Download PDF
Synthesis 2010(15): 2670-2678  
DOI: 10.1055/s-0029-1218845
PSP
© Georg Thieme Verlag Stuttgart ˙ New York

Efficient Preparation of Polyfunctional Organometallics via Directed ortho-Metalation

Stefan H. Wunderlich, Tomke Bresser, Cora Dunst, Gabriel Monzon, Paul Knochel*
Ludwig-Maximilians-Universität München, Department Chemie und Biochemie, Butenandtstr. 5-13, Haus F, 81377 München, Germany
Fax: +49(89)218077680; e-Mail: paul.knochel@cup.uni-muenchen.de;
Further Information

Publication History

Received 22 April 2010
Publication Date:
29 June 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

Highly functionalized organometallics are efficiently prepared in larger quantities (up to 4 g) by directed ortho-metalation using the previously reported amide bases TMP2Mn˙2MgCl2˙4LiCl (TMP = 2,2,6,6-tetramethylpiperidyl), TMP2Fe˙2MgCl2˙4LiCl and TMP3La˙3MgCl2˙5LiCl. The resulting organometallics undergo various reactions with electrophiles like acid chlorides, alkyl iodides, or aldehydes and provide the corresponding products in good to excellent yields.

Key words

directed metalation - organometallics - metal amides - catalysis - LiCl

    References

  • 1a Snieckus V. Chem. Rev.  1990,  90:  879 
    Google Scholar
  • 1b Whisler MC. MacNeil S. Beak P. Snieckus V. Angew. Chem. Int. Ed.  2004,  43:  2206 
    Google Scholar
  • 1c Schlosser M. Angew. Chem. Int. Ed.  2005,  44:  376 
    Google Scholar
  • 1d Turck A. Plé N. Mongin F. Quéguiner G. Tetrahedron  2001,  57:  4489 
    Google Scholar
  • 1e Mongin F. Quéguiner G. Tetrahedron  2001,  57:  4059 
    Google Scholar
  • 1f Leroux F. Jeschke P. Schlosser M. Chem. Rev.  2005,  105:  827 
    Google Scholar
  • 1g Chinchilla R. Nájera C. Yus M. Chem. Rev.  2004,  104:  2667 
    Google Scholar
  • 2a Naka H. Uchiyama M. Matsumoto Y. Wheatley AEH. McPartlin M. Morey JV. Kondo Y. J. Am. Chem. Soc.  2007,  129:  1921 
    Google Scholar
  • 2b Mulvey RE. Mongin F. Uchiyama M. Kondo Y. Angew. Chem. Int. Ed.  2007,  46:  3802 
    Google Scholar
  • 2c Naka H. Morey JV. Haywood J. Eisler DJ. McPartlin M. Garcia F. Kudo H. Kondo Y. Uchiyama M. Wheatley AEH. J. Am. Chem. Soc.  2008,  130:  16193 
    Google Scholar
  • 2d Uchiyama M. Kobayashi Y. Furuyama T. Nakamura S. Kajihara Z. Miyoshi T. Sakamoto T. Kondo Y. Morokuma K. J. Am. Chem. Soc.  2008,  130:  472 
    Google Scholar
  • 2e Usui S. Hashimoto Y. Morey JV. Wheatley AEH. Uchiyama M. J. Am. Chem. Soc.  2007,  129:  15102 
    Google Scholar
  • 2f Chevallier F. Mongin F. Chem. Soc. Rev.  2008,  37:  595 
    Google Scholar
  • 2g Seggio A. Chevallier F. Vaultier M. Mongin F. J. Org. Chem.  2007,  72:  6602 
    Google Scholar
  • 2h L’Helgoual’ch J.-M. Seggio A. Chevallier F. Yonehara M. Jeanneau E. Uchiyama M. Mongin F. J. Org. Chem.  2008,  73:  177 
    Google Scholar
  • 2i Clegg W. Dale SH. Hevia E. Hogg LM. Honeyman GW. Mulvey RE. O’Hara CT. Russo L. Angew. Chem. Int. Ed.  2008,  47:  731 
