Lessons from 1,3-Hydride Shifts in Sesquiterpene Cyclizations

J. Rinkel; P. Rabe; P.V. Garbeva; Jeroen Dickschat

doi:10.1002/anie.201608042

Lessons from 1,3-Hydride Shifts in Sesquiterpene Cyclizations

J. Rinkel
, P. Rabe
, P.V. Garbeva
, Jeroen Dickschat

NIOO - Microbial Ecology (ME)

Research output: Contribution to journal/periodical › Article › Scientific › peer-review

51 Citations (Scopus)

8 Downloads (Pure)

Abstract

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.

Original language	English
Pages (from-to)	13593-13596
Journal	Angewandte Chemie
Volume	55
Issue number	43
Early online date	26 Sept 2016
DOIs	https://doi.org/10.1002/anie.201608042
Publication status	Published - 2016

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international

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AU - Dickschat, Jeroen

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Lessons from 1,3-Hydride Shifts in Sesquiterpene Cyclizations

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