Cardiff University | Prifysgol Caerdydd ORCA
Online Research @ Cardiff 
WelshClear Cookie - decide language by browser settings

Stabilisation of transition states prior to and following eudesmane cation in aristolochene synthase

Forcat, Silvia and Allemann, Rudolf Konrad ORCID: https://orcid.org/0000-0002-1323-8830 2006. Stabilisation of transition states prior to and following eudesmane cation in aristolochene synthase. Organic & Biomolecular Chemistry 4 (13) , pp. 2563-2567. 10.1039/b604147g

Full text not available from this repository.

Abstract

The mechanistic details of the cyclisation of farnesylpyrophosphate (FPP) by aristolochene synthase (AS) from Penicillium roqueforti have only recently begun to emerge, mainly through the analysis of the reaction products generated by AS-mutants. The reaction proceeds through several intermediates including germacrene A and eudesmane cation. Previous work suggested that the side chain of phenylalanine 178 promoted the conversion of eudesmane cation to aristolochene. We now report that the catalytic function of this residue during the conversion of eudesmane cation to aristolochene is mainly due to the large size of its side chain, which facilitates the hydride shift from C2 to C3, rather than its aromatic character. In addition, F178 appears to control the regioselectivity of the final deprotonation step and, together with F112, helps stabilise the developing positive charge on C1 after the expulsion of pyrophosphate from the substrate. These results complete a screen of likely active-site aromatic residues and establish their respective roles in the conversion of FPP to aristolochene.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Subjects: Q Science > QD Chemistry
Publisher: RSC Publishing
ISSN: 1477-0520
Last Modified: 18 Oct 2022 13:19
URI: https://orca.cardiff.ac.uk/id/eprint/13495

Citation Data

Cited 24 times in Scopus. View in Scopus. Powered By Scopus® Data

Actions (repository staff only)

Edit Item Edit Item