    Google Scholar
  • 2j Alborés P. Carrella L. Clegg W. García-Álvarez P. Kennedy AR. Klett J. Mulvey RE. Rentschler E. Russo L. Angew. Chem. Int. Ed.  2009,  48:  3317 
    Google Scholar
  • 2k Mulvey RE. Acc. Chem. Res.  2009,  42:  743 
    Google Scholar
  • 2l Carrella LM. Clegg W. Graham DV. Hogg LM. Kennedy AR. Klett J. Mulvey RE. Rentschler E. Russo L. Angew. Chem. Int. Ed.  2007,  46:  4662 
    Google Scholar
  • 2m Blair VL. Clegg W. Conway B. Hevia E. Kennedy A. Klett J. Mulvey RE. Russo L. Chem. Eur. J.  2008,  14:  65 
    Google Scholar
  • 2n Blair VL. Carrella LM. Clegg W. Conway B. Harrington RW. Hogg LM. Klett J. Mulvey RE. Rentschler E. Russo L. Angew. Chem. Int. Ed.  2008,  47:  6208 
    Google Scholar
  • 2o Blair VL. Carrella LM. Clegg W. Klett J. Mulvey RE. Rentschler E. Russo L. Chem. Eur. J.  2009,  15:  856 
    Google Scholar
  • 3a Krasovskiy A. Krasovskaya V. Knochel P. Angew. Chem. Int. Ed.  2006,  45:  2958 
    Google Scholar
  • 3b Lin W. Baron O. Knochel P. Org. Lett.  2006,  8:  5673 
    Google Scholar
  • 3c Boudet N. Lachs JR. Knochel P. Org. Lett.  2007,  9:  5525 
    Google Scholar
  • 3d Boudet N. Dubbaka SR. Knochel P. Org. Lett.  2008,  10:  1715 
    Google Scholar
  • 3e Stoll AH. Knochel P. Org. Lett.  2008,  10:  113 
    Google Scholar
  • 3f Mosrin M. Knochel P. Org. Lett.  2008,  10:  2497 
    Google Scholar
  • 4a Wunderlich SH. Knochel P. Angew. Chem. Int. Ed.  2007,  46:  7685 
    Google Scholar
  • 4b Wunderlich SH. Knochel P. Org. Lett.  2008,  10:  4705 
    Google Scholar
  • 4c Wunderlich SH. Knochel P. Chem. Commun.  2008,  6387 
    Google Scholar
  • 5 Wunderlich SH. Kienle M. Knochel P. Angew. Chem. Int. Ed.  2009,  48:  7256 
    CrossrefPubMedGoogle Scholar
  • 6 Wunderlich SH. Knochel P. Angew. Chem. Int. Ed.  2009,  48:  9717 
    CrossrefPubMedGoogle Scholar
  • 7 Wunderlich SH. Knochel P. Chem. Eur. J.  2010,  16:  3304 
    CrossrefGoogle Scholar
  • 8 Solinas I. Lutz HD. J. Solid State Chem.  1995,  117:  34 
    CrossrefGoogle Scholar
  • 9a Krasovskiy A. Kopp F. Knochel P. Angew. Chem. Int. Ed.  2006,  45:  497 
    Google Scholar
  • 9b Metzger A. Gavryushin A. Knochel P. Synlett  2009,  1433 
    Google Scholar
  • 10a Knochel P. Yeh MCP. Berk SC. Talbert J. J. Org. Chem.  1988,  53:  2390 
    Google Scholar
  • 10b Knochel P. Rao SA. J. Am. Chem. Soc.  1990,  112:  6146 
    Google Scholar
  • 11a Devasagayaraj A. Stüdemann T. Knochel P. Angew. Chem. Int. Ed.  1995,  34:  2723 
    Google Scholar
  • 11b Giovannini R. Stüdemann T. Dussin G. Knochel P. Angew. Chem. Int. Ed.  1998,  37:  2387 
    Google Scholar
  • 11c Giovannini R. Stüdemann T. Devasagayaraj A. Dussin G. Knochel P. J. Org. Chem.  1999,  64:  3544 
    Google Scholar
  • 11d Jensen AE. Knochel P. J. Org. Chem.  2002,  67:  79 
    Google Scholar
  • 11e Korn TJ. Knochel P. Angew. Chem. Int. Ed.  2005,  44:  2947 
    Google Scholar