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Synthesis 2009(7): 1105-1112  
DOI: 10.1055/s-0028-1088000
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of 2-[(Arylmethylene)amino]cyclopropanecarbonitriles via a Two-Step Ring Transformation of 2-(Cyanomethyl)aziridines

Sven Mangelinckx, Matthias D’hooghe, Sietske Peeters, Norbert De Kimpe*
Department of Organic Chemistry, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, 9000 Ghent, Belgium
Fax: +32(9)2646243; e-Mail: norbert.dekimpe@UGent.be;
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Publikationsverlauf

Received 22 August 2008
Publikationsdatum:
06. März 2009 (online)

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Abstract

Reaction of 2-(cyanomethyl)aziridines with N-bromosuccinimide in dichloromethane results in the formation of 3-[(arylmethylene)amino]-4-bromobutanenitriles in high yield. The latter β-amino-γ-bromobutanenitriles were converted into separable trans- and cis-2-[(arylmethylene)amino]cyclopropanecarbonitriles through a 1,3-cyclization by reaction with potassium tert-butoxide, thus culminating in a two-step ring transformation of 2-(cyano­methyl)aziridines into 2-[(arylmethylene)amino]cyclopropanecarbonitriles.

Key words

amino nitriles - cyclizations - 2-(cyanomethyl)aziridines - carbocycles - ring opening

