Download PDF
Synlett 2011(17): 2513-2516  
DOI: 10.1055/s-0030-1260338
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Iron-Catalyzed Ring-Opening of meso-Aziridines with Amines

Alex Marti, Luise Richter, Christoph Schneider*
Institut für Organische Chemie, Universität Leipzig, Johannisallee 29, 04103 Leipzig, Germany
Fax: +49(341)9736599; e-Mail: schneider@chemie.uni-leipzig.de;
Further Information

Publication History

Received 19 August 2011
Publication Date:
27 September 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

A cationic iron complex has been found to catalyze the aminolysis of meso-N-aryl aziridines very efficiently furnishing valuable 1,2-diamines in typically excellent yields. This protocol is compatible with a range of functional groups both in the aziridine and amine components.

Key words

amine - aziridine - catalysis - 1,2-diamine - iron

    References and Notes

  • Selected reviews:
  • 1a Schneider C. Angew. Chem. Int. Ed.  2009,  48:  2082 
    Search in Google Scholar
  • 1b Aziridines and Epoxides in Organic Synthesis   Yudin AK. Wiley-VCH; Weinheim: 2006. 
  • 1c Pineschi M. Eur. J. Org. Chem.  2006,  4979 
  • 1d Hu XE. Tetrahedron  2004,  60:  2701 
    Search in Google Scholar
  • 1e McCoull W. Davis FA. Synthesis  2000,  1347 
  • Most recent catalytic, enantioselective ring-opening reactions:
  • 2a Xu Y. Lin L. Kanai M. Matsunaga S. Shibasaki M. J. Am. Chem. Soc.  2011,  133:  5791 
    Search in Google Scholar
  • 2b Wu B. Gallucci JC. Parquette JR. RajanBabu TV. Angew. Chem. Int. Ed.  2009,  48:  1126 
    Search in Google Scholar
  • 2c Rowland EB. Rowland GB. Rivera-Otero E. Antilla JC. J. Am. Chem. Soc.  2007,  129:  12084 
    Search in Google Scholar
  • 2d Fukuta Y. Mita T. Fukuda N. Kanai M. Shibasaki M. J. Am. Chem. Soc.  2006,  128:  6312 
    Search in Google Scholar
  • 2e Mita T. Fujimori I. Wada R. Wen J. Kanai M. Shibasaki M. J. Am. Chem. Soc.  2005,  127:  11252 
    Search in Google Scholar
  • For selected catalytic processes, see:
  • 3a Hong D. Lin X. Zhu Y. Lei M. Wang Y. Org. Lett.  2009,  11:  5678 
    Search in Google Scholar
  • 3b Wu J. Sun X. Li Y. Eur. J. Org. Chem.  2005,  4271 
  • 3c Bisai A. Bhanu Prasad BA. Singh VK. Tetrahedron Lett.  2005,  46:  7935 
    Search in Google Scholar
  • 3d Watson IDG. Yudin AK. J. Org. Chem.  2003,  68:  5160 
    Search in Google Scholar
  • 3e Swamy NR. Venkateswarlu Y. Synth. Commun.  2003,  33:  547 
    Search in Google Scholar
  • 3f Yadav JS. Reddy BVS. Rao KV. Raj KS. Prasad AR. Synthesis  2002,  1061 
  • 3g Cossy J. Bellosta V. Alauze V. Desmurs JR. Synthesis  2002,  2211 
  • 3h Hou X.-L. Fan R.-H. Dai L.-X. J. Org. Chem.  2002,  67:  5295 
    Search in Google Scholar
  • 3i Chandrasekhar M. Sekar G. Singh VK. Tetrahedron Lett.  2000,  41:  10079 
    Search in Google Scholar
  • 3j Sekar G. Singh VK. J. Org. Chem.  1999,  64:  2537 
    Search in Google Scholar
  • For catalytic, enantioselective protocols, see:
  • 3k Arai K. Lucarini S. Salter MS. Ohta K. Yamashita Y. Kobayashi S. J. Am. Chem. Soc.  2007,  129:  8103 
    Search in Google Scholar
  • 3l Yu R. Yamashita Y. Kobayashi S. Adv. Synth. Catal.  2009,  351:  147 
    Search in Google Scholar
  • 3m Seki K. Yu R. Yamazaki Y. Yamashita Y. Kobayashi S. Chem. Commun.  2009,  5722 
  • 3n

    See ref. 9.

