Synthesis 2008(7): 1153-1157  
DOI: 10.1055/s-2007-990935
PSP
© Georg Thieme Verlag Stuttgart · New York

Catalytic Enantioselective 5-Hydroxyisoxazolidine Synthesis: An Asymmetric Entry to β-Amino Acids

Ismail Ibrahem, Ramon Rios, Jan Vesely, Gui-Ling Zhao, Armando Córdova*
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm, Sweden
Fax: +46(8)154908; e-Mail: [email protected];
Further Information

Publication History

Received 16 August 2007
Publication Date:
28 November 2007 (online)

Abstract

The highly chemo- and enantioselective organocatalytic tandem reaction between N-carbamate-protected hydroxylamines and α,β-unsaturated aldehydes is presented. The reaction represents a unique entry for the asymmetric synthesis of 5-hydroxyisoxazolidines, oxazolidin-5-ones or γ-hydroxyamino alcohols in high yields and 90-99% ee. A procedure for the conversion of the oxazolidin-5-ones into the corresponding β-amino acids is also described.

    References

  • 1a Baldwin JE. Harwood LM. Lombard MJ. Tetrahedron  1984,  40:  4363 
  • 1b Sibi MP. Prabagaran N. Ghorpade SG. Jasperse GP. J. Am. Chem. Soc.  2003,  125:  11796 
  • 1c Sibi MP. Liu M. Org. Lett.  2001,  3:  4181 
  • 1d Mukherjee S. Prasad AK. Parmar VS. Howarth OW. Bioorg. Med. Chem. Lett.  2001,  11:  2117 
  • 1e Keirs D. Moffat D. Overton K. Tomanek R. J. Chem. Soc., Perkin Trans. 1  1999,  1041 
  • 1f Panfil I. Maciejewski S. Belzecki C. Chielewski M. Tetrahedron Lett.  1989,  30:  1527 
  • 1g Shindo M. Itoh K. Tsuchiya C. Shishido K. Org. Lett.  2002,  4:  3119 
  • 1h Luisi R. Capriati V. Florio S. Vista T. J. Org. Chem.  2003,  68:  2961 
  • 1i Lee H.-S. Park J.-S. Kim BM. Gellman SH. J. Org. Chem.  2003,  68:  1575 
  • 1j Xiang Y. Gi H.-J. Niu D. Schinazi RF. Zhao K. J. Org. Chem.  1997,  62:  7439 
  • 1k Zelenin KN. Motorina IA. Sviridova LA. Bezhan IP. Ershov AY. Golubeva GA. Bundel YG. Chem. Heterocycl. Compd. (Engl. Transl.)  1987,  23:  1018 
  • For reviews, see:
  • 2a Liu M. Sibi MP. Tetrahedron  2002,  58:  7991 
  • 2b Sewald N. Angew. Chem. Int. Ed.  2003,  42:  5794 
  • For examples of catalytic conjugate aminations, see:
  • 3a Sibi MP. Shay JJ. Liu M. Jasperse CP. J. Am. Chem. Soc.  2001,  123:  9708 
  • 3b Hortsmann TE. Guerin DJ. Miller SJ. Angew. Chem. Int. Ed.  2000,  39:  3635 
  • 3c Doi H. Sakai T. Iguchi M. Yamada K. Tomioka K. J. Am. Chem. Soc.  2003,  125:  2886 
  • 3d Myers JK. Jacobsen EN. J. Am. Chem. Soc.  1999,  121:  8959 
  • 3e Zhuang W. Hazell RG. Jørgensen KA. Chem. Commun.  2001,  1240 
  • 3f Palomo C. Oiarbide M. Halder R. Kelso M. Gómez-Bengoa E. García JM. J. Am. Chem. Soc.  2004,  126:  9188 
