Download PDF
Synlett 2009(18): 2997-2999  
DOI: 10.1055/s-0029-1218004
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Total Synthesis of Horsfiline: A Palladium-Catalyzed Domino Heck-Cyanation Strategy

Stéphanie Jaeglia, Jean-Pierre Vorsb, Luc Neuville*a, Jieping Zhu*a
a Institut de Chimie des Substances Naturelles, CNRS, 91198 Gif-sur-Yvette Cedex, France
Fax: +33(1)69077247; e-Mail: zhu@icsn.cnrs-gif.fr; e-Mail: neuville@icsn.cnrs-gif.fr;
b Bayer CropScience SA, 14-20 Rue Pierre Baizet, 69009 Lyon, France
Further Information

Publication History

Received 20 July 2009
Publication Date:
08 October 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

A total synthesis of horsfiline has been accomplished featuring a key intramolecular palladium-catalyzed domino Heck-cyanation sequence for the formation of the 3,3′-disubstituted oxindole.

Key words

domino reaction - palladium - Heck - cyanation - oxindole - horsfiline

    References and Notes

  • For reviews, see:
  • 1a Marti C. Carreira EM. Eur. J. Org. Chem.  2003,  2209 
    Google Scholar
  • 1b Galliford CV. Sheidt KA. Angew. Chem. Int. Ed.  2007,  46:  8748 
    Google Scholar
  • 2 James MNG. Williams GJB. Can. J. Chem.  1972,  50:  2407 
    CrossrefGoogle Scholar
  • 3a Cui CB. Kakeya H. Osada H. J. Antibiot.  1996,  49:  832 
    Google Scholar
  • 3b Cui C.-B. Kakeya H. Ckada H. Tetrahedron  1996,  52:  12651 
    Google Scholar
  • 4 Elderfield RC. Gilman RE. Phytochemistry  1972,  11:  339 
    CrossrefGoogle Scholar
  • 5 Pellegrin C. Weber M. Borschberg H.-J. Helv. Chim. Acta  1996,  79:  151 ; and references therein
    CrossrefGoogle Scholar
  • 6 Edmondson S. Danishefsky SJ. Sepp-Lorenzino L. Rosen N. J. Am. Chem. Soc.  1999,  121:  2147 
    CrossrefGoogle Scholar
  • 7 Jossang A. Jossang P. Hadi HA. Sevenet T. Bodo B. J. Org. Chem.  1991,  56:  6527 
    CrossrefGoogle Scholar
  • 8a Jones K. Wilkinson J. Chem. Commun.  1992,  1767 
    Google Scholar
  • 8b Bascop S. Sapi J. Laronze J. Levy J. Heterocycles  1994,  38:  725 
    Google Scholar
  • 8c Pellegrini C. Strässler C. Weber M. Borschberg H. Tetrahedron: Asymmetry  1994,  5:  1979 
    Google Scholar
  • 8d Palmisano G. Annunziata R. Papeo G. Sisti M. Tetrahedron: Asymmetry  1996,  7:  1 
    Google Scholar
  • 8e Lakshmaiah G. Kawabata T. Shang M. Fuji K. J. Org. Chem.  1999,  64:  1699 
    Google Scholar
  • 8f Fischer C. Meyers C. Carreira EM. Helv. Chim. Acta  2000,  83:  1175 
    Google Scholar
  • 8g Cravotto G. Giovenzana G. Pilati T. Sisti M. Palmisano G. J. Org. Chem.  2001,  66:  8447 
    Google Scholar
  • 8h Kumar UKS. Illa H. Junjappa H. Org. Lett.  2001,  3:  4193 
    Google Scholar
  • 8i Lizos D. Tripoli R. Murphy JA. Chem. Commun.  2001,  2732 
    Google Scholar
  • 8j Selvakumar N. Azhagan AM. Srinivas D. Krishna GG. Tetrahedron Lett.  2002,  43:  9175 
    Google Scholar
  • 8k Lizos DE. Murphy JA. Org. Biomol. Chem.  2003,  1:  117 
    Google Scholar
  • 8l Chang MY. Pai C.-L. Kung Y.-H. Tetrahedron Lett.  2005,  46:  8463 
    Google Scholar
  • 8m Murphy JA. Tripoli R. Khan TA. Mali UW. Org. Lett.  2005,  7:  3287 
    Google Scholar
  • 8n Trost BM. Brennan MK. Org. Lett.  2006,  8:  2027 
    Google Scholar
  • 9a Bonnaterre F. Bois-Choussy M. Zhu J. Org. Lett.  2006,  8:  4351 
    Google Scholar
  • 9b Salcedo A. Neuville L. Zhu J. J. Org. Chem.  2008,  73:  3600 
    Google Scholar
  • 9c Erb W. Neuville L. Zhu J. J. Org. Chem.  2009,  74:  3109 
    Google Scholar
