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Synthesis 2001(12): 1866-1872
DOI: 10.1055/s-2001-17523
PAPER
© Georg Thieme Verlag Stuttgart · New York

Selective Hydrolysis of Aliphatic Dinitriles to Monocarboxylic Acids by a Nitrilase from Arabidopsis thaliana [1]

Franz Effenberger*, Steffen Oßwald
Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
Fax: +49(711)6854269; e-Mail: franz.effenberger@po.uni-stuttgart.de;
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Publication History

Received 10 April 2001
Publication Date:
12 August 2004 (online)

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Abstract

The hydrolysis of a variety of dinitriles including α,ω-dicyanoalkanes 1, β-substituted glutaronitriles 5, and γ-cyanopimelonitrile 7 with a recombinant plant nitrilase from Arabidopsis thaliana, expressed in E. coli, is described. Conversion rate and selectivity of the hydrolysis of dinitriles 1a-f to ω-cyanocarboxylic acids 2a-f depend on the chain length. The enzyme activity markedly increases from malononitrile (1a) to octanedinitrile (1f). The selectivity, however, does not correlate with the rates. Up to a chain length of 6 C-atoms, the cyanocarboxylic acid is the only product, even at complete conversion of the starting material. Pimelonitrile (1e) is hydrolyzed to the cyanocarboxylic acid 2e without formation of diacid (<1%) up to 73% conversion. Glutaronitriles 5a-c were also hydrolyzed to the corresponding cyanobutanoic acids 6a-c with perfect selectivity. The nitrilase hydrolyzes exclusively the primary cyano group of 7 to give 3,5-dicyanoheptanoic acid (8a), whereby the selectivity is slightly reduced compared to the unsubstituted pimelonitrile (1e). If the hydrolysis is terminated at conversions ≤90%, pure 8a can be isolated in 72% yield (92% referred to conversion). After esterification of 8a to the methyl ester 8b, only the 5-cyano group but not the ester function was hydrolyzed enzymatically to give cyanoheptanedioic acid monoester (10).

Key words

catalysis - enzymes - hydrolyses - nitriles - regioselectivity

9

Oßwald, S.; Wajant, H.; Effenberger, F., in preparation.