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Synthesis 2004(15): 2555-2559  
DOI: 10.1055/s-2004-831199
PAPER
© Georg Thieme Verlag Stuttgart · New York

Lithiation of a Pyrrolo-Annulated Tetrathiafulvalene

Bo M. Petersen, Jan O. Jeppesen*, Jan Becher
Department of Chemistry, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark
Fax: +45(66)158780; e-Mail: joj@chem.sdu.dk;
Further Information

Publication History

Received 3 June 2004
Publication Date:
26 August 2004 (online)

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Abstract

Mono- and bis-lithiations of N-tosyl monopyrrolo­tetrathiafulvalene provide novel methods for the introduction of substituents, such as alkyl and halogens, into the 4- and 6-positions of monopyrrolotetrathiafulvalenes.

Key words

carbanions - halogenation - organometallic - pyrrole - tetrathiafulvalene

    References

  • For recent reviews; see:
  • 1a Bryce MR. Adv. Mater.  1999,  11:  11 
    CrossrefPubMedGoogle Scholar
  • 1b Nielsen MB. Lomholt C. Becher J. Chem. Soc. Rev.  2000,  29:  153 
    CrossrefPubMedGoogle Scholar
  • 1c Segura JL. Martín N. Angew. Chem. Int. Ed.  2001,  40:  1372 
    CrossrefPubMedGoogle Scholar
  • 1d Jeppesen JO. Becher J. Eur. J. Org. Chem.  2003,  3245 
    CrossrefPubMedGoogle Scholar
  • 1e Schukat G. Fanghänel E. Sulfur Rep.  2003,  24:  1 
    CrossrefPubMedGoogle Scholar
  • 1f Otsubo T. Takimiya K. Bull. Chem. Soc. Jpn.  2004,  77:  43 
    CrossrefPubMedGoogle Scholar
  • 3a Liu HL. Liu S. Echegoyen L. Chem. Commun.  1999,  1493 
    CrossrefGoogle Scholar
  • 3b Bryce MR. Batsanov AS. Finn T. Hansen TK. Howard JAK. Kamenjicki M. Lednev IK. Asher SA. Chem. Commun.  2000,  295 
    CrossrefGoogle Scholar
  • 3c Le Derf F. Mazari M. Mercier N. Levillain E. Trippé G. Riou A. Richomme P. Becher J. Garin J. Orduna J. Gallego-Planas N. Gorgues A. Sallé M. Chem. Eur. J.  2001,  7:  447 
    CrossrefGoogle Scholar
  • 3d Trippé G. Levillain E. Le Derf F. Gorgues A. Sallé M. Jeppesen JO. Nielsen K. Becher J. Org. Lett.  2002,  4:  2461 
    CrossrefGoogle Scholar
  • 3e Nielsen KA. Jeppesen JO. Levillain E. Becher J. Angew. Chem. Int. Ed.  2003,  42:  187 
    CrossrefGoogle Scholar
  • 4a Baguley PA. Walton JC. Angew. Chem. Int. Ed.  1998,  37:  3072 
    CrossrefGoogle Scholar
  • 4b Fletcher RJ. Lampard C. Murphy JA. Lewis N. J. Chem. Soc., Perkin Trans. 1  1995,  623 
    CrossrefGoogle Scholar
  • 4c Lampard C. Murphy JA. Lewis N. J. Chem. Soc., Chem. Commun.  1993,  295 
    CrossrefGoogle Scholar
  • 5a Asakawa M. Ashton PR. Balzani V. Credi A. Hamers C. Mattersteig G. Montalti M. Shipway AN. Spencer N. Stoddart JF. Tolley MS. Venturi M. White AJP. Williams DJ. Angew. Chem. Int. Ed.  1998,  37:  333 
    CrossrefGoogle Scholar
  • 5b Balzani V. Credi A. Mattersteig G. Matthews OA. Raymo FM. Stoddart JF. Venturi M. White AJP. Williams DJ. J. Org. Chem.  2000,  65:  1924 
    CrossrefGoogle Scholar
  • 5c Farren C. Christensen CA. FitzGerald S. Bryce MR. Beeby A. J. Org. Chem.  2002,  67:  9130 
    CrossrefGoogle Scholar
  • 5d Li H. Jeppesen JO. Levillain E. Becher J. Chem. Commun.  2003,  846 
    CrossrefGoogle Scholar
  • 5e Tseng H.-R. Vignon SA. Stoddart JF. Angew. Chem. Int. Ed.  2003,  42:  1491 
    CrossrefGoogle Scholar
  • 5f Tseng H.-R. Vignon SA. Celestre PC. Perkins J. Jeppesen JO. Di Fabio A. Ballardini R. Gandolfi MT. Venturi M. Balzani V. Stoddart JF. Chem. Eur. J.  2004,  10:  155 
    CrossrefGoogle Scholar
  • 5g Kang S. Vignon SA. Tseng H.-R. Stoddart JF. Chem. Eur. J.  2004,  10:  2555 
    CrossrefGoogle Scholar
  • 6a Collier CP. Mattersteig G. Wong EW. Lou Y. Beverly K. Sampaio J. Raymo FM. Stoddart JF. Heath JR. Science  2000,  289:  1172 
