Download PDF
Synthesis 2010(18): 3174-3178  
DOI: 10.1055/s-0030-1257912
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Chemo- and Regiospecific Modification of d,l-Tryptophan by Reaction with α,β-Acetylenic γ-Hydroxy Nitriles

Boris A. Trofimov*, Anastasiya G. Mal’kina, Angela P. Borisova, Olesya A. Shemyakina, Valentina V. Nosyreva, Alexander I. Albanov
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., 664033, Irkutsk, Russian Federation
Fax: +7(3952)419346; e-Mail: boris_trofimov@irioch.irk.ru;
Further Information

Publication History

Received 28 April 2010
Publication Date:
04 August 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

d,l-Tryptophan reacts with α,β-acetylenic γ-hydroxy nitriles, chemo- and regiospecifically, under mild, green conditions via a hydroamination-type process involving the primary amine group. The hydroxycyanopropanyl substituent of the initial adducts undergoes cyclization to afford a 2,5-dihydro-5-iminofuranyl moiety. Several novel amino acids are obtained in almost quantitative yields (95-98%), which exist in an unusual zwitterionic form where the positive charge is located on the remote nitrogen atom of the imino group of the dihydrofuran ring.

Key words

d,l-tryptophan - α,β-acetylenic γ-hydroxy nitriles - nucleophilic addition - hydroamination - amino acids - 2,5-dihydroiminofurans

