Download PDF
Synlett 2011(19): 2849-2851  
DOI: 10.1055/s-0031-1289537
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

C-Quaternary Vinylglycinols by Metal-Catalyzed Cyclization of Allylic Bistrichloroacetimidates

Kristine Klimovica, Liene Grigorjeva, Ansis Maleckis, Juris Popelis, Aigars Jirgensons*
Latvian Institute of Organic Synthesis, Riga, 1006, Latvia
Fax: +3717541408; e-Mail: aigars@osi.lv;
Further Information

Publication History

Received 2 August 2011
Publication Date:
19 October 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

Bistrichloroacetimidates derived from 2-substituted but-2-ene-1,4-diols are transformed into 4-substituted 4-vinyloxazolines in high yields and excellent regioselectivities when Lewis acids AlCl3, FeCl3, TMSOTf, BF3˙OEt2, and AgBF4 are used as catalysts as well as with the Pd(PPh3)2Cl2/AgBF4 catalytic system. Lower regioselectivity is achieved with a neutral PdCl2(MeCN)2 catalyst and this could be a consequence of a switch to a competitive but less selective reaction mechanism. It is demonstrated that 4-substituted 4-vinyloxazolines can be efficiently transformed to N-Boc-protected C -quaternary vinylglycinols in a one-pot procedure.