    CrossrefGoogle Scholar
  • 6b Pease AR. Jeppesen JO. Stoddart JF. Luo Y. Collier CP. Heath JR. Acc. Chem. Res.  2001,  34:  433 
    CrossrefGoogle Scholar
  • 6c Collier CP. Jeppesen JO. Luo Y. Perkins J. Wong EW. Heath JR. Stoddart JF. J. Am. Chem. Soc.  2001,  123:  12632 
    CrossrefGoogle Scholar
  • 6d Luo Y. Collier CP. Jeppesen JO. Nielsen KA. Delonno E. Ho G. Perkins J. Tseng H.-R. Yamamoto T. Stoddart JF. Heath JR. ChemPhysChem  2002,  3:  519 
    CrossrefGoogle Scholar
  • 6e Chen Y. Ohlberg DAA. Li X. Stewart DR. Williams RS. Jeppesen JO. Nielsen KA. Stoddart JF. Olynick DL. Anderson E. Appl. Phys. Lett.  2003,  82:  1610 
    CrossrefGoogle Scholar
  • 6f Chen Y. Jung G.-Y. Ohlberg DAA. Li X. Stewart DR. Jeppesen JO. Nielsen KA. Stoddart JF. Williams RS. Nanotechnology  2003,  14:  462 
    CrossrefGoogle Scholar
  • 6g Stewart DR. Ohlberg DAA. Beck P. Chen Y. Williams RS. Jeppesen JO. Nielsen KA. Stoddart JF. Nano Lett.  2004,  4:  133 
    CrossrefGoogle Scholar
  • 6h Tseng H.-R. Wu D. Fang NX. Zhang X. Stoddart JF. ChemPhysChem  2004,  5:  111 
    CrossrefGoogle Scholar
  • 7a Jeppesen JO. Takimiya K. Jensen F. Becher J. Org. Lett.  1999,  1:  1291 
    CrossrefGoogle Scholar
  • 7b Jeppesen JO. Takimiya K. Jensen F. Brimert T. Nielsen K. Thorup N. Becher J. J. Org. Chem.  2000,  65:  5794 
    CrossrefGoogle Scholar
  • 8 Nielsen K. Jeppesen JO. Thorup N. Becher J. Org. Lett.  2002,  4:  1327 
    CrossrefGoogle Scholar
  • 9 Nielsen K. Jeppesen JO. Levillain E. Thorup N. Becher J. Org. Lett.  2002,  4:  4189 
    CrossrefGoogle Scholar
  • 10a Jeppesen JO. Perkins J. Becher J. Stoddart JF. Org. Lett.  2000,  2:  3547 
    CrossrefGoogle Scholar
  • 10b Jeppesen JO. Perkins J. Becher J. Stoddart JF. Angew. Chem. Int. Ed.  2001,  40:  1216 
    CrossrefGoogle Scholar
  • 10c Jeppesen JO. Nielsen KA. Perkins J. Vignon SA. Di Fabio A. Ballardini R. Gandolfi MT. Venturi N. Balzani V. Becher J. Stoddart JF. Chem. Eur. J.  2003,  9:  2982 
    CrossrefGoogle Scholar
  • 10d Jeppesen JO. Vignon SA. Stoddart JF. Chem. Eur. J.  2003,  9:  4611 
    CrossrefGoogle Scholar
  • 11 Becher J. Brimert T. Jeppesen JO. Pedersen JZ. Zubarev R. Bjørnholm T. Reitzel N. Jensen TR. Kjaer K. Levillain E. Angew. Chem. Int. Ed.  2001,  40:  2497 
    CrossrefGoogle Scholar
  • 12 Bird CW. Comprehensive Heterocyclic Chemistry II   Vol. 2:  Katritzky AR. Rees CW. Scriven EFV. Pergamon; Oxford: 1996.  p.1-257 
    Google Scholar
  • 13a Hasan I. Marinelli ER. Lin L.-CC. Fowler FW. Levy AB. J. Org. Chem.  1981,  46:  157 
    CrossrefGoogle Scholar
  • 13b Groenendaal L. van Loo ME. Vekemans JAJM. Meijer EW. Synth. Commun.  1995,  25:  1589 
    CrossrefGoogle Scholar
  • 15 Groenendaal L. Meijer EW. Vekemans JAJM. Electronic Materials: The Oligomeric Approach   Chap. 3:  Wegner G. Müllen K. VCH; Weinheim: 1996. 
    Google Scholar
  • 16 Hansen JA. Becher J. Jeppesen JO. Levillain E. Nielsen MB. Petersen BM. Conrad J. abin Y. J. Mater. Chem.  2004,  14:  179 
    CrossrefGoogle Scholar
  • 17 Burchat AF. Chong JM. Nielsen N. J. Organomet. Chem.  1997,  542:  281 
    CrossrefGoogle Scholar
  • 18 Perrin DD. Armarego WLF. Purification of Laboratory Chemicals   Pergamon; New York: 1988. 
    Google Scholar
  • 19 Gottlieb HH. Kotlyar V. Nudelman A. J. Org. Chem.  1997,  62:  7512 
    CrossrefPubMedGoogle Scholar
2

Jeppesen, J. O.; Nielsen, M. B.: Becher, J. Chem. Rev. 2004, in press.

14

Other lithium bases, such as n-BuLi and tert-BuLi were also tested. However, addition of n-BuLi or tert-BuLi to a solution of 3 caused detosylation producing the unprotected MPTTF derivative.13a

20

1H NMR spectroscopy revealed that the isolated product contained ca. 5% of 3.