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Synthesis 2009(22): 3860-3868  
DOI: 10.1055/s-0029-1217012
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

N-Substitution Reactions of 20-π-Electron β-Tetrakis(trifluoromethyl)-meso-tetraphenylporphyrin

Xiao-Guang Chen, Chao Liu, Dong-Mei Shen, Qing-Yun Chen*
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, 200032 Shanghai, P. R. of China
Fax: +86(21)64166128; e-Mail: chenqy@mail.sioc.ac.cn;
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Publication History

Received 23 June 2009
Publication Date:
23 September 2009 (online)

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Abstract

The N-substitution reactions of 20-π-electron β-tetrakis(trifluoromethyl)-meso-tetraphenylporphyrin 2 with α,ω-dibromoalkanes in N,N-dimethylformamide at room temperature in the presence of various bases gave a variety of N-substituted isophlorins, the nature of which depended on the chain length of α,ω-dibromoalkanes and the reaction conditions. When 1,4-dibromobutane was used, a fascinating N,N′-bridged isophlorin 14 was obtained. In the case of 1,3-dibromopropane or 1,5-dibromopentane, N-monoalkylated or N,N′-dialkylated isophlorins were produced under similar conditions. The reactions of these N-alkylated isophlorins with activated zinc powder were complicated and reduction, hydrolysis, elimination, and intramolecular cyclization were all observed.

Key words

isophlorin - substitutions - porphyrins - cyclizations

    References

  • 1 Liu C. Shen DM. Chen QY. J. Am. Chem. Soc.  2007,  129:  5814 
    CrossrefGoogle Scholar
  • 2 Setsune J. Kashihara K. Wada K. Shiozaki H. Chem. Lett.  1999,  847 
    CrossrefGoogle Scholar
  • 3a Pohl M. Schmickler H. Lex J. Vogel E. Angew. Chem., Int. Ed. Engl.  1991,  30:  1693 
    Google Scholar
  • 3b Bachmann R. Gerson F. Gescheidt G. Vogel E. J. Am. Chem. Soc.  1992,  114:  10855 
    Google Scholar
  • 3c Vogel E. Pohl M. Herrmann A. Wiss T. König C. Lex J. Gross M. Gisselbrecht JP. Angew. Chem., Int. Ed. Engl.  1996,  35:  1520 
    Google Scholar
  • 3d Vogel E. Grigat I. Köcher M. Lex J. Angew. Chem., Int. Ed. Engl.  1989,  28:  1655 
    Google Scholar
  • 4 Matano Y. Nakabuchi T. Fujishige S. Nakano H. Imahori H. J. Am. Chem. Soc.  2008,  130:  16446 
    CrossrefGoogle Scholar
  • 5 Reddy JS. Anand VG. J. Am. Chem. Soc.  2008,  130:  3718 
    CrossrefGoogle Scholar
  • 6 Weiss A. Hodgson MC. Boyd PDW. Siebert W. Brothers PJ. Chem. Eur. J.  2007,  13:  5982 
    CrossrefGoogle Scholar
  • 7 Matsuo T. Ito K. Kanehisa N. Hayashi T. Org. Lett.  2007,  9:  5303 
    CrossrefGoogle Scholar
  • 8a Cissell JA. Vaid TP. Yap GPA. J. Am. Chem. Soc.  2007,  129:  7841 
    Google Scholar
  • 8b Song H. E. Cissell JA. Vaid TP. Holten D. J. Phys. Chem. B  2007,  111:  2138 
    Google Scholar
  • 8c Cissell JA. Vaid TP. Yap GPA. Org. Lett.  2006,  8:  2401 
    Google Scholar
  • 8d Cissell JA. Vaid TP. Rheingold AL. Inorg. Chem.  2006,  45:  2367 
    Google Scholar
  • 8e Cissell JA. Vaid TP. Rheingold AL. J. Am. Chem. Soc.  2005,  127:  12212 
    Google Scholar
  • 8f Cissell JA. Vaid TP. DiPasquale AG. Rheingold AL. Inorg. Chem.  2007,  46:  7713 
    Google Scholar
  • 9 Yamamoto Y. Yamamoto A. Furuta SY. Horie M. Kodama M. Sato W. Akiba KY. Tsuzuki S. Uchimaru T. Hashizume D. Iwasaki F. J. Am. Chem. Soc.  2005,  127, 14540 
    Google Scholar
  • 10a Shen DM. Liu C. Chen XG. Chen QY. J. Org. Chem.  2009,  74:  206 
    Google Scholar
  • 10b Shen DM. Liu C. Chen QY. Synlett  2009,  945 
    Google Scholar
  • 10c Jin LM. Chen L. Yin JJ. Guo C. C. Chen QY. Eur. J. Org. Chem.  2005,  3994 
    Google Scholar
  • 10d Jin LM. Yin JJ. Chen L. Guo C. C. Chen QY. Synlett  2005,  2893 
    Google Scholar
  • 11 Shen DM. Liu C. Chen QY. Chem. Commun.  2005,  4982 
    CrossrefGoogle Scholar