  • For selected catalytic processes, see:
  • 4a Bhadra S. Adak L. Samanta S. Maidul Islam AKM. Mukherjee M. Ranu BC. J. Org. Chem.  2010,  75:  8533 
    Search in Google Scholar
  • 4b Bhanu Prasad BA. Sanghi R. Singh VK. Tetrahedron  2002,  58:  7355 
    Search in Google Scholar
  • 4c Hou X.-L. Fan R.-H. Dai L.-X. J. Org. Chem.  2002,  67:  5295 
    Search in Google Scholar
  • 4d Bhanu Prasad BA. Sekar G. Singh VK. Tetrahedron Lett.  2000,  41:  4677 
    Search in Google Scholar
  • For selected catalytic processes, see:
  • 5a Zeng F. Alper H. Org. Lett.  2010,  12:  5567 
    Search in Google Scholar
  • 5b Yadav JS. Reddy BVS. Baishya G. Venkatram Reddy P. Narsaiah AV. Catal. Commun.  2006,  7:  807 
    Search in Google Scholar
  • 5c Wu J. Sun X. Li Y. Eur. J. Org. Chem.  2005,  4271 
  • 5d Yadav JS. Subba Reddy BV. Baishya G. Reddy PV. Harshavardhan SJ. Synthesis  2004,  1854 
  • 5e Hou X.-L. Fan R.-H. Dai L.-X. J. Org. Chem.  2002,  67:  5295 
    Search in Google Scholar
  • 5f Wu J. Hou X.-L. Dai L.-X. J. Chem. Soc., Perkin Trans. 1  2001,  1314 
  • For catalytic, enantioselective protocols, see:
  • 5g Luo Z.-B. Hou X.-L. Dai L.-X. Tetrahedron: Asymmetry  2007,  18:  443 
    Search in Google Scholar
  • 5h Wang Z. Sun X. Ye S. Wang W. Wang B. Wu J. Tetrahedron: Asymmetry  2008,  19:  964 
    Search in Google Scholar
  • 5i Larson SE. Baso JC. Li G. Antilla JC. Org. Lett.  2009,  11:  5186 
    Search in Google Scholar
  • 5j Della Salla G. Lattanzi A. Org. Lett.  2009,  11:  3330 
    Search in Google Scholar
  • 5k Lattanzi A. Della Salla G. Eur. J. Org. Chem.  2009,  1845 
  • 5l Zhang Y. Wee Kee C. Lee R. Fu X. Soh JYT. Loh EMF. Huang KW. Tan CH. Chem. Commun.  2011,  47:  3897 
    Search in Google Scholar
  • 6a Kobayashi S. Sugiura M. Kitagawa H. Lam WWL. Chem. Rev.  2002,  102:  2227 
    Search in Google Scholar
  • 6b Kobayashi S. Eur. J. Org. Chem.  1999,  15 
  • Selected reviews:
  • 7a Bolm C. Legros J. Le Paih J. Zani L. Chem. Rev.  2004,  104:  6217 
    Search in Google Scholar
  • 7b Enthaler S. Junge K. Beller M. Angew. Chem. Int. Ed.  2008,  47:  3317 
    Search in Google Scholar
  • 7c Fürstner A. Angew. Chem. Int. Ed.  2009,  48:  1364 
    Search in Google Scholar
  • 7d Kazmaier U. Angew. Chem. Int. Ed.  2009,  48:  5790 
    Search in Google Scholar
  • 8a

    Ligand: mep = N,N-dimethyl-N,N-bis(2-pyridylmethyl)-ethane-1,2-diamine; BPMEN is another commonly employed abbreviation for this ligand.

  • 8b Toftlund H. Pedersen E. Yde-Andersen S. Acta Chem. Scand. A  1984,  38:  693 
    Search in Google Scholar
  • For cationic iron mep complexes as oxidation catalysts, see e.g.:
  • 8c Costas M. Tipton AK. Chen K. Jo D.-H. Que L. J. Am. Chem. Soc.  2001,  123:  6722 
    Search in Google Scholar
  • 8d White MC. Doyle AG. Jacobsen EN. J. Am. Chem. Soc.  2001,  123:  7194 
    Search in Google Scholar
  • 9 For a highly enantioselective Ti-catalyzed ring-opening of meso-aziridines with amines, see: Peruncheralathan S. Teller H. Schneider C. Angew. Chem. Int. Ed.  2009,  48:  4849 
    CrossrefSearch in Google Scholar
  • For scandium- and indium-catalyzed ring-opening reactions of aziridines, see:
  • 10a Peruncheralathan S. Henze M. Schneider C. Synlett  2007,  2289 
  • 10b Peruncheralathan S. Henze M. Schneider C. Tetrahedron Lett.  2007,  48:  6743 
    Search in Google Scholar
  • Silver salts are known to be capable of abstracting chloride anions of transition-metal complexes resulting in cationic metal complexes, see e.g.:
  • 11a Evans DA. Murry JA. Von Matt P. Norcross RD. Miller SJ. Angew. Chem., Int. Ed. Engl.  1995,  34:  798 
    Search in Google Scholar
  • 11b Usuda H. Kuramochi A. Kanai M. Shibasaki M. Org. Lett.  2004,  6:  4387 
    Search in Google Scholar
  • 11c Cochran BM. Michael FE. Org. Lett.  2008,  10:  329 
    Search in Google Scholar
12

General Procedure for the Iron-Catalyzed Ring-Opening of meso -Aziridines with Amines
FeCl2(mep) (24 mg, 0.05 mmol, 5 mol%) was dissolved in CH2Cl2 (2 mL) and mixed with AgSbF6 (34 mg, 0.10 mmol, 10 mol%), under an argon atmosphere, for 30 min at r.t. Subsequently, a solution of the aniline (1.20 mmol) in CH2Cl2 (1 mL) was added followed by a solution of the respective aziridine (1.00 mmol) in CH2Cl2 (1 mL). Stirring was continued at r.t. until the reaction was judged complete by GC analysis. The GC yields were determined against iodobenzene as internal standard. The solvents were removed under nitrogen flux, and the crude product was purified with chromatography over silica gel using pentane-EtOAc (30:1) as eluent. For analytical and spectroscopic details of the products, see ref. 3.