Synlett 2005(16): 2469-2472  
DOI: 10.1055/s-2005-917079
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Ring-A-Substituted Tryptophan by a Palladium-Catalyzed Heteroannulation Reaction

Yanxing Jia, Jieping Zhu*
Institut de Chimie des Substances Naturelles, CNRS, 91198 Gif-sur-Yvette Cedex, France
Fax: +33(1)69077247; e-Mail: zhu@icsn.cnrs-gif.fr;
Further Information

Publication History

Received 15 July 2005
Publication Date:
21 September 2005 (online)

Abstract

Coupling of substituted o-iodoanilines with methyl (S)-2-N,N-di-tert-butoxycarbonyl-5-oxo-pentanoate, derived from glutamic acid, in DMF in the presence of palladium acetate and DABCO provides substituted tryptophans in good to excellent yields.

    References

  • For examples, see:
  • 1a Hamaker LK. Cook JM. In Alkaloids: Chemical and Biological Perspectives   Vol 9:  Pelletiers SW. Elsevier Science; New York: 1995.  p.23-84  
  • 1b Lounasmaa M. Hanhinen P. Westersund M. In Alkaloids   Vol 52:  Cordell GA. Academic Press; San Diego: 1999.  p.103-195  
  • 2 Campagnuolo C. Fattorusso E. Taglialatela-Scafati O. Eur. J. Org. Chem.  2003,  284 
  • 3a Raverty WD. Thomson RH. King TJ. J. Chem. Soc., Perkin Trans. 1  1977,  1204 
  • 3b 6-Bromo d-hypa-phorine has also been isolated, see: Kondo K. Nishi J. Ishibashi M. Kobayashi J.-I. J. Nat. Prod.  1994,  57:  1008 
  • 4 Kerr SJ. Armati PJ. Pemberton LA. Smythe G. Tattam B. Brew BJ. Neurology  1997,  49:  1671 
  • 5 Peterson AC. Migawa MT. Martin MJ. Hamaker LK. Czerwinski KM. Zhang W. Arend RA. Fisette PL. Ozaki Y. Will JA. Brown RR. Cook JM. Med. Chem. Res.  1994,  4:  531 
  • 6 Munn D. Zhou M. Attwood J. Bondarev I. Conway S. Marshall B. Brown C. Mellor A. Science  1998,  281:  1191 
  • 7a Gouda H. Matsuzaki K. Tanaka H. Hirono S. Omura S. McCauley JA. Sprengeler PA. Furst GT. Smith AB. J. Am. Chem. Soc.  1996,  118:  13087 
  • 7b For the total synthesis: Deng H. Jung J.-K. Liu T. Kuntz KW. Snapper ML. Hoveyda AH. J. Am. Chem. Soc.  2003,  125:  9032 
  • 8 Kobayashi J. Suzuki H. Shimbo K. Takeya K. Morita H. J. Org. Chem.  2001,  66:  6626 
  • 9 For a recent general review on the construction of indole ring, see: Gribble GW. J. Chem. Soc., Perkin Trans. 1  2000,  1045 
  • 10a Allen MC. Brundish DE. Wade R. J. Chem. Soc., Perkin Trans. 1  1980,  1928 
  • 10b Konda-Yamada Y. Okada C. Yoshida K. Umeda Y. Arima S. Sato N. Kai T. Takayanagi H. Harigaya Y. Tetrahedron  2002,  58:  7851 
  • 11a Lee M. Philips RS. Bioorg. Med. Chem. Lett.  1992,  2:  1563 
  • 11b Kaiser M. Groll M. Renner C. Huber R. Moroder L. Angew. Chem. Int. Ed.  2002,  41:  780 
  • 12a Hino T. Taniguchi M. J. Am. Chem. Soc.  1978,  100:  5564 
  • 12b Taniguchi M. Anjiki T. Nakagawa M. Hino T. Chem. Pharm. Bull.  1984,  32:  2544 
  • 13a Yokoyama Y. Matsumoto T. Murakami Y. J. Org. Chem.  1995,  60:  1486 
  • 13b Wang W. Xiong C. Yang J. Hruby VJ. Tetrahedron Lett.  2001,  42:  7717 
  • 14 Liu R. Zhang P. Gan T. Cook JM. J. Org. Chem.  1997,  62:  7447 
  • 15 Berthelot A. Piguel S. Le Dour G. Vidal J. J. Org. Chem.  2003,  68:  9835 
  • 16a Elder AM. Rich DH. Org. Lett.  1999,  1:  1443 
  • 16b Drury WJ. Ferraris D. Cox C. Young B. Lectka T. J. Am. Chem. Soc.  1998,  120:  11006 
  • 17a Larock RC. Yum EK. J. Am. Chem. Soc.  1991,  113:  6689 
  • 17b Larock RC. Yum EK. Refvik MD. J. Org. Chem.  1998,  63:  7652 
  • 18a Ma C. Liu X. Li X. Flippen-Anderson J. Yu S. Cook JM. J. Org. Chem.  2001,  66:  4525 
  • 18b Li X. Yin W. Srirama Sarma PVV. Zhao H. Ma J. Cook JM. Tetrahedron Lett.  2004,  45:  8569 
  • 18c Castle SL. Srikanth GSC. Org. Lett.  2003,  5:  3611 
  • 19 Link JT. In Organic Reactions   Vol 60:  Overman LE. John Wiley and Sons, Inc.; New Jersey: 2002.  p.157-534  
  • 20 Mori M. Chiba K. Ban Y. Tetrahedron Lett.  1977,  1037 
  • 21 Odle R. Blevins B. Ratcliff M. Hegedus LS. J. Org. Chem.  1980,  45:  2709 
  • 22 Chen C.-Y. Lieberman DR. Larsen RD. Verhoeven TR. Reider PJ. J. Org. Chem.  1997,  62:  2676 
  • 23 Baran PS. Guerrero CA. Ambhaikar NB. Hafensteiner BD. Angew. Chem. Int. Ed.  2005,  44:  606 
  • Prepared in four steps from glutamic acid in 80% overall yield according to Martin, see:
  • 25a Kokotos G. Padron JM. Martin T. Gibbons WA. Martin VS. J. Org. Chem.  1998,  63:  3741 
  • 25b Padron JM. Kokotos G. Martin T. Markidis T. Gibbons WA. Martin VS. Tetrahedron: Asymmetry  1998,  9:  3381 
  • 26 Typical Experimental Procedure. A solution of o-iodoaniline 3a (73.0 mg, 0.33 mmol), aldehyde 6 (104.0 mg, 0.30 mmol), and DABCO (101.0 mg, 0.9 mmol) and Pd(OAc)2 (3.4 mg, 0.015 mmol) in dry DMF (1.5 mL) was degassed. The reaction mixture was heated to 85 °C until the reaction was complete (usually 8-12 h). The reaction mixture was cooled to r.t. and was diluted with H2O. The aqueous phase was extracted with EtOAc and the combined organic phase was washed with brine, dried (Na2SO4), and evaporated to dryness under reduced pressure. Purification of crude product by flash column chromatography (silica gel, 20% EtOAc in heptane) provided the desired product 7 (101 mg, 81%; yellow oil). [α]D 23 -60.0 (c 1.00, CHCl3). IR (CHCl3): 3348, 2980, 2359, 1782, 1741, 1457, 1369, 1273, 1140, 1092, 852 cm-1. 1H NMR (300 MHz, CDCl3): δ = 8.45 (br s, 1 H), 7.58 (d, 1 H, J = 7.7 Hz), 7.34 (d, 1 H, J = 7.9 Hz), 7.15 (dt, 1 H, J = 1.2, 7.7 Hz), 7.09 (dt, 1 H, J = 1.2, 7.9 Hz), 6.98 (d, 1 H, J = 2.1 Hz), 5.20 (dd, 1 H, J = 4.7, 10.3 Hz), 3.77 (s, 3 H), 3.62 (dd, 1 H, J = 4.7, 14.9 Hz), 3.40 (dd, 1 H, J = 10.3, 14.9 Hz), 1.28 (s, 18 H). 13C NMR (75 MHz, CDCl3): δ = 171.1, 151.5, 136.3, 127.5, 123.2, 121.7, 119.2, 118.5, 111.2, 82.8, 58.9, 52.1, 27.6 (6 C), 25.8. MS (ESI): m/z = 441 [M + Na]. HRMS (ESI): m/z calcd for C22H30N2O6Na [M + Na]: 441.2002; found: 441.1975.
  • 27 Yadav JS. Reddy BVS. Reddy KS. Synlett  2002,  468 
  • 28a Lizos DE. Murphy JA. Org. Biomol. Chem.  2003,  1:  117 
  • 28b Kondo Y. Kojima S. Sakamoto T. J. Org. Chem.  1997,  62:  6507 
  • 29 Sy W.-W. Synth. Commun.  1992,  22:  3215 
  • For intramolecular Heck reaction involving a formal 5-endo cyclization on the enamine unit see:
  • 30a

    Ref. 21.

  • 30b Iida H. Yuasa Y. Kibayashi C. J. Org. Chem.  1980,  45:  2938 
  • 30c Kasahara A. Izumi T. Murakami S. Yanai H. Takatori M. Bull. Chem. Soc. Jpn.  1986,  59:  927 
  • 30d Shaw KJ. Luly JR. Rappoport H. J. Org. Chem.  1985,  50:  4515 
  • 30e Sakamoto T. Nagano T. Kondo Y. Yamanaka H. Synthesis  1990,  215 
  • 30f Michael JP. Chang SF. Wilson C. Tetrahedron Lett.  1993,  34:  8365 
  • 30g Koerber-Plé K. Massiot G. Synlett  1994,  759 
  • 30h Latham EJ. Stanforth SP. Chem. Commun.  1996,  2253 
  • 30i Watanabe T. Arai S. Nishida A. Synlett  2004,  907 
24

l-Try was isolated in 10% yield under Baran’s modified conditions.