Download PDF
Synthesis 2008(20): 3331-3350  
DOI: 10.1055/s-0028-1083158
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

Enantioselective Iridium-Catalyzed Allylic Aminations of Allylic Carbonates with Functionalized Side Chains. Asymmetric Total Synthesis of (S)-Vigabatrin

Christian Gnamm, Géraldine Franck, Nicole Miller, Timon Stork, Kerstin Brödner, Günter Helmchen*
Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Fax: +49(6221)544205 ; e-Mail: g.helmchen@oci.uni-heidelberg.de ;
Further Information

Publication History

Received 10 April 2008
Publication Date:
25 September 2008 (online)

    Permissions and Reprints All articles of this category

Abstract

Iridium-catalyzed aminations of allylic carbonates containing a variety of O-functional groups have been explored. High degrees of regio- as well as enantioselectivity were achieved with diacylamides under salt-free conditions and with arylamines. The results allowed the antiepilepsy drug (S)-vigabatrin to be prepared via a very short route.

Key words

aminations - iridium - asymmetric catalysis - nucleophiles - regioselectivity

    References

  • 1a Trost BM. Lee C. In Catalytic Asymmetric Synthesis   2nd ed.:  Ojima I. Wiley-VCH; New York: 2000.  p.593 
    Google Scholar
  • 1b Pfaltz A. Lautens M. In Comprehensive Asymmetric Catalysis I-III   Jacobsen EN. Pfaltz A. Yamamoto H. Springer; Berlin: 1999.  p.833 
    Google Scholar
  • 2a Dai L.-X. Tu T. You S.-L. Deng W.-P. Hou X.-L. Acc. Chem. Res.  2003,  36:  659 
    Google Scholar
  • 2b Trost BM. Jiang C. Org. Lett.  2003,  5:  1563 ; and literature cited
    Google Scholar
  • 2c Johns AM. Liu Z. Hartwig JF. Angew. Chem. Int. Ed.  2007,  46:  7259 
    Google Scholar
  • Reviews:
  • 3a Helmchen G. Dahnz A. Dübon P. Schelwies M. Weihofen R. Chem. Commun.  2007,  675 
    Google Scholar
  • 3b Takeuchi R. Kezuka S. Synthesis  2006,  3349 
    Google Scholar
  • 3c Miyabe H. Takemoto Y. Synlett  2005,  1641 
    Google Scholar
  • 4a Feringa BL. Acc. Chem. Res.  2000,  33:  346 
    Google Scholar
  • 4b Tissot-Croset K. Polet D. Gille S. Hawner C. Alexakis A. Synthesis  2004,  2586 
    Google Scholar
  • 5a Bartels B. Helmchen G. Chem. Commun.  1999,  741 
    Google Scholar
  • 5b Bartels B. Garcia-Yebra C. Helmchen G. Eur. J. Org. Chem.  2003,  1097 
    Google Scholar
  • 5c Lipowsky G. Miller N. Helmchen G. Angew. Chem. Int. Ed.  2004,  43:  4595 ; Angew. Chem. 2004, 116, 4695
    Google Scholar
  • 5d Streiff S. Welter C. Schelwies M. Lipowsky G. Miller N. Helmchen G. Chem. Commun.  2005,  2957 
    Google Scholar
  • 5e Polet D. Alexakis A. Tissot-Croset K. Corminboeuf C. Ditrich K. Chem.-Eur. J.  2006,  12:  3596 ; and literature cited
    Google Scholar
  • 5f Kanayama T. Yoshida K. Miyabe H. Takemoto Y. Angew. Chem. Int. Ed.  2003,  42:  2054 ; Angew. Chem. 2003, 115, 2100
    Google Scholar
  • 6a Ohmura T. Hartwig JF. J. Am. Chem. Soc.  2002,  124:  15164 
    Google Scholar
  • 6b Kiener CA. Shu C. Incarvito C. Hartwig JF. J. Am. Chem. Soc.  2003,  125:  14272 
    Google Scholar
  • 6c Lipowsky G. Helmchen G. Chem. Commun.  2004,  116 
    Google Scholar
  • 6d Welter C. Koch O. Lipowsky G. Helmchen G. Chem. Commun.  2004,  896 
    Google Scholar
  • 6e Welter C. Dahnz A. Brunner B. Streiff S. Dübon P. Helmchen G. Org. Lett.  2005,  7:  1239 
    Google Scholar
  • 6f Leitner A. Shu C. Hartwig JF. Org. Lett.  2005,  7:  1093 
    Google Scholar
  • 6g Polet D. Alexakis A. Org. Lett.  2005,  7:  1621 
    Google Scholar
  • 6h Welter C. Moreno RM. Streiff S. Helmchen G. Org. Biomol. Chem.  2005,  3:  3266 
    Google Scholar
  • 6i

    See ref. 3c.

