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Synthesis 2006(4): 637-640  
DOI: 10.1055/s-2006-926292
PAPER
© Georg Thieme Verlag Stuttgart · New York

Cyanide Ion Addition to α,β-Acetylenic γ-Hydroxyacid Nitriles

Anastasiya G. Mal’kina, Olesya A. Shemyakina, Valentina V. Nosyreva, Alexander I. Albanov, Ludmila V. Klyba, Elena R. Zhanchipova, Boris A. Trofimov*
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Street, Irkutsk 664033, Russia
Fax: +7(3952)419346; e-Mail: boris_trofimov@irioch.irk.ru;
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Publication History

Received 29 April 2005
Publication Date:
11 January 2006 (online)

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Abstract

Cyanide ion readily adds in a chemo-, regio- and stereoselective manner to α,β-acetylenic γ-hydroxyacid nitriles 1a-c under mild conditions (KCN, NH4Cl, H2O, MeOH, 20-25 °C, 24 h) to form (Z)-2-(1-hydroxy-1-alkyl)-2-butenedinitriles 2a-c in 70-95% yield. Without NH4Cl, the reaction results in 2-imino-5,5-dialkyl-4-carboxyamide-2,5-dihydrofurans 4a-c (37-45%) along with minor products 4-hydroxy-3-methoxy-4-alkyl-2-alkenenitriles 5a-c and 2-imino-5,5-dialkyl-4-methoxycarbimide-2,5-dihydrofurans 6a,b (total yield 21-35%). Methanolysis of dinitrile 2a (NaOH, 20-25 °C, 1 h) gives iminodihydrofuran 6a (76%) as the only product.

Key words

cyanide ion - α,β-acetylenic γ-hydroxyacid nitriles - dinitriles - 2-iminodihydrofurans - nucleophilic addition