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Lessons from 1,3‐Hydride Shifts in Sesquiterpene Cyclizations
Author(s) -
Rinkel Jan,
Rabe Patrick,
Garbeva Paolina,
Dickschat Jeroen S.
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201608042
Subject(s) - sesquiterpene , absolute configuration , hydride , chemistry , stereochemistry , absolute (philosophy) , enzyme , computational chemistry , organic chemistry , hydrogen , philosophy , epistemology
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.