  • 10a Pinto A. Neuville L. Retailleau P. Zhu J. Org. Lett.  2006,  8:  4927 
    Google Scholar
  • 10b Pinto A. Neuville L. Retailleau P. Zhu J. Angew. Chem. Int. Ed.  2007,  46:  3291 
    Google Scholar
  • 10c Pinto A. Neuville L. Zhu J. Tetrahedron Lett.  2009,  50:  3602 
    Google Scholar
  • For general reviews on the domino process, see:
  • 11a Tietze LF. Chem. Rev.  1996,  96:  115 
    Google Scholar
  • 11b Nicolaou KC. Edmonds DJ. Bulger PG. Angew. Chem. Int. Ed.  2006,  45:  7134 
    Google Scholar
  • 11c For a recent book, see: Domino Reactions in Organic Synthesis   Tietze LF. Brasche G. Gericke K. Wiley-VCH; Weinheim: 2006. 
    Google Scholar
  • 12 Pinto A. Jia X. Neuville L. Zhu J. Chem. Eur. J.  2007,  13:  961 
    CrossrefGoogle Scholar
  • For the seminal use of K4[Fe(CN)6] in palladium-mediated cyanation, see:
  • 13a Schareina T. Zapf A. Beller M. Chem. Commun.  2004,  1388 
    Google Scholar
  • See also:
  • 13b Weissman SA. Zewge D. Chen C. J. Org. Chem.  2005,  70:  1508 
    Google Scholar
  • 13c Gelman D. Grossman O. Org. Lett.  2006,  8:  1189 
    Google Scholar
  • 13d Li LH. Pan Z.-L. Liang Y.-M. Synlett  2006,  2094 
    Google Scholar
  • 13e Schareina T. Zapf A. Magerlein W. Muller N. Beller M. Tetrahedron Lett.  2007,  48:  1087 
    Google Scholar
  • 13f For related domino palladium-catalyzed cyanation process, see: Mariampillai B. Alliot J. Li M. Lautens M. J. Am. Chem. Soc.  2007,  129:  15372 
    Google Scholar
  • 13g Cheng Y.-N. Duan Z. Yu L. Li Z. Zhu Y. Wu Y. Org. Lett.  2008,  10:  901 
    Google Scholar
  • 13h For a general review on palladium-catalyzed cross-coupling involving metal cyanides, see: Takagi K. In Handbook of Organopalladium Chemistry for Organic Synthesis   Vol.1:  Negishi E. de Meijere A. Wiley; New York: 2002.  p.657-672  
    Google Scholar
  • 14a Byun HS. Reddy KC. Bittman R. Tetrahedron Lett.  1994,  35:  1371 
    Google Scholar
  • 14b Yu C. Liu B. Hu L. J. Org. Chem.  2001,  66:  5413 
    Google Scholar
  • For reviews, see:
  • 14c Basavaiah D. Rao AJ. Satyanarayana T. Chem. Rev.  2003,  103:  811 
    Google Scholar
  • 14d Masson G. Housseman C. Zhu J. Angew. Chem. Int. Ed.  2007,  46:  4614 
    Google Scholar
  • 15a Villieras J. Rambaud M. Synthesis  1982,  924 
    Google Scholar
  • 15b Villieras J. Rambaud M. Org. Synth.  1988,  66:  220 
    Google Scholar
  • 16 Kondo Y. Kojima S. Sakamoto T. J. Org. Chem.  1997,  62:  6507 
    CrossrefGoogle Scholar
  • 17 Bald E. Saigo K. Mukaiyama T. Chem. Lett.  1975,  4:  1163 
    Google Scholar
  • 19 Such reduction product has been reported in a related domino Heck reaction recently: Ruck RT. Huffman MA. Kim MK. Shevlin M. Kandur WV. Davies IW. Angew. Chem. Int. Ed.  2008,  47:  4711 
    Google Scholar
  • 20 Zawisza AM. Muzart J. Tetrahedron Lett.  2007,  48:  6738 ; and references cited herein
    CrossrefGoogle Scholar
  • 21a Satoh T. Suzuki S. Suzuki Y. Miyagi Y. Imai Z. Tetrahedron Lett.  1969,  4555 
    Google Scholar
  • 21b Osby JO. Heinzman SW. Ganem B. J. Am. Chem. Soc.  1986,  108:  67 
    Google Scholar
  • 21c Caddick S. Haynes AK. Judd DB. Williams MRV. Tetrahedron Lett.  2000,  41:  3513 
    Google Scholar
  • 22a Appel R. Angew. Chem. Int. Ed.  1976,  14:  801 
    Google Scholar
  • 22b Shishido Y. Kibayashi C. J. Org. Chem.  1992,  57:  2876 
    Google Scholar
  • 22c Wittenberger SJ. McLaughlin MA. Tetrahedron Lett.  1999,  40:  7175 
    Google Scholar
  • 22d Harris JM. Padwa A. J. Org. Chem.  2003,  68:  4371 
    Google Scholar
18

