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Theoretical and Experimental Analysis of the Reaction Mechanism of MrTPS2, a Triquinane‐Forming Sesquiterpene Synthase from Chamomile
Author(s) -
Hong Young J.,
Irmisch Sandra,
Wang Selina C.,
Garms Stefan,
Gershenzon Jonathan,
Zu Liansuo,
Köllner Tobias G.,
Tantillo Dean J.
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201301018
Subject(s) - sesquiterpene , terpene , chemistry , protonation , stereochemistry , reaction mechanism , atp synthase , organic chemistry , enzyme , catalysis , ion
Terpene synthases, as key enzymes of terpene biosynthesis, have garnered the attention of chemists and biologists for many years. Their carbocationic reaction mechanisms are responsible for the huge variety of terpene structures in nature. These mechanisms are amenable to study by using classical biochemical approaches as well as computational analysis, and in this study we combine quantum‐chemical calculations and deuterium‐labeling experiments to elucidate the reaction mechanism of a triquinane forming sesquiterpene synthase from chamomile. Our results suggest that the reaction from farnesyl diphosphate to triquinanes proceeds through caryophyllyl and presilphiperfolanyl cations and involves the protonation of a stable (−)‐( E )‐β‐caryophyllene intermediate. A tyrosine residue was identified that appears to be involved in the proton‐transfer process.