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Blocking Deprotonation with Retention of Aromaticity in a Plant ent ‐Copalyl Diphosphate Synthase Leads to Product Rearrangement
Author(s) -
Potter Kevin C.,
Zi Jiachen,
Hong Young J.,
Schulte Samuel,
Malchow Brandi,
Tantillo Dean J.,
Peters Reuben J.
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.201509060
Subject(s) - deprotonation , chemistry , atp synthase , blocking (statistics) , aromaticity , stereochemistry , biochemistry , organic