    References

  • 2a O’Donnell MJ. Bruder WA. Eckrich TM. Shullenberger DF. Staten GS. Synthesis  1984,  127 
  • 2b Isogai K. Sakai J.-i. Yamauchi K. Watanabe K. Bull. Chem. Soc. Jpn.  1986,  59:  2839 
    Suche in Google Scholar
  • 2c Salaün J. Marguerite J. Karkour B. J. Org. Chem.  1990,  55:  4276 
    Suche in Google Scholar
  • 2d Gaucher A. Ollivier J. Salaün J. Synlett  1991,  151 
  • 2e Salaün J, and Tondu S. inventors; Fr. Demande FR2652082  A1.  ; Chem. Abstr. 1991, 115, 207567
  • For some recent reviews on the synthesis of α-ACC, see:
  • 3a Brackmann F. de Meijere A. Chem. Rev.  2007,  107:  4493 
    Suche in Google Scholar
  • 3b Cativiela C. Díaz-de-Villegas MD. Tetrahedron: Asymmetry  2000,  11:  645 
    Suche in Google Scholar
  • 4 For a review on α-amino nitriles, see: Enders D. Shilvock JP. Chem. Soc. Rev.  2000,  29:  359 
    CrossrefSuche in Google Scholar
  • 5 Vergne F. Aitken DJ. Husson H.-P. J. Org. Chem.  1992,  57:  6071 
    CrossrefSuche in Google Scholar
  • 6 Vergne F. Partogyan K. Aitken DJ. Husson H.-P. Tetrahedron  1996,  52:  2421 
    CrossrefSuche in Google Scholar
  • 7 Khlebnikov AF. Novikov MS. Nikiforova TY. Kostikov RR. Russ. J. Org. Chem.  1999,  35:  91 
    Suche in Google Scholar
  • 8 Khlebnikov AF. Nikiforova TY. Kostikov RR. Russ. J. Org. Chem.  1999,  35:  707 
    Suche in Google Scholar
  • 9a Link JO, Mossman CJ, and Liu J. inventors; PCT Int. Appl.  042968.  ; Chem. Abstr. 2008, 148, 449919
  • 9b Mossman CJ. inventors; PCT Int. Appl.  102535.  ; Chem. Abstr. 2006, 145, 377572
  • 9c Woo SH, Vivian RW, and Link JO. inventors; PCT Int. Appl.  060810.  ; Chem. Abstr. 2006, 145, 46274
  • 9d Setti EL. inventors; PCT Int. Appl.  060494.  ; Chem. Abstr. 2006, 145, 46273
  • 9e Li J. inventors; PCT Int. Appl.  034004.  ; Chem. Abstr. 2006, 144, 350977
  • 9f Zipfel SM, Woo SH, and Yang D. inventors; PCT Int. Appl.  034006.  ; Chem. Abstr. 2006, 144, 331694
  • 9g Link JO, and Graupe M. inventors; PCT Int. Appl.  074904.  ; Chem. Abstr. 2005, 143, 229992
  • 9h Link JO, Mossman CJ, Woo SH, and Zipfel SM. inventors; PCT Int. Appl.  028429.  ; Chem. Abstr. 2005, 142, 355571
  • 10a Reissig H.-U. Zimmer R. Chem. Rev.  2003,  103:  1151 
    Suche in Google Scholar
  • 10b Reissig H.-U. Top. Curr. Chem.  1988,  144:  73 
    Suche in Google Scholar
  • 10c Yu M. Pagenkopf BL. Tetrahedron  2005,  61:  321 
    Suche in Google Scholar
  • For some recent reviews on the application of alicyclic β-amino acids in peptide synthesis, see:
  • 11a Miller JA. Nguyen ST. Mini-Rev. Org. Chem.  2005,  2:  39 
    Suche in Google Scholar
  • 11b Fülöp F. Martinek TA. Tóth GK. Chem. Soc. Rev.  2006,  35:  323 
    Suche in Google Scholar
  • For applications of β-ACC derivatives in peptide synthesis, see:
  • 12a Urman S. Gaus K. Yang Y. Strijowski U. Sewald N. De Pol S. Reiser O. Angew. Chem. Int. Ed.  2007,  46:  3976 
    Suche in Google Scholar
  • 12b De Pol S. Zorn C. Klein CD. Zerbe O. Reiser O. Angew. Chem. Int. Ed.  2004,  43:  511 
    Suche in Google Scholar
  • 12c Koglin N. Zorn C. Beumer R. Cabrele C. Bubert C. Sewald N. Reiser O. Beck-Sickinger AG. Angew. Chem. Int. Ed.  2003,  42:  202 
    Suche in Google Scholar
  • 12d Godier-Marc E. Aitken DJ. Husson H.-P. Tetrahedron Lett.  1997,  38:  4065 
    Suche in Google Scholar
  • 12e Díaz M. Jiménez J. Ortuño RM. Tetrahedron: Asymmetry  1997,  8:  2465 
    Suche in Google Scholar
  • 12f Díaz M. Ortuño RM. Tetrahedron: Asymmetry  1996,  7:  3465 
    Suche in Google Scholar
  • 12g Paulini K. Reissig H.-U. Liebigs Ann. Chem.  1994,  549 
  • 13 Gnad F. Reiser O. Chem. Rev.  2003,  103:  1603 
    CrossrefPubMedSuche in Google Scholar
  • 14 For a review on the chemistry of N-cyclopropylimines, see: Soldevilla A. Sampedro D. Org. Prep. Proced. Int.  2007,  39:  561 
    CrossrefSuche in Google Scholar
  • 15a Caramella P. Huisgen R. Schmolke B. J. Am. Chem. Soc.  1974,  96:  2997 
    Suche in Google Scholar
  • 15b Caramella P. Huisgen R. Schmolke B. J. Am. Chem. Soc.  1974,  96:  2999 
    Suche in Google Scholar
  • 15c Campos PJ. Soldevilla A. Sampedro D. Rodr íguez MA. Tetrahedron Lett.  2002,  43:  8811 
    Suche in Google Scholar
  • 16a Campos PJ. Soldevilla A. Sampedro D. Rodrí guez MA. Org. Lett.  2001,  3:  4087 
    Suche in Google Scholar
  • 16b Sampedro D. Soldevilla A. Rodrí guez MA. Campos PJ. Olivucci M. J. Am. Chem. Soc.  2005,  127:  441 
    Suche in Google Scholar
  • 16c Soldevilla A. Sampedro D. Campos PJ. Rodrí guez MA. J. Org. Chem.  2005,  70:  6976 
    Suche in Google Scholar
  • 16d Campos PJ. Sampedro D. Rodríguez MA. Organometallics  2002,  21:  4076 
    Suche in Google Scholar
  • 17 D’hooghe M. Mangelinckx S. Persyn E. Van Brabandt W. De Kimpe N. J. Org. Chem.  2006,  71:  4232 
    CrossrefSuche in Google Scholar
  • 18a D’hooghe M. Van Speybroeck V. Van Nieuwenhove A. Waroquier M. De Kimpe N. J. Org. Chem.  2007,  72:  4733 
    Suche in Google Scholar
  • 18b D’hooghe M. Vervisch K. Van Nieuwenhove A. De Kimpe N. Tetrahedron Lett.  2007,  48:  1771 
    Suche in Google Scholar
  • 19 De Kimpe N. De Smaele D. Bogaert P. Synlett  1994,  287 
    Thieme Connect
  • 20a De Kimpe N. Sulmon P. Synlett  1990,  161 
  • 20b De Kimpe N. Sulmon P. Stevens C. Tetrahedron  1991,  47:  4723 
    Suche in Google Scholar
  • 21a Dauben HJ. McCoy LL. J. Am. Chem. Soc.  1959,  81:  4863 
    Suche in Google Scholar
  • 21b Kundi T. Synlett  2006,  498 
  • 22a Adam J. Gosselain PA. Goldfinger P. Nature (London)  1953,  171:  704 
    Suche in Google Scholar
  • 22b Gosselain PA. Adam J. Goldfinger P. Bull. Soc. Chim. Belg.  1956,  65:  533 
    Suche in Google Scholar
  • 23 Henniges H. Gussetti C. Militzer HC. Baird MS. de Meijere A. Synthesis  1994,  1471 
    Thieme Connect
  • 24 Díez D. García P. Fernández P. Marcos IS. Garrido NM. Basabe P. Broughton HB. Synlett  2005,  158 
    Thieme Connect
  • 25 For a review on the cyclization of nitrile anions to cyclopropanes, see: Fleming FF. Shook BC. Tetrahedron  2002,  58:  1 
    CrossrefSuche in Google Scholar
  • 26a Morris JM. Dunmire RB. Koenig PE. Newkome GR. J. Org. Chem.  1972,  37:  1244 
    Suche in Google Scholar
  • 26b Atanassov PK. Zhou Y. Linden A. Heimgartner H. Helv. Chim. Acta  2002,  85:  1102 
    Suche in Google Scholar
  • 27 Wessjohann L. McGaffin G. de Meijere A. Synthesis  1989,  359 
    Thieme Connect
  • 28 Deller K. Kleemann A. Martens J. Weigel H. Arch. Pharm. (Weinheim, Ger.)  1981,  314:  648 
    CrossrefSuche in Google Scholar
  • 29a Trabocchi A. Guarna F. Guarna A. Curr. Org. Chem.  2005,  9:  1127 
    Suche in Google Scholar
  • 29b Ordóñez M. Cativiela C. Tetrahedron: Asymmetry  2007,  18:  3 
    Suche in Google Scholar
1

Postdoctoral Fellow of the Research Foundation - Flanders (FWO).