
    CrossrefGoogle Scholar
  • 22 Kinbara K. Katsumata Y. Saigo K. Chem. Lett.  2003,  266 
    CrossrefGoogle Scholar
  • 23 Barkworth PMR. Crabb TA. J. Chem. Soc., Perkin Trans. 1  1983,  2807 
    CrossrefGoogle Scholar
  • 24 Mitrochkine A. Gil G. Reglier M. Tetrahedron: Asymmetry  1995,  6:  1535 
    CrossrefGoogle Scholar
  • 25 Desimoni G. Faita G. Mellerio G. Righetti PP. Zanelli C. Gazz. Chim. Ital.  1992,  122:  269 
    Google Scholar
  • 26 Gernez D. C. R. Acad. Sci.  1866,  63:  843 
    Google Scholar
  • 27 Amiard G. Bull. Soc. Chim. Fr.  1956,  447 
    Google Scholar
  • 28a Addadi L. Van Mil J. Lahav M. J. Am. Chem. Soc.  1981,  103:  1249 
    CrossrefGoogle Scholar
  • 28b Addadi L. Gati E. Lahav M. J. Am. Chem. Soc.  1981,  103:  1251 
    CrossrefGoogle Scholar
  • 28c Van Mil J. Addadi L. Gati E. Lahav M. J. Am. Chem. Soc.  1982,  104:  3429 
    CrossrefGoogle Scholar
  • 28d Addadi L. Weinstein S. Gati E. Weissbuch I. Lahav M. J. Am. Chem. Soc.  1982,  104:  4610 
    CrossrefGoogle Scholar
  • 28e Addadi L. Berkovitch-Yellin Z. Domb N. Gati E. Lahav M. Leiserowitz L. Nature  1982,  296:  21 
    CrossrefGoogle Scholar
  • Recently, simultaneous addition of structurally related resolving agents which act as inhibitors for nucleation of the undesired enantiomer was found to remarkably improve the efficiency of resolution in diastereomeric resolution, see:
  • 29a Vries T. Wynberg H. van Echten E. Koek J. ten Hoeve W. Kellogg RM. Broxterman QB. Minnaard A. Kaptein B. van der Sluis S. Hulshof L. Kooistra J. Angew. Chem. Int. Ed.  1998,  37:  2349 
    CrossrefGoogle Scholar
  • 29b Nieuwenhuijzen JW. Grimbergen RFP. Koopman C. Kellogg RM. Vries TR. Pouwer K. van Echten E. Kaptein B. Hulshof LA. Broxterman QB. Angew. Chem. Int. Ed.  2002,  41:  4281 
    CrossrefGoogle Scholar
  • 30 Jacques J. Leclercq M. Brienne M.-J. Tetrahedron  1981,  37:  1727 
    CrossrefGoogle Scholar
  • 31 Kinbara K. Tagawa Y. Saigo K. Tetrahedron: Asymmetry  2001,  12:  2927 
    CrossrefGoogle Scholar
  • 32 Brock CP. Dunitz JD. Chem. Mater.  1994,  6:  1118 
    CrossrefGoogle Scholar
  • 33a Dufour F. Gervais C. Petit MN. Perez G. Coquerel G. J. Chem. Soc., Perkin Trans. 2  2001,  2022 
    CrossrefGoogle Scholar
  • 33b Dufour F. Perez G. Coquerel G. Bull. Chem. Soc. Jpn.  2004,  77:  79 
    CrossrefGoogle Scholar