Experimental Procedure: To a degassed solution of iodoanilide 14 (1.90 g, 3.29 mmol, 1.0 equiv) in DMF (16 mL) were added K4Fe(CN)6˙3H2O (306.0 mg, 0.72 mmol, 0.22 equiv), Na2CO3 (350.0 mg, 3.30 mmol, 1.0 equiv) and Pd(OAc)2 (22.0 mg, 0.1 mmol, 0.03 equiv). After being stirred at 120 ˚C under an argon atmosphere for 3 h, the reaction mixture was quenched with H2O and extracted with EtOAc. The combined organic layers were washed with brine, dried (Na2SO4) and concentrated. The residue was purified by flash chromatography (SiO2, heptane-EtOAc, 95:5 → 90:10) to give the corresponding oxindole 15 (0.94 g, 60%) as a light orange solid. Compound 15: ¹H NMR (500 MHz, CDCl3): δ = 7.06 (d, J = 2.6 Hz, 1 H), 7.02 (d, J = 8.6 Hz, 1 H), 6.88 (dd, J = 8.6, 2.6 Hz, 1 H), 5.17 (d, J = 11.0 Hz, 1 H), 5.11 (d, J = 11.0 Hz, 1 H), 3.92 (d, J = 9.7 Hz, 1 H), 3.80 (s, 3 H), 3.73 (d, J = 9.7 Hz, 1 H), 3.62-3.51 (m, 2 H), 3.02 (d, J = 16.7 Hz, 1 H), 2.79 (d, J = 16.7 Hz, 1 H), 0.92 (t, J = 8.2 Hz, 2 H), 0.84 (s, 9 H), 0.00 (s, 3 H), -0.01 (s, 3 H), -0.03 (s, 9 H). ¹³C NMR (75 MHz, CDCl3): δ = 175.4, 156.4, 135.4, 129.1, 116.2, 114.3, 111.2, 110.6, 69.9, 66.5, 66.1, 55.8, 51.9, 25.7, 21.7, 18.1, 17.7, -1.4, -5.6, -5.7. HRMS (ES+): m/z [M + Na]+ calcd for C24H40N2O4Si2Na: 499.2424; found: 499.2415.