  • 3g Yamagiwa N. Qin H. Matunaga S. Shibasaki M. J. Am. Chem. Soc.  2005,  127:  13419 ; and references therein
  • 3h Xu L.-W. Xia C.-G. Eur. J. Org. Chem.  2005,  633 
  • 4a Dalko PI. Moisan L. Angew. Chem. Int. Ed.  2001,  40:  3726 
  • 4b List B. Chem. Commun.  2006,  819 
  • 4c Duthaler RO. Angew. Chem. Int. Ed.  2003,  42:  975 
  • 4d Dalko PI. Moisan L. Angew. Chem. Int. Ed.  2004,  43:  5138 
  • 4e Enders D. Grondal C. Hüttl MRM. Angew. Chem. Int. Ed.  2007,  46:  1545 
  • Selected examples see:
  • 5a Halland N. Aburell PS. Jørgensen KA. Angew. Chem. Int. Ed.  2004,  43:  1272 
  • 5b Huang Y. Walji AM. Larsen CH. MacMillan DWC. J. Am. Chem. Soc.  2005,  127:  15051 
  • 5c Yang JW. Hechavarria Fonseca MT. List B. J. Am. Chem. Soc.  2005,  127:  15036 
  • 5d Marigo M. Schulte T. Franén J. Jørgensen KA. J. Am. Chem. Soc.  2005,  127:  15710 
  • 5e Yamamoto Y. Momiyama N. Yamamoto H. J. Am. Chem. Soc.  2004,  126:  5962 
  • 5f Ramachary DB. Chowdari NS. Barbas CF. Angew. Chem. Int. Ed.  2003,  42:  4233 
  • 5g Sundén H. Ibrahem I. Eriksson L. Córdova A. Angew. Chem. Int. Ed.  2005,  44:  4877 
  • 5h Enders D. Hüttl MRM. Grondal C. Raabe G. Nature  2006,  441:  861 
  • For organocatalytic β-amino acid synthesis, see:
  • 5i Yang J. W. Stadler M. List B. Angew. Chem. Int. Ed.  2007,  46:  609 
  • 5j Vesely J. Ibrahem I. Rios R. Córdova A. Tetrahedron Lett.  2007,  48:  421 
  • For excellent reviews on the concept of domino and tandem reactions see:
  • 6a Tietze LF. Chem. Rev.  1996,  96:  115 
  • 6b Wasilke JC. Obrey SJ. Baker RT. Bazan GC. Chem. Rev.  2005,  105:  1001 
  • 7 Sundén H. Rios R. Ibrahem I. Zhao G.-L. Eriksson L. Córdova A. Adv. Synth. Catal.  2007,  349:  827 
  • During the preparation of our initial communication, MacMillan and co-workers reported an elegant imidazolidinone amine-catalyzed conjugate addition of silyloxycarbamates to enals. Catalyst 4 did not catalyze this transformation with cinnamaldehydes under our reaction conditions. However, amine 4 catalyzes this transformation when aliphatic enals are used as substrates.
  • 8a Ibrahem I. Rios R. Vesely J. Zhao G.-L. Córdova A. Chem. Commun.  2007,  849 
  • 8b Chen YK. Yoshida M. MacMillan DWC. J. Am. Chem. Soc.  2006,  128:  9328 
  • 8c Vesely J. Ibrahem I. Rios R. Zhao G.-L. Xu Y. Córdova A. Tetrahedron Lett.  2007,  48:  2193 
  • 9a Marigo M. Wabnitz TC. Fielenbach D. Jørgensen KA. Angew. Chem. Int. Ed.  2005,  44:  794 
  • 9b Hayashi Y. Gotoh H. Hayashi T. Shoji M. Angew. Chem. Int. Ed.  2005,  44:  4212 
  • 10 Rios R. Ibrahem I. Vesely J. Zhao G.-L. Córdova A. Tetrahedron Lett.  2007,  48:  5701 
  • 11 Graf E. Boeddeker H. Justus Liebigs Ann. Chem.  1958,  613:  111