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Synthesis 2012(1): 27-36  
DOI: 10.1055/s-0031-1289611
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

Cationic Late-Transition-Metal Complexes Catalyze the Ring Opening of Aziridines with Amines

Alex Marti, Saravanan Peruncheralathan¹, Christoph Schneider*
Institut für Organische Chemie, Universität Leipzig, Johannisallee 29, 04103 Leipzig, Germany
Fax: +49(341)9736599; e-Mail: schneider@chemie.uni-leipzig.de;
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Publication History

Received 20 September 2011
Publication Date:
18 November 2011 (online)

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Abstract

Cationic palladium and nickel complexes have been found to catalyze the ring-opening of meso-N-aryl aziridines with anilines very efficiently and furnish valuable 1,2-diamines in typically excellent yields. The active catalysts were generated in situ from the corresponding metal dichloride bis(triphenylphosphine) complexes through chloride abstraction with a silver salt. This new protocol is applicable across a broad substrate range with both cyclic as well as acyclic aziridines. In addition, cationic gold-phosphine complexes proved to be highly reactive as well as delivering products in comparable rates and yields.

Key words

aziridine - catalysis - 1,2-diamine - nickel - palladium

    References

  • Selected reviews:
  • 2a Schneider C. Synthesis  2006,  3919 
  • 2b Pastor IM. Yus M. Curr. Org. Chem.  2005,  9:  1 
    Search in Google Scholar
  • 2c Jacobsen EN. Wu MH. Comprehensive Asymmetric Catalysis   Vol. 2:  Jacobsen EN. Pfaltz A. Yamamoto H. Springer; Berlin: 1999.  p.649 
    Search in Google Scholar
  • Selected reviews:
  • 3a Schneider C. Angew. Chem. Int. Ed.  2009,  48:  2082 
    Search in Google Scholar
  • 3b Yudin AK. Aziridines and Epoxides in Organic Synthesis   Wiley-VCH; Weinheim: 2006. 
  • 3c Pineschi M. Eur. J. Org. Chem.  2006,  4979 
  • 3d Hu XE. Tetrahedron  2004,  60:  2701 
    Search in Google Scholar
  • 3e McCoull W. Davis FA. Synthesis  2000,  1347 
  • For selected catalytic processes, see:
  • 4a Hong D. Lin X. Zhu Y. Lei M. Wang Y. Org. Lett.  2009,  11:  5678 
    Search in Google Scholar
  • 4b Bisai A. Bhanu Prasad BA. Singh VK. Tetrahedron Lett.  2005,  46:  7935 
    Search in Google Scholar
  • 4c Wu J. Sun X. Li Y. Eur. J. Org. Chem.  2005,  4271 
  • 4d Watson IDG. Yudin AK.
    J. Org. Chem.  2003,  68:  5160 
    Search in Google Scholar
  • 4e Swamy NR. Venkateswarlu Y. Synth. Commun.  2003,  33:  547 
    Search in Google Scholar
  • 4f Yadav JS. Reddy BVS. Rao KV. Raj KS. Prasad AR. Synthesis  2002,  1061 
  • 4g Cossy J. Bellosta V. Alauze V. Desmurs JR. Synthesis  2002,  2211 
  • 4h Hou X.-L. Fan R.-H. Dai L.-X. J. Org. Chem.  2002,  67:  5295 
    Search in Google Scholar
  • 4i Chandrasekhar M. Sekar G. Singh VK. Tetrahedron Lett.  2000,  41:  10079 
    Search in Google Scholar
  • 4j Sekar G. Singh VK. J. Org. Chem.  1999,  64:  2537 
    Search in Google Scholar
  • 4k Meguro M. Asao N. Yamamoto Y. Tetrahedron Lett.  1994,  35:  7395 
    Search in Google Scholar
  • For selected catalytic processes, see:
  • 5a Bhadra S. Adak L. Samanta S. Maidul Islam AKM. Mukherjee M. Ranu BC. J. Org. Chem.  2010,  75:  8533 
    Search in Google Scholar
  • 5b Bera M. Roy S. J. Org. Chem.  2009,  74:  8814 
    Search in Google Scholar
  • 5c Bhanu Prasad BA. Sanghi R. Singh VK. Tetrahedron  2002,  58:  7355 
    Search in Google Scholar
  • 5d Hou X.-L. Fan R.-H. Dai L.-X. J. Org. Chem.  2002,  67:  5295 
    Search in Google Scholar
  • 5e Bhanu Prasad BA. Sekar G. Singh VK. Tetrahedron Lett.  2000,  41:  4677 