  • 7a Shu C. Leitner A. Hartwig JF. Angew. Chem. Int. Ed.  2004,  43:  4797 ; Angew. Chem. 2004, 116, 4901
    Google Scholar
  • 7b Leitner A. Shekhar S. Pouy MJ. Hartwig JF. J. Am. Chem. Soc.  2005,  127:  1239 
    Google Scholar
  • 8a Weihofen R. Tverskoy O. Helmchen G. Angew. Chem. Int. Ed.  2006,  45:  5546 ; Angew. Chem. 2006, 118, 5673
    Google Scholar
  • 8b Weihofen R. Dahnz A. Tverskoy O. Helmchen G. Chem. Commun.  2005,  3541 
    Google Scholar
  • 8c Spiess S. Berthold C. Weihofen R. Helmchen G. Org. Biomol. Chem.  2007,  5:  2357 
    Google Scholar
  • 8d Singh OV. Han H. Tetrahedron Lett.  2007,  48:  7094 
    Google Scholar
  • 9a Lopéz F. Ohmura T. Hartwig JF. J. Am. Chem. Soc.  2003,  125:  3426 
    Google Scholar
  • 9b Ueno S. Hartwig JF. Angew. Chem. Int. Ed.  2008,  47:  1928 ; Angew. Chem. 2008, 120, 1954
    Google Scholar
  • 9c Miyabe H. Yoshida K. Yamauchi M. Takemoto Y. J. Org. Chem.  2005,  70:  2148 
    Google Scholar
  • 9d Lyothier I. Defieber C. Carreira EM. Angew. Chem. Int. Ed.  2006,  45:  6204 ; Angew. Chem. 2006, 118, 6350
    Google Scholar
  • Reviews:
  • 10a Trost BM. J. Org. Chem.  2004,  69:  5813 
    Google Scholar
  • 10b Trost BM. Fandrick DR. Aldrichimica Acta  2007,  40:  59 
    Google Scholar
  • We found deprotection of phthalimide derivatives with 1,2-diaminoethane particularly effective:
  • 11a Kanie O. Crawley SC. Palcie MM. Hindsgaul O. Carbohydr. Res.  1993,  243:  139 
    Google Scholar
  • Deprotection of nitrobenzene-sulfonylamides:
  • 11b Fukuyama T. Jow CK. Cheung M. Tetrahedron Lett.  1995,  36:  6373 
    Google Scholar
  • 11c Fukuyama T. Cheung M. Jow CK. Hidai Y. Kan T. Tetrahedron Lett.  1997,  38:  5831 
    Google Scholar
  • 12 Characterization of this compound see the supplementary information in: Berkowitz DB. Bose M. Choi S. Angew. Chem. Int. Ed.  2002,  41:  1603 ; Angew. Chem. 2002, 114, 1673
    CrossrefPubMedGoogle Scholar
  • 13 Trost BM. Bunt RC. Lemoine RC. Calkins TL. J. Am. Chem. Soc.  2000,  122:  5968 
    CrossrefGoogle Scholar
  • 14a Kwon TW. Keusenkothen PF. Smith MB. J. Org. Chem.  1992,  57:  6169 
    Google Scholar
  • 14b Wey ZY. Knaus EE. Tetrahedron  1994,  50:  5569 
    Google Scholar
  • 14c Alcon M. Poch M. Moyano A. Pericas MA. Riera A. Tetrahedron: Asymmetry  1997,  8:  2967 
    Google Scholar
  • 14d Overman LE. Anderson CE. J. Am. Chem. Soc.  2003,  125:  12412 
    Google Scholar
  • 15 Fernández-Rivas C. Méndez M. Nieto-Oberhuber C. Echavarren AM. J. Org. Chem.  2002,  67:  5197 
    CrossrefGoogle Scholar
  • 16a Krapcho AP. Synthesis  1982,  805 
    Google Scholar
  • 16b Krapcho AP. Synthesis  1982,  893 
    Google Scholar
  • 16c Dahnz A. Helmchen G. Synlett  2006,  697 
    Google Scholar
  • 17a Marshall JA. Garofalo AW. J. Org. Chem.  1996,  61:  8732 
    Google Scholar
  • 17b Roush WR. Straub JA. VanNieuwenhze MS. J. Org. Chem.  1991,  56:  1636 
    Google Scholar
  • 18 Hernández AI. Balzarini J. Karlsson A. Camarasa MJ. Pérez-Pérez MJ. J. Med. Chem.  2002,  45:  4254 
    CrossrefGoogle Scholar
  • 19 Organ MG. Cooper JT. Rogers LR. Soleymanzadeh F. Paul T. J. Org. Chem.  2000,  65:  7959 
    CrossrefGoogle Scholar
  • 20 Mulzer J. Berger M. J. Org. Chem.  2004,  69:  891 
    CrossrefPubMedGoogle Scholar
  • 21 Thurner A. Faigl F. Töke L. Mordini A. Valacchi M. Reginato G. Czira G. Tetrahedron  2001,  57:  8173 
    CrossrefGoogle Scholar
  • 22 Massacret M. Lakhmiri R. Lhoste P. Nguefack C. Abdelouahab FB. Fadel R. Sinou D. Tetrahedron: Asymmetry  2000,  11:  3561 
    CrossrefGoogle Scholar
  • 23 Cerezo S. Cortés J. López-Romero JM. Moreno-Mañas M. Parella T. Pleixats R. Roglans A. Tetrahedron  1998,  54:  14885 
    CrossrefGoogle Scholar
  • 24 Amine (-)-(R)-3a was previously described, of the physical properties only the optical rotation was reported: [α]D -26.6 (c 0.98, CHCl3): Campbell AD. Raynham TM. Taylor RJK. J. Chem. Soc., Perkin Trans. 1  2000,  3194 
    CrossrefGoogle Scholar
  • 26 Ohfune Y. Kurokawa N. Tetrahedron Lett.  1984,  25:  1071 
    CrossrefGoogle Scholar
  • 27 Fernández I. Muñoz L. Tetrahedron: Asymmetry  2006,  17:  2548 
    CrossrefGoogle Scholar
  • 28 Haidoune M. Mornet R. J. Heterocycl. Chem.  1994,  31:  1461 
    CrossrefGoogle Scholar
25

Gnamm, C.; Helmchen, G. unpublished results.