Key words

amino alcohols - Lewis acids - palladium - cyclization - regioselectivity

    References

  • Selected examples:
  • 1a Jones MC. Marsden SP. Munoz Subtil DM. Org. Lett.  2006,  8:  5509 
    Google Scholar
  • 1b Jones MC. Marsden SP. Org. Lett.  2008,  10:  4125 
    Google Scholar
  • 1c Fukuda T. Sugiyama K. Arima S. Harigaya Y. Nagamitsu T. Omura S. Org. Lett.  2008,  10:  4239 
    Google Scholar
  • 1d Ariza X. Cornell J. Font-Bardia M. Garcia J. Ortiz J. Sanchez C. Solans X. Angew. Chem. Int. Ed.  2007,  46:  7704 
    Google Scholar
  • 1e Oe K. Shinada T. Ohfune Y. Tetrahedron Lett.  2008,  49:  7426 
    Google Scholar
  • 2 Berkowitz DB. Karukurichi KR. Salud-Bea R. Maiti G. McFadden JM. Morris ML. In Asymmetric Synthesis and Application of α-Amino Acids, ACS Symposium Series   Vol. 1009; Chap. 18:  Soloshonok VA. Izawa K. American Chemical Society; Washington DC: 2009.  p.288 
    Google Scholar
  • α-Alkylation of vinyl amino acid derivatives or their precursors:
  • 3a Seebach D. Burger HM. Schickli CP. Liebigs Ann. Chem.  1991,  669 
    Google Scholar
  • 3b Di Giacomo M. Vinci V. Serra M. Colombo L. Tetrahedron: Asymmetry  2008,  19:  247 
    Google Scholar
  • 3c Weber T. Aeschimann R. Maetzke T. Seebach D. Helv. Chim. Acta  1986,  69:  1365 
    Google Scholar
  • Formal α-vinylation of amino acids:
  • 4a Ma D. Zhu W.
    J. Org. Chem.  2000,  66:  348 
    Google Scholar
  • 4b Pedersen ML. Berkowitz DB. J. Org. Chem.  1993,  58:  6966 
    Google Scholar
  • 5 Addition of vinylmetals to α-imino esters: Wipf P. Stephenson CRJ. Org. Lett.  2003,  5:  2449 
    Google Scholar
  • Olefination of α-formyl amino acids:
  • 6a Berkowitz DB. Chisowa E. McFadden JM. Tetrahedron  2001,  57:  6329 
    Google Scholar
  • 6b Colson PJ. Hegedus LS. J. Org. Chem.  1993,  58:  5918 
    Google Scholar
  • 7 [2,3]-Sigmatropic rearrangement of selenimides: Armstrong A. Emmerson DPG. Org. Lett.  2011,  13:  1040 
    Google Scholar
  • 8 Murga J. Portolés R. Falomir E. Carda M. Marco JA. Tetrahedron: Asymmetry  2005,  16:  1807 
    Google Scholar
  • 9 Berkowitz DB. Pumphrey JA. Shen Q. Tetrahedron Lett.  1994,  35:  8743 
    Google Scholar
  • 10a Berkowitz DB. Wu B. Li H. Org. Lett.  2006,  8:  971 
    Google Scholar
  • 10b Fischer DF. Xin Z. Peters R. Angew. Chem. Int. Ed.  2007,  46:  7704 
    Google Scholar
  • 10c Fischer DF. Barakat A. Xin Z. Weiss ME. Peters R. Chem. Eur. J.  2009,  15:  8722 
    Google Scholar
  • 11 Matsukawa Y. Isobe M. Kotsuki H. Ichikawa Y. J. Org. Chem.  2005,  70:  5339 
    Google Scholar
  • 12a Avenoza A. Cativiela C. Corzana F. Peregrina JM. Zurbano MM. J. Org. Chem.  1999,  64:  8220 
    Google Scholar
  • 12b Avenoza A. Cativiela C. Peregrina JM. Sucunza D. Zurbano MM. Tetrahedron: Asymmetry  1999,  10:  4653 
    Google Scholar
  • 12c Nakamura T. Tsuji T. Iio Y. Miyazaki S. Takemoto T. Nishi T. Tetrahedron: Asymmetry  2006,  17:  2781 
    Google Scholar
  • 12d Wybrow RAJ. Edwards AS. Stevenson NG. Adams H. Johnstone C. Harrity JPA. Tetrahedron  2004,  60:  8869 
    Google Scholar
  • 12e Flock S. Frauenrath H. Synlett  2001,  839 
    Google Scholar
  • 13a Trost BM. Bunt RC. Lemoine RC. Calkins TL. J. Am. Chem. Soc.  2000,  122:  5968 
    Google Scholar
  • 13b Trost BM. Jiang C. Hammer K. Synthesis  2005,  3335 
    Google Scholar
  • 13c Trost BM. Fandrick DR. J. Am. Chem. Soc.  2003,  125:  11836 
    Google Scholar
  • 13d Trost BM. Calkins TL. Oertelt C. Zambrano J. Tetrahedron Lett.  1998,  39:  1713 
    Google Scholar
  • 13e Keith F. Lautens M. Org. Lett.  2000,  2:  2319 
    Google Scholar
  • 14 Portolés R. Murga J. Falomir E. Carda M. Uriel S. Marco JA. Synlett  2002,  711 
    Google Scholar
  • 15 Sugiyama S. Arai S. Kiriyama M. Ishii K. Chem. Pharm. Bull.  2005,  53:  100 
    Google Scholar
  • 16 Bach T. Koerber C. J. Org. Chem.  2000,  65:  2358 
    Google Scholar
  • 17 Hatakeyama S. Yoshida M. Esumi T. Iwabuchi Y. Irle H. Kawamoto T. Yamada H. Nishizawa M. Tetrahedron Lett.  1997,  38:  7887 
    Google Scholar
  • 18a Maleckis A. Jaunzeme I. Jirgensons A. Eur. J. Org. Chem.  2009,  6407 
    Google Scholar
  • The first precedent for Pd (II)-catalyzed formation of 4-vinyloxazoline from allylic bistrichloro-acetimidate:
  • 18b Sabat M. Johnson CR. Org. Lett.  2000,  2:  1089 
    Google Scholar
  • 19 Jaunzeme I. Jirgensons A. Tetrahedron  2008,  64:  5794 
    Google Scholar
  • 20 Grigorjeva L. Jirgensons A. Eur. J. Org. Chem.  2011,  2421 
    Google Scholar
  • 21 For discussion on different reaction pathways of cationic and neutral Pd(II) complexes with allylic imidates, see: Overman LE. Hollis TK. J. Organomet. Chem.  1999,  576:  290 
    Google Scholar