    Search in Google Scholar
  • For selected catalytic processes, see:
  • 6a 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
  • 6b Zeng F. Alper H. Org. Lett.  2010,  12:  5567 
    Search in Google Scholar
  • 6c Yadav JS. Reddy BVS. Baishya G. Venkatram Reddy P. Narsaiah AV. Catal. Commun.  2006,  7:  807 
    Search in Google Scholar
  • 6d Wu J. Sun X. Li Y. Eur. J. Org. Chem.  2005,  4271 
  • 6e Yadav JS. Subba Reddy BV. Baishya G. Reddy PV. Harshavardhan SJ. Synthesis  2004,  1854 
  • 6f Hou X.-L. Fan R.-H. Dai L.-X. J. Org. Chem.  2002,  67:  5295 
    Search in Google Scholar
  • 6g Wu J. Hou X.-L. Dai L.-X. J. Chem. Soc., Perkin Trans. 1  2001,  1314 
  • 7 Li Z. Fernandez M. Jacobsen EN. Org. Lett.  1999,  1:  1611 
    Search in Google Scholar
  • 8a Yabu K. Masumoto S. Yamasaki S. Hamashima Y. Kanai M. Du W. Curran DP. Shibasaki M. J. Am. Chem. Soc.  2001,  123:  9908 
    Search in Google Scholar
  • 8b Mita T. Fujimori I. Wada R. Wen J. Kanai M. Shibasaki M. J. Am. Chem. Soc.  2005,  127:  11252 
    Search in Google Scholar
  • 8c Fukuta Y. Mita T. Fukuda N. Kanai M. Shibasaki M. J. Am. Chem. Soc.  2006,  128:  6312 
    Search in Google Scholar
  • 8d Fujimori I. Mita T. Maki K. Shiro M. Sato A. Furusho S. Kanai M. Shibasaki M. J. Am. Chem. Soc.  2006,  128:  16438 
    Search in Google Scholar
  • 8e Xu Y. Lin L. Kanai M. Matsunaga S. Shibasaki M. J. Am. Chem. Soc.  2011,  133:  5791 
    Search in Google Scholar
  • 9a Arai K. Lucarini S. Salter MS. Ohta K. Yamashita Y. Kobayashi S. J. Am. Chem. Soc.  2007,  129:  8103 
    Search in Google Scholar
  • 9b Yu R. Yamashita Y. Kobayashi S. Adv. Synth. Catal.  2009,  351:  147 
    Search in Google Scholar
  • 9c Seki K. Yu R. Yamazaki Y. Yamashita Y. Kobayashi S. Chem. Commun.  2009,  5722 
  • 10a Wu B. Gallucci JC. Parquette JR. RajanBabu TV. Angew. Chem. Int. Ed.  2009,  48:  1126 
    Search in Google Scholar
  • 10b Wu B. Parquette JR. RajanBabu TV. Science  2009,  326:  1662 
    Search in Google Scholar
  • 11a Rowland EB. Rowland GB. Rivera-Otero E. Antilla JC. J. Am. Chem. Soc.  2007,  129:  12084 
    Search in Google Scholar
  • 11b Larson SE. Baso JC. Li G. Antilla JC. Org. Lett.  2009,  11:  5186 
    Search in Google Scholar
  • 12a Della Sala G. Lattanzi A. Org. Lett.  2009,  11:  3330 
    Search in Google Scholar
  • 12b Lattanzi A. Della Sala G. Eur. J. Org. Chem.  2009,  1845 
  • 13a Luo Z.-B. Hou X.-L. Dai L.-X. Tetrahedron: Asymmetry  2007,  18:  443 
    Search in Google Scholar
  • 13b Wang Z. Sun X. Ye S. Wang W. Wang B. Wu J. Tetrahedron: Asymmetry  2008,  19:  964 
    Search in Google Scholar
  • 14a Slaman SM. Schwab RS. Alberto EE. Vargas J. Dornelles L. Rodrigues OED. Braga AL. Synlett  2011,  69 
  • 14b Ghorai MK. Tiwari DP. J. Org. Chem.  2010,  75:  6173 
    Search in Google Scholar
  • 14c Yadav LDS. Rai VK. Singh S. Singh P. Tetrahedron Lett.  2010,  51:  1657 
    Search in Google Scholar
  • 15 Peruncheralathan S. Teller H. Schneider C. Angew. Chem. Int. Ed.  2009,  48:  4849 
    Search in Google Scholar
  • 16a Peruncheralathan S. Henze M. Schneider C. Synlett  2007,  2289 
  • 16b Marti A. Richter L. Schneider C. Synlett  2011,  2513 
  • 17 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.:
  • 18a Evans DA. Murry JA. Von Matt P. Norcross RD. Miller SJ. Angew. Chem., Int. Ed. Engl.  1995,  34:  798. 
    Search in Google Scholar
  • 18b Usuda H. Kuramochi A. Kanai M. Shibasaki M. Org. Lett.  2004,  6:  4387 
    Search in Google Scholar
  • 18c Cochran BM. Michael FE. Org. Lett.  2008,  10:  329 
    Search in Google Scholar
1

Current address: National Institute of Science Education and Research, Bhubaneswar 751 005, India.