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.
Rinkel, J., Rabe, P., Garbeva, P. V., & Dickschat, J. (2016). Lessons from 1,3-Hydride Shifts in Sesquiterpene Cyclizations. Angewandte Chemie, 55(43), 13593-13596. https://doi.org/10.1002/anie.201608042