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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;
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Publication History

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

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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

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