    References

  • 1a Gul W. Hamann MT. Life Sci.  2005,  78:  442 
    Google Scholar
  • 1b Humphrey GR. Kuethe JT. Chem. Rev.  2006,  106:  2875 
    Google Scholar
  • 1c Tanimori S. Ura H. Kirihata M. Eur. J. Org. Chem.  2007,  3977 
    Google Scholar
  • 1d de Sá Alves FR. Barreiro EJ. Fraga CAM. Mini Rev. Med. Chem.  2009,  9:  782 
    Google Scholar
  • 2a Sundberg RJ. The Chemistry of Indoles   Academic Press; New York: 1970. 
    Google Scholar
  • 2b Brown RK. In Indoles   Houlihan WJ. Wiley-Interscience; New York: 1972. 
    Google Scholar
  • 2c Sundberg RJ. Pyrroles and Their Benzo Derivatives: Synthesis and Applications, In Comprehensive Heterocyclic Chemistry   Vol. 4:  Katritzky AR. Rees CW. Pergamon; Oxford: 1984.  p.313-376  
    Google Scholar
  • 2d Sundberg RJ. Indoles (Best Synthetic Methods Key Systems and Functional Groups)   Academic Press; New York: 1996.  p.7-11  
    Google Scholar
  • 2e Sundberg RJ. In Comprehensive Heterocyclic Chemistry II   Vol. 2:  Katritzky AR. Rees CW. Scriven EFV. Bird CW. Pergamon Press; Oxford: 1996.  p.119 
    Google Scholar
  • 2f Gribble GW. In Comprehensive Heterocyclic Chemistry II   Vol. 2:  Katritzky AR. Rees CW. Scriven EFV. Bird CW. Pergamon Press; Oxford: 1996.  p.207 
    Google Scholar
  • 2g Indoles   Sundberg RJ. Academic Press; London: 1996. 
    Google Scholar
  • 2h Sundberg RJ. The Chemistry of Indoles   Academic Press; San Diego: 1997.  p.267 
    Google Scholar
  • 2i Joule JA. Indole and its Derivatives, In Science of Synthesis: Houben-Weyl Methods of Molecular Transformations   Vol. 10:  Thomas EJ. George Thieme Verlag; Stuttgart: 2000.  Chap. 10.13.
    Google Scholar
  • 3a Evans BE. Rittle KE. Bock MG. DiPardo RM. Freidinger RM. Whitter WL. Lundell GF. Verber DF. Anderson PS. Chang RSL. Lotti VJ. Cerino DJ. Chen TB. Kling PJ. Kunkel KA. Springer JP. Hirshfield J. J. Med. Chem.  1988,  31:  2235 
    Google Scholar
  • 3b Ohba H. Yamasaki N. Funatsu G. Agric. Biol. Chem.  1991,  55:  1579 
    Google Scholar
  • 3c Carlier PR. Lam PC.-H. Wong DM. J. Org. Chem.  2002,  67:  6256 
    Google Scholar
  • 3d Horton DA. Bourne GT. Smythe ML. Chem. Rev.  2003,  103:  893 ; and references cited therein
    Google Scholar
  • 3e de la Herrán G. Segura A. Csákÿ AG. Org. Lett.  2007,  9:  961 
    Google Scholar
  • 4 Conigrave AD. Quinn SJ. Brown EM. Proc. Natl. Acad. Sci. U.S.A.  2000,  97:  4814 
    CrossrefGoogle Scholar
  • 5a Friedman M. Cug J.-L. J. Agric. Food Chem.  1988,  36:  1079 
    Google Scholar
  • 5b Lee DG. Cho NJ. Choi JD. J. Biochem. Mol. Biol.  1996,  29:  321 
    Google Scholar
  • 5c Murch SJ. KrishnaRaj S. Saxena PK. Plant Cell Rep.  2000,  19:  698 
    Google Scholar
  • 5d Hirasawa M. Nakayama M. Kim S.-K. Hase T. Knaff DB. Photosynth. Res.  2005,  86:  325 
    Google Scholar
  • 5e Bender J. Celenza JL. Phytochem Rev.  2009,  8:  25 
    Google Scholar
  • 6 Somei M, Hattori A, and Suzuki N. inventors; WO 2007010723,  .  (National University Corporation, Kanazawa University, Japan, National University Corporation, Tokyo Medical and Dental University, Japan) ; Chem. Abstr. 2007, 146, 163392
  • 7 Walther D, and Bader M. inventors; WO  2002074309.  , (Max-Delbruck-Centrum fuer Moleculare Medizin, Germany) ; Chem. Abstr. 2002, 137, 242150
  • 8 Watanabe F. inventors; US  6727266.  , (Shionogi and Co., Ltd., Japan) ; Chem. Abstr. 2001, 135, 137709
  • 9a Ybarra J. Prasad ARS. Nishimura JS. Biochemistry  1986,  25:  7174 
    Google Scholar
  • 9b Tsubota T. Hagiwara Y. Murakami N. Ohno T. Diamond Relat. Mater.  2009,  18:  1174 
    Google Scholar
  • 10 Stachel SJ. Habeeb RL. Van Vranken DL. J. Am. Chem. Soc.  1996,  118:  1225 
    CrossrefGoogle Scholar
  • 11a Seradj H. Cai W. Erasga NO. Chenault DV. Knuckles KA. Ragains JR. Behforouz M. Org. Lett.  2004,  6:  473 
    Google Scholar
  • 11b Hassani M. Cai W. Holley DC. Lineswala JP. Maharjan BR. Ebrahimian GR. Seradj H. Stocksdale MG. Mohammadi F. Marvin CC. Gerdes JM. Beall HD. Behforouz M. J. Med. Chem.  2005,  48:  7733 
    Google Scholar
  • 11c Liu J. Cui G. Zhao M. Cui C. Jub J. Peng S. Bioorg. Med. Chem.  2007,  15:  7773 
    Google Scholar
  • 12 Sakiyan I. Logoglu E. Arslan S. Sari N. Sakiyan N. BioMetals  2004,  17:  115 
    CrossrefGoogle Scholar
  • 13a Skvortsov YM. Mal’kina AG. Trofimov BA. Zh. Org. Khim.  1983,  19:  1351 
    Google Scholar
  • 13b Skvortsov YM. Mal’kina AG. Trofimov BA. Kositsyna EI. Voronov VK. Baikalova LV. Zh. Org. Khim.  1984,  20:  1108 
    Google Scholar
  • 13c Trofimov BA. Mal’kina AG. Skvortsov YM. Zh. Org. Khim.  1993,  29:  1268 
    Google Scholar
  • 13d Mal’kina AG. Nosyreva VV. Kositsyna EI. Trofimov BA. Zh. Org. Khim.  1997,  33:  449 
    Google Scholar
  • 13e Trofimov BA. Mal’kina AG. Heterocycles  1999,  51:  2485 
    Google Scholar
  • 14 Skvortsov YM. Mal’kina AG. Trofimov BA. Volkov AN. Glaskova NP. Proidakov AG. Zh. Org. Khim.  1982,  18:  983 
    Google Scholar
  • 15 Nosyreva VV. Mal’kina AG. Shemyakina OA. Kositsyna EI. Albanov AI. Trofimov BA. Zh. Org. Khim.  2005,  41:  1225 
    Google Scholar
  • 16a Trofimov BA. Mal’kina AG. Shemyakina OA. Borisova AP. Nosyreva VV. Dyachenko OA. Kazheva ON. Alexandrov GG. Synthesis  2007,  2641 
    Google Scholar
  • 16b Trofimov BA. Mal’kina AG. Shemyakina OA. Nosyreva VV. Borisova AP. Khutsishvili SS. Krivdin LB. Synthesis  2009,  3136 
    Google Scholar
  • 17 Trofimov BA. Mal’kina AG. Shemyakina OA. Nosyreva VV. Borisova AP. Albanov AI. Kazheva ON. Alexandrov GG. Chekhlov AN. Dyachenko OA. Tetrahedron  2009,  65:  2472 
    CrossrefGoogle Scholar
  • 18a Effenberger F. Syed J. Tetrahedron: Asymmetry  1998,  9:  817 
    Google Scholar
  • 18b Shenoy G. Kim P. Goodwin M. Nguyen Q.-A. Barry CE. Dowd CS. Heterocycles  2004,  63:  519 
    Google Scholar
  • 18c Rajaram AR. Pu L. Org. Lett.  2006,  8:  2019 
    Google Scholar
  • 18d Zografos AI. Georgiadis D. Synthesis  2006,  3157 
    Google Scholar
  • 19 Tahir H. Hindsgaul O. J. Org. Chem.  2000,  65:  911 
    CrossrefGoogle Scholar
  • 20a Gao WY. Agbaria R. Driscoll JS. Mitsuya H.
    J. Biol. Chem.  1994,  269:  12633 
    Google Scholar
  • 20b Meier C. Synlett  1998,  233 
    Google Scholar
  • 20c Saboulard D. Naesens L. Cahard D. Salgado A. Pathirana R. Velazquez S. McGuigan C. De Clercq E. Balzarini J. Mol. Pharm.  1999,  56:  693 
    Google Scholar
  • 20d Bradshaw PC. Li J. Samuels DC. Biochem. J.  2005,  392:  363 
    Google Scholar
  • 21 Lichtenthaler FW. Cuny E. Sakanaka O. Angew. Chem. Int. Ed.  2005,  44:  4944 ; Angew. Chem. 2005, 117, 5024
    CrossrefGoogle Scholar
  • 22a Gunasekera SP. McCarthy PJ. Kelly-Borges M.
    J. Am. Chem. Soc.  1996,  118:  8759 
    Google Scholar
  • 22b Corey EJ. Roberts BE. J. Am. Chem. Soc.  1997,  119:  12425 
    Google Scholar
  • 22c Takahashi M. Dodo K. Sugimoto Y. Aoyagi Y. Yamada Y. Hashimoto Y. Shirai R. Bioorg. Med. Chem. Lett.  2000,  10:  2571 
    Google Scholar
  • 22d Miyaoka H. Kajiwara Y. Hara Y. Yamada Y. J. Org. Chem.  2001,  66:  1429 
    Google Scholar
  • 22e Brohm D. Philippe N. Metzger S. Bhargava A. Muller O. Lieb F. Waldmann H. J. Am. Chem. Soc.  2002,  124:  13171 
    Google Scholar
  • 23a Soriente A. Crispino A. De Rosa M. De Rosa S. Scettri A. Scognamiglio G. Villano R. Sodano G. Eur. J. Org. Chem.  2000,  943 
    Google Scholar
  • 23b Basabe P. Delgado S. Marcos IS. Diez D. Diego A. De Roman M. Urones JG. J. Org. Chem.  2005,  70:  9480 
    Google Scholar
  • 24a Mangnus EM. Stommen PLA. Zwanenburg B.
    J. Plant Growth Regul.  1992,  11:  91 
    Google Scholar
  • 24b Kuad P. Borkovec M. Desage-El Murr M. Le Gall T. Mioskowski C. Spiess B. J. Am. Chem. Soc.  2005,  127:  1323 
    Google Scholar
  • 25a Mangnus EM. Zwanenburg B. J. Agric. Food Chem.  1992,  40:  1066 
    Google Scholar
  • 25b Thuring JWJF. van Gaal AAMA. Hornes SJ. de Kok MM. Nefkens GHL. Zwanenburg B. J. Chem. Soc., Perkin Trans. 1  1997,  767 
    Google Scholar
  • 26a Landor SR. Demetriou B. Grzeskowiak R. Pavey DF. J. Organomet. Chem.  1975,  93:  129 
    Google Scholar
  • 26b Hopf H. Witulski B. In Modern Acetylene Chemistry   Stang PJ. Diederich F. Wiley-VCH; Weinheim: 1995.  Chap. 2. p.33-67  
    Google Scholar
  • 26c Trofimov BA. Andriyankova LV. Shaikhudinova SI. Kazantseva TI. Mal’kina AG. Zhivet’ev SA. Afonin AV. Synthesis  2002,  853 
    Google Scholar
  • 27 Trofimov BA. Curr. Org. Chem.  2002,  6:  1121 
    CrossrefGoogle Scholar