Lessons from 1,3-Hydride Shifts in Sesquiterpene Cyclizations.
Angew Chem Int Ed Engl
; 55(43): 13593-13596, 2016 10 17.
Article
in En
| MEDLINE
| ID: mdl-27666571
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 germacreneâ
D-4-ol.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Angew Chem Int Ed Engl
Year:
2016
Document type:
Article
Affiliation country:
Germany