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Probing eudesmane cation−π interactions in catalysis by aristolochene synthase with non-canonical amino acids

Faraldos, Juan A., Antonczak, Alicja K., Gonzalez, Veronica, Fullerton, Rebecca, Tippmann, Eric Michael and Allemann, Rudolf Konrad 2011. Probing eudesmane cation−π interactions in catalysis by aristolochene synthase with non-canonical amino acids. Journal of the American Chemical Society 133 (35) , pp. 13906-13909. 10.1021/ja205927u

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Abstract

Stabilization of the reaction intermediate eudesmane cation (3) through interaction with Trp 334 during catalysis by aristolochene synthase from Penicillium roqueforti was investigated by site-directed incorporation of proteinogenic and non-canonical aromatic amino acids. The amount of germacrene A (2) generated by the mutant enzymes served as a measure of the stabilization of 3. 2 is a neutral intermediate, from which 3 is formed during PR-AS catalysis by protonation of the C6,C7 double bond. The replacement of Trp 334 with para-substituted phenylalanines of increasing electron-withdrawing properties led to a progressive accumulation of 2 that showed a good correlation with the interaction energies of simple cations such as Na+ with substituted benzenes. These results provide compelling evidence for the stabilizing role played by Trp 334 in aristolochene synthase catalysis for the energetically demanding transformation of 2 to 3.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Cardiff Catalysis Institute (CCI)
Chemistry
Subjects: Q Science > QD Chemistry
Publisher: American Chemical Society
ISSN: 0002-7863
Funders: BBSRC
Last Modified: 10 Oct 2017 13:29
URI: http://orca.cf.ac.uk/id/eprint/14506

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