Download PDF
Synthesis 2008(6): 903-912  
DOI: 10.1055/s-2008-1032208
PAPER
© Georg Thieme Verlag Stuttgart · New York

Palladium-Catalyzed Synthesis of 3-Indolecarboxylic Acid Derivatives

Björn C. G. Söderberg*, Serge R. Banini, Michael R. Turner, Aaron R. Minter, Amanda K. Arrington
C. Eugene Bennett Department of Chemistry, West Virginia University, Morgantown, WV 26506-6045, USA
Fax: +1(304)2934904; e-Mail: bjorn.soderberg@mail.wvu.edu;
Further Information

Publication History

Received 11 September 2007
Publication Date:
28 February 2008 (online)

    Permissions and Reprints All articles of this category

Corrected by:

Palladium-Catalyzed Synthesis of 3-Indolecarboxylic Acid DerivativesSynthesis 2008; 2008(20): 3360-3360
DOI: 10.1055/s-0028-1083166

Abstract

Indoles having an ester functionality in the 3-position were prepared from 2-(2-nitrophenyl)propenoic acid derivatives via a palladium-catalyzed reductive N-heteroannulation using carbon monoxide as the ultimate reducing agent. The starting materials were prepared either by a Stille coupling of 2-halo-1-nitrobenzenes with ethyl 2-(tributylstannyl)-2-propenoate or by vicarious nucleophilic substitution of nitrobenzenes followed by a Knoevenagel-type condensation with an aldehyde. Synthesis of an example of a 3-nitrile- and a 3-sulfone-substituted indole is also described using the same type of methodologies.

Key words

palladium - catalysis - reductions - indoles - cyclizations

    References

  • 1a Kuethe JT. Davies IW. Tetrahedron  2006,  62:  11381 
    CrossrefGoogle Scholar
  • 1b Clawson RW. Deavers RE. Akhmedov NG. Söderberg BCG. Tetrahedron  2006,  62:  10829 
    CrossrefGoogle Scholar
  • 1c Davies IW. Smitrovich JH. Sidler R. Qu C. Gresham V. Bazaral C. Tetrahedron  2005,  61:  6425 
    CrossrefGoogle Scholar
  • 1d Söderberg BCG. Hubbard JW. Rector SR. O’Neil SN. Tetrahedron  2005,  61:  3637 
    CrossrefGoogle Scholar
  • 1e Söderberg BC. Shriver JA. J. Org. Chem.  1997,  62:  5838 
    CrossrefGoogle Scholar
  • 1f Akazome M. Kondo T. Watanabe Y. J. Org. Chem.  1994,  59:  3375 
    CrossrefGoogle Scholar
  • 1g Tollari S. Cenini S. Crotti C. Gianella E. J. Mol. Catal.  1994,  87:  203 
    CrossrefGoogle Scholar
  • 2 For reactions using Fe(CO)5, Ru3(CO)12 or Rh6(CO)16 catalysts under CO, see: Crotti C. Cenini S. Rindone B. Tollari S. Demartin F. Chem. Commun.  1986,  784 
    Google Scholar
  • 3 For reactions using catalytic amounts of selenium under CO, see: Nishiyama Y. Maema R. Ohno K. Hirose M. Sonoda N. Tetrahedron Lett.  1999,  40:  5717 
    CrossrefGoogle Scholar
  • 4 For reactions using catalytic amounts of MoO2Cl2(dmf)2 with PPh3 as oxygen acceptor, see: Sanz R. Escribano J. Pedrosa MR. Aguado R. Arnaiz FJ. Adv. Synth. Catal.  2007,  349:  713 
    CrossrefGoogle Scholar
  • 5 Kuethe JT. Wong A. Davies IW. Org. Lett.  2003,  5:  3721 
    CrossrefGoogle Scholar
  • 6 Kuethe JT. Wong A. Qu C. Smitrovich J. Davies IW. Hughes DL. J. Org. Chem.  2005,  70:  2555 
    CrossrefGoogle Scholar
  • 7 Scott TL. Söderberg BCG. Tetrahedron  2003,  59:  6323 
    CrossrefGoogle Scholar
  • 8 Dantale SW. Söderberg BCG. Tetrahedron  2003,  59:  5507 
    Google Scholar
  • 9 Scott TL. Yu X. Gorunatula SP. Carrero-Martínez G. Söderberg BCG. Tetrahedron  2006,  62:  10835 
    CrossrefGoogle Scholar
  • 10 Söderberg BC. Chisnell AC. O’Neil SN. Shriver JA. J. Org. Chem.  1999,  64:  9731 
    CrossrefGoogle Scholar
  • 11 For a recent review, see: Humphrey GR. Kuethe JT. Chem. Rev.  2006,  106:  2875 
    CrossrefPubMedGoogle Scholar
  • 12 Allen GR. Org. React.  1973,  20:  337 
    Google Scholar
  • 13 Islam MS. Brennan C. Wang Q. Hossain MM. J. Org. Chem.  2006,  71:  4675 
    CrossrefGoogle Scholar
  • 14a Sakamoto T. Nagano T. Kondo Y. Yamanaka H. Synthesis  1990,  215 
    CrossrefPubMedGoogle Scholar
  • 14b Yamazaki K. Nakamura Y. Kondo Y. J. Org. Chem.  2003,  68:  6011 
    CrossrefPubMedGoogle Scholar
  • 15 Kondo Y. Shiga F. Murata N. Sakamoto T. Yamanaka H. Tetrahedron  1994,  50:  11803 
    CrossrefGoogle Scholar
  • 16 Pedras MSC. Sarwar MG. Suchy M. Adio AM. Phytochemistry  2006,  67:  1503 
    CrossrefGoogle Scholar
  • 17 Ovenden SBP. Capon RJ. J. Nat. Prod.  1999,  62:  1246 
    CrossrefGoogle Scholar
  • 18 Sakurai M. Kohno J. Nishio M. Yamamoto K. Okuda T. Kawano K. Nakanishi N. J. Antibiot.  2001,  54:  628 
    CrossrefGoogle Scholar
  • 19 Holan G, and Walser RA. inventors; Eur. Pat. Appl. EP 3670  19790822. Adapted from: ; Chem. Abstr. 1979, 92, 94079
  • 20 Davies IW, Smitrovich JH, and Qu C. inventors; PCT Int. Appl. WO  2005000804. Using methyl 2-(2-nitro-4-trifluoromethoxyphenyl)-3-phenylpropenoate. No yield was given. See: ; Chem. Abstr. 2005, 142, 113888
  • 21 For a review, see: Makosza M. Wojciechowski K. Liebigs Ann./Recl.  1997,  1805 
    Google Scholar
  • For related trans-etherifications using the same substrate, see:
  • 22a Jonczyk A. Kowalkowska A. Synthesis  2002,  674 
    CrossrefGoogle Scholar
  • 22b Andreassen EJ. Bakke JM. Sletvold I. Svensen H. Org. Biomol. Chem.  2004,  2:  2671 
    CrossrefGoogle Scholar
  • For examples, see:
  • 23a Arraya C. Guillard J. Renard P. Audinot V. Boutin Jean A. Delagrange P. Bennejean C. Viaud-Massuard M.-C. Eur. J. Med. Chem.  2004,  39:  515 
    CrossrefGoogle Scholar
  • 23b Seko S. Miyake K. Chem. Commun.  1998,  1519 
    CrossrefGoogle Scholar
  • 23c Makosza M. Bialecki M. J. Org. Chem.  1998,  63:  4878 
    CrossrefGoogle Scholar
  • 23d Makosza M. Owczarczyk Z. J. Org. Chem.  1989,  54:  5094 
    CrossrefGoogle Scholar
  • 24 Makosza M. Tyrala A. Synth. Commun.  1986,  419 
    CrossrefGoogle Scholar
  • 25 For a review, see: Farina V. Krishnamurthy V. Scott VJ. Org. React.  1997,  50:  1 
    Google Scholar
  • To our knowledge, only two condensation reactions of 2-(2-nitrophenyl)ethanoates with aliphatic aldehydes have been reported:
  • 26a Palmer FN. Lach F. Poriel C. Pepper AG. Bagley MC. Slawin AMZ. Moody CJ. Org. Biomol. Chem.  2005,  3:  3805 
    CrossrefGoogle Scholar
  • 26b Wrobel Z. Makosza M. Tetrahedron  1993,  49:  5315 
    CrossrefGoogle Scholar
  • Formation of quinolines have been observed in transition-metal-catalyzed reductive annulations of β-(2-nitrophenyl)-α,β-unsaturated ketones and aldehydes. These reactions probably occur by initial reduction of the nitro-group to an amine, followed by condensation with the carbonyl. See:
  • 27a Watanabe Y. Takatsuki K. Shim SC. Bull. Chem. Soc. Jpn.  1978,  51:  3397 
    CrossrefGoogle Scholar
  • 27b

    See also reference 1f.
    CrossrefGoogle Scholar
  • 28 Chen G, Yee DJ, Gubernator N, and Sames D. inventors; PCT Int. Appl.,  WO2006026368. This compound was recently prepared in 55% yield using a similar procedure, see: ; Chem. Abstr. 2006, 144, 292572
  • 29 For a preparation in 77% yield using tert-butyl 2-phenylthio-ethanoate, see: Makosza M. Winiarski J. J. Org. Chem.  1984,  49:  1494 
    CrossrefGoogle Scholar
  • 30 Selvakumar N. Azhagan AM. Srinivas D. Krishna GG. Tetrahedron Lett.  2002,  43:  9175 
    CrossrefGoogle Scholar
  • 32 Woon ECY. Dhaami A. Mahon MF. Threadgill MD. Tetrahedron  2006,  62:  4829 
    CrossrefGoogle Scholar
  • 33 Golinski J. Makosza M. Tetrahedron Lett.  1978,  3495 
    CrossrefGoogle Scholar
  • 34 Kosugi M. Ohya T. Migita T. Bull. Chem. Soc. Jpn.  1983,  56:  3855 
    CrossrefGoogle Scholar
  • 35 Huang Z. Yu X. Huang X. J. Org. Chem.  2002,  67:  8261 
    CrossrefGoogle Scholar
  • 36 Michell G. Rees CW. J. Chem. Soc., Perkin Trans. 1  1987,  413 
    CrossrefGoogle Scholar
  • 37 Bergman J. J. Heterocycl. Chem.  1977,  14:  1123 
    CrossrefGoogle Scholar
  • 38 Kasahara A. Izumi T. Murakami S. Yanai H. Takatori M. Bull. Chem. Soc. Jpn.  1986,  59:  927 
    Google Scholar
31

One carbon resonance was not observed.

39

The reported mp for the dimethyl diester is 143-144 °C.