Download PDF
Synthesis 2010(5): 741-748  
DOI: 10.1055/s-0029-1218602
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

A Highly Versatile Octasubstituted Phthalocyanine Scaffold for ex post Chemical Diversification

Herwig J. Bertholda, Theo Schotten*b, Frank Hoffmanna, Joachim Thiema
a University of Hamburg, Department of Chemistry, Martin-Luther-King-Platz 6, 20146 Hamburg, Germany
b CAN GmbH, Grindelallee 117, 20146 Hamburg, Germany
Fax: +49(40)428385797; e-Mail: schotten@can-hamburg.de;
Further Information

Publication History

Received 11 September 2009
Publication Date:
11 December 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

The TBDPS protecting group was conveniently employed for the convergent synthesis of a highly soluble, fully protected octa-peripheral (op) substituted phthalocyanine (Pc). After facile deprotection, ex post modification of this full-fledged Pc scaffold by various linkers was successfully achieved. This strategy overcomes the downsides of widely established linear convergent approaches under harsh conditions, which are not only destructive to chemically sensitive substituents, but also detrimental to rapid diversification towards Pc libraries.

Key words

heterocycles - dendrimers - protecting groups - phthalocyanine - ex post diversification - divergent strategy

    References

  • 1a Lee H, Jung J, Deno T, and Ohwa M. inventors; WO  2008,095,801.  ; Chem. Abstr. 2008, 149, 269526
  • 1b Metz T, and Schaefer W. inventors; DE  102,007,033,191.  ; Chem. Abstr. 2009, 150, 170268
  • 2a Emmelius M. Pawlowski G. Vollmann HW. Angew. Chem., Int. Ed. Engl.  1989,  28:  1445 
    Google Scholar
  • 2b Roth K. Chem. Unserer Zeit  2007,  41:  334 
    Google Scholar
  • 3a McKeown NB. Phthalocyanine Materials: Synthesis, Structure and Function   Vol. 6:  Cambridge University Press; Cambridge UK: 1998. 
    Google Scholar
  • 3b Leznoff CC. Lever ABP. Phthalocyanines: Properties and Applications   Vol. 1-4:  VCH; New York: 1989-1996. 
    Google Scholar
  • 4 Juríček M. Kouwer PHJ. Rehák J. Sly J. Rowan AE. J. Org. Chem.  2009,  74:  21 
    CrossrefGoogle Scholar
  • 5a Savage PB. Gellman SH. J. Am. Chem. Soc.  1993,  115:  10448 
    Google Scholar
  • 5b Corey EJ. Venkateswarlu A. J. Am. Chem. Soc.  1972,  94:  6190 
    Google Scholar
  • 5c Farooq O. Synthesis  1994,  1035 
    Google Scholar
  • 5d McKillop A. Kemp D. Tetrahedron  1989,  45:  3299 
    Google Scholar
  • 5e Woehrle D. Eskes M. Shigehara K. Yamada A. Synthesis  1993,  194 
    Google Scholar
  • 6 Overman LE. Okazaki ME. Mishra P. Tetrahedron Lett.  1986,  27:  4391 
    CrossrefGoogle Scholar
  • 7 Uchida H. Yoshiyama H. Reddy PY. Nakamura S. Toru T. Synlett  2003,  2083 
    Article in Thieme ConnectGoogle Scholar
  • 8a Liu W. Jensen TJ. Fronczek FR. Hammer RP. Smith KM. Vicente MGH. J. Med. Chem.  2005,  48:  1033 
    Google Scholar
  • 8b Kobayashi T. Uyeda N. Suito E. J. Phys. Chem.  1968,  72:  2446 
    Google Scholar
  • 8c Stillman MJ. Thomson AJ. J. Chem. Soc., Faraday Trans. 2  1974,  805 
    Google Scholar
  • 9 Hassan BM. Li H. McKeown NB. J. Mater. Chem.  2000,  10:  39 
    CrossrefGoogle Scholar
  • 10 Wang H. Sun L. Glazebnik S. Zhao K. Tetrahedron Lett.  1995,  36:  2953 
    CrossrefGoogle Scholar
  • 11 Bock VD. Hiemstra H. Maarseveen JH. Eur. J. Org. Chem.  2006,  51 
    Google Scholar
  • 12a Bertozzi CR, Agard NJ, Prescher JA, Baskin JM, and Sletten EM. inventors; US  2009,068,738.  ; Chem. Abstr. 2009, 150, 330128
  • 12b Sletten EM. Bertozzi CR. Org. Lett.  2008,  10:  3097 
    Google Scholar
  • 14a Plusquellec D. Lefeuvre M. Tetrahedron Lett.  1987,  28:  4165 
    Google Scholar
  • 14b Lin TS. Antonini I. Cosby LA. Sartorelli AC. J. Med. Chem.  1984,  27:  813 
    Google Scholar
  • 14c Duggan ME. Imagire JS. Synthesis  1989,  131 
    Google Scholar
13

Alternatively, the axial ligand of 12 might be interpreted as H2O. However, there are two indications that the axial ligand is NH3: 1. The distance is in accordance with a typical Zn-N bond in such compounds, 2. calculation of both structural models resulted in the smaller R value for NH3.