Lessons from 1,3-Hydride Shifts in Sesquiterpene Cyclizations.
Stereospecifically labelled precursors were subjected to conversion by seven bacterial sesquiterpene cyclases to investigate the stereochemistry of their initial 1,10-cyclisation-1,3-hydride shift cascades. Enzymes with products of known absolute configuration showed a coherent stereochemical course, except for (-)-α-amorphene synthase, for which the obtained results are better explained by an initial 1,6-cyclisation. The link between the absolute configuration of the product and the stereochemical course of the 1,3-hydride shifts enabled assignment of the absolute configurations of three enzyme products, which were confirmed independently through the absolute configuration of the common byproduct germacrene D-4-ol.
Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Straße 1, 53121, Bonn, Germany.
Jan
J
Rinkel
Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Straße 1, 53121, Bonn, Germany.
Patrick
P
Rabe
Nederlands Instituut voor Ecologie, Koninklijke Nederlandse Akademie van Wetenschappen, Droevendaalsesteeg 10, 6708 PB, Wageningen, The Netherlands.
Paolina
P
Garbeva
Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Straße 1, 53121, Bonn, Germany. dickschat@uni-bonn.de.|Nederlands Instituut voor Ecologie, Koninklijke Nederlandse Akademie van Wetenschappen, Droevendaalsesteeg 10, 6708 PB, Wageningen, The Netherlands. dickschat@uni-bonn.de.
Jeroen S
0000-0002-0102-0631
JS
Dickschat
biosynthesis; hydride shifts; isotopes; stereochemistry; terpenes