Download PDF
Synlett 2010(18): 2808-2812  
DOI: 10.1055/s-0030-1258818
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Copper-Catalyzed Aerobic Oxidative Coupling of Aminocarbazoles and Aminoindoles: Synthesis of Diindolophenazines and Dipyrrolophenazines

Ramu Meesala, Rajagopal Nagarajan*
School of Chemistry, University of Hyderabad, Hyderabad 500046, India
Fax: +91(40)23012460; e-Mail: rnsc@uohyd.ernet.in;
Further Information

Publication History

Received 26 July 2010
Publication Date:
08 October 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

We have developed a simple method for the synthesis of diindolophenazine and dipyrrolophenazine derivatives by the aerobic oxidative coupling of 3-aminocarbazole and 2,3-dimethyl-5-aminoindole derivatives, respectively, in the presence of catalytic CuBr (10 mol%) in DMSO at 80 ˚C while open to air.

Key words

copper - aerobic oxidative coupling - 3-aminocarbazole - 2,3-dimethyl-5-aminoindole - diindolophenazine - dipyrrolophenazine

    References and Notes

  • 1a Alberico D. Scott ME. Lautens M. Chem. Rev.  2007,  107:  174 
    Google Scholar
  • 1b Godula K. Sames D. Science  2006,  312:  67 
    Google Scholar
  • 1c Kakiuchi F. Chatani N. Adv. Synth. Catal.  2003,  345:  1077 
    Google Scholar
  • 1d Ritleng V. Sirlin C. Pfeffer M. Chem. Rev.  2002,  102:  1731 
    Google Scholar
  • 1e Fumitoshi K. Takuya K. Synthesis  2008,  3013 
    Google Scholar
  • 1f Lewis JC. Bergman RG. Ellman JA. Acc. Chem. Res.  2008,  41:  1013 
    Google Scholar
  • 1g Ackermann L. Vicente R. Kapdi AR. Angew. Chem. Int. Ed.  2009,  48:  9792 
    Google Scholar
  • 2a Matsuura Y. Tamura M. Kochi T. Sato M. Chatani N. Kakiuchi F. J. Am. Chem. Soc.  2007,  129:  9858 
    Google Scholar
  • 2b Ackermann L. Althammer A. Born R. Angew. Chem. Int. Ed.  2006,  45:  2619 
    Google Scholar
  • 3a Stokes BJ. Dong H. Leslie BE. Pumphrey AL. Driver TG. J. Am. Chem. Soc.  2007,  129:  7500 
    Google Scholar
  • 3b Williams Fiori K. Du Bois J. J. Am. Chem. Soc.  2007,  129:  562 
    Google Scholar
  • 3c Ravisekhara PR. Davies HML. Org. Lett.  2006,  8:  5013 
    Google Scholar
  • 3d Nakamura E. Yoshikai M. J. Am. Chem. Soc.  2002,  124:  7181 
    Google Scholar
  • 4a Stuart DR. Villemure E. Fagnou K. J. Am. Chem. Soc.  2007,  129:  12072 
    Google Scholar
  • 4b Firmansjah L. Fu GC. J. Am. Chem. Soc.  2007,  129:  11340 
    Google Scholar
  • 4c Hull KL. Sanford MS. J. Am. Chem. Soc.  2007,  129:  11904 
    Google Scholar
  • 4d Yang S. Li B. Wan X. Shi Z. J. Am. Chem. Soc.  2007,  129:  6066 
    Google Scholar
  • 4e Inamoto K. Saito T. Katsuno M. Sakamoto T. Hiroya K. Org. Lett.  2007,  9:  2931 
    Google Scholar
  • 4f Delcamp JH. White MC. J. Am. Chem. Soc.  2006,  128:  15076 
    Google Scholar
  • 4g Knölker H.-J. O’Sullivan N. Tetrahedron  1994,  50:  10893 
    Google Scholar
  • 4h Knölker H.-J. Fröhner W. Reddy KR. Synthesis  2002,  557 
    Google Scholar
  • 4i Knölker H.-J. Fröhner W. J. Chem. Soc., Perkin Trans. 1  1998,  173 
    Google Scholar
  • 4j Knölker H.-J. Forke R. Jäger A. Org. Biomol. Chem.  2008,  6:  2481 
    Google Scholar
  • 4k Knölker H.-J. Gruner KK. Org. Biomol. Chem.  2008,  6:  3902 
    Google Scholar
  • 4l Knölker H.-J. Chem. Lett.  2009,  38:  8 
    Google Scholar
  • 4m Li JJ. Gribble GW. Palladium in Heterocyclic Chemistry   Pergamon; Amsterdam: 2000.  p.2-4  
    Google Scholar
  • 4n Li JJ. Gribble GW. Palladium in Heterocyclic Chemistry   Pergamon; Amsterdam: 2000.  p.83-84  
    Google Scholar
  • 5a Do H.-Q. Daugulis O. J. Am. Chem. Soc.  2007,  129:  12404 
    Google Scholar
  • 5b Chen X. Hao X.-S. Goodhue CE. Yu J.-Q. J. Am. Chem. Soc.  2006,  128:  6790 
    Google Scholar
  • 5c Do H.-Q. Daugulis O. J. Am. Chem. Soc.  2008,  130:  1128 
    Google Scholar
  • 5d Borduas N. Powell DA. J. Org. Chem.  2008,  73:  7822 
    Google Scholar
  • 5e Monguchi D. Fujiwara T. Furukawa H. Mori A. Org. Lett.  2009,  11:  1607 
    Google Scholar
  • 5f Zhao L. Li C.-J. Angew. Chem. Int. Ed.  2008,  47:  7075 
    Google Scholar
  • 5g Strieter ER. Bhayana B. Buchwald SL. J. Am Chem. Soc.  2009,  131:  78 
    Google Scholar
  • 5h Yotphan S. Bergman RG. Ellman JA. Org. Lett.  2009,  11:  1511 
    Google Scholar
  • 5i Ackermann L. Potukuchi HK. Landsberg D. Vicente R. Org. Lett.  2008,  10:  3081 
    Google Scholar
  • 5j Li C.-J. Acc. Chem. Res.  2009,  42:  335 
    Google Scholar
  • 5k Brasche G. Buchwald SL. Angew. Chem. Int. Ed.  2008,  47:  1932 
    Google Scholar
  • 6a Gribble GW. In The Alkaloids   Brossi A. Academic Press; San Diego: 1990.  p.239-352  
    Google Scholar
  • 6b Knölker H.-J. Reddy KR. Chem. Rev.  2002,  102:  4303 
    Google Scholar
  • 6c Knölker H.-J. Reddy KR. In The Alkaloids   65:  Cordell GA. Academic Press; Amsterdam: 2008.  p.1 
    Google Scholar
  • 6d Wakim S. Bouchard J. Blouin B. Michaud A. Leclerc M. Org. Lett.  2004,  6:  3413 
    Google Scholar
  • 7a Trost BA. Acc. Chem. Res.  2002,  35:  695 
    Google Scholar
  • 7b Sheldon RA. Arends IWCE. ten Brink GJ. Dijksman A. Acc. Chem. Res.  2002,  35:  774 
    Google Scholar
  • 7c Punniyamurthy T. Velusamy S. Iqbal J. Chem. Rev.  2005,  105:  2329 
    Google Scholar
  • 7d Hill CH. Angew. Chem. Int. Ed.  2004,  43:  402 
    Google Scholar
  • 7e Stahl SS. Angew. Chem. Int. Ed.  2004,  43:  3400 
    Google Scholar
  • 8 Murahashi S.-I. Komiya N. Terai H. Nakae T. J. Am. Chem. Soc.  2003,  125:  15312 
    CrossrefPubMedGoogle Scholar
  • 9a Murahashi S.-I. Okano Y. Sato H. Nakae T. Komiya N. Synlett  2007,  1675 
    Google Scholar
  • 9b Samec JSM. Ell AH. Backväll JE. Chem. Eur. J.  2005,  11:  2327 
    Google Scholar
  • 10a Yamaguchi K. Mizuno N. Angew. Chem. Int. Ed.  2003,  42:  1480 
    Google Scholar
  • 10b Mori K. Yamaguchi K. Mizugaki T. Ebitani K. Kaneda K. Chem. Commun.  2001,  461 
    Google Scholar
  • 11 Imada Y. Iida H. Ono S. Murahashi S.-I. J. Am. Chem. Soc.  2003,  125:  2868 
    CrossrefGoogle Scholar
  • 12 Urleb U. In Methods of Organic Chemistry (Houben-Weyl)   Part 2, 4th ed., Vol. E9b:  Schaumann E. Thieme; Stuttgart: 1998.  p.266-303  
    Google Scholar
  • 13a Ćirić-Marjanović G. Konyushenko EN. Trchová M. Stejskal J. Synth. Met.  2008,  158:  200 
    Google Scholar
  • 13b Surwade SP. Dua V. Manohar N. Manohar SK. Beck EB. Ferraris JP. Synth. Met.  2009,  159:  445 
    Google Scholar
  • 13c Heichert C. Hartmann H. Z. Naturforsch., B: J. Chem. Sci.  2009,  64:  747 
    Google Scholar
  • 13d Cross B. Williams PJ. Woodall RE. J. Chem. Soc., Chem. Commun.  1971,  2085 
    Google Scholar
  • 13e Challand SR. Herbert RB. Holliman FG. J. Chem. Soc., Chem. Commun.  1970,  1423 
    Google Scholar
  • 13f Vivian DL. J. Org. Chem.  1956,  21:  565 
    Google Scholar
  • 13g Waterman HC. Vivian DL. J. Org. Chem.  1949,  14:  289 
    Google Scholar
  • 13h Hedayatullah M. Dechatre JP. Denivelle L. Tetrahedron Lett.  1975,  16:  2039 
    Google Scholar
  • 13i Balogh-Hergovich E. Bodnar G. Speier G. Acta Chim. Hung.  1981,  108:  37 
    Google Scholar
  • 13j Rewcastle GW. Denny WA. Synth. Commun.  1987,  17:  1171 
    Google Scholar
  • 13k Gaertner G. Gray A. Holliman FG. Tetrahedron  1962,  18:  1105 
    Google Scholar
  • 13l Ley SV. Thomas AW. Angew. Chem. Int. Ed.  2003,  42:  5400 
    Google Scholar
  • 13m Kunz K. Scholz U. Ganzer D. Synlett  2003,  2428 
    Google Scholar
  • 13n Goldberg AA. Kelly W. J. Chem. Soc.  1947,  595 
    Google Scholar
  • 13o Crank G. Makin MIH. Tetrahedron Lett.  1983,  24:  3159 
    Google Scholar
  • 15 Kosugi Y. Itoho K. Okazaki H. Yanai T. J. Org. Chem.  1995,  60:  5690 
    CrossrefGoogle Scholar
  • 16 Kyziol JB. Chem. Pap.  2007,  61:  398 
    CrossrefGoogle Scholar
14

CCDC number of 2d is 760485.

17

General Procedure for the Synthesis of 1,9-Dihydrodiindolo[3,2- a :3,2- h ]phenazine (2a) A mixture of 3-aminocarbazole (1.0 mmol) and CuBr (10 mol%) in DMSO was heated at 80 ˚C open to air for 6 h. After completion of the reaction, the reaction mixture was poured on to H2O and extracted with EtOAc (3 × 30 mL). The solvent was dried over anhyd Na2SO4 and evaporated under reduced pressure. The crude material was purified by column chromatography using silica gel (100-200 mesh size) and eluted with a mixture of hexane and EtOAc to obtain the pure product of diindolophenazine. IR (KBr): 3393, 3053, 2926, 2854, 1726, 1601, 1462, 1379, 1265, 1074, 895, 742 cm-¹. ¹H NMR (400 MHz, DMSO-d 6): δ = 12.18 (2 H, s), 9.06 (2 H, d, J = 7.6 Hz), 8.30 (2 H, d, J = 9.2 Hz), 8.23 (2 H, d, J = 8.8 Hz), 7.73 (2 H, d, J = 8.0 Hz), 7.49 (2 H, t, J = 7.2 Hz), 7.43 (2 H, t, J = 7.6 Hz). ¹³C NMR (100 MHz, DMSO-d 6): δ = 139.9, 139.0, 138.9, 138.5, 127.5, 125.2, 123.8, 123.2, 121.0, 120.3, 114.3, 112.4. LC-MS (pos. mode): m/z = 359 [M + H+]. Anal. Calcd for C24H14N4: C, 80.43; H, 3.94; N, 15.63. Found: C, 80.25; H, 3.89; N, 15.77.