Lessons from 1,3-Hydride Shifts in Sesquiterpene Cyclizations

TY - JOUR

T1 - Lessons from 1,3-Hydride Shifts in Sesquiterpene Cyclizations

AU - Rinkel, J.

AU - Rabe, P.

AU - Garbeva, P.V.

AU - Dickschat, Jeroen

N1 - 6159, ME;

PY - 2016

Y1 - 2016

N2 - 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.

AB - 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.

KW - international

U2 - 10.1002/anie.201608042

DO - 10.1002/anie.201608042

M3 - Article

SN - 1433-7851

VL - 55

SP - 13593

EP - 13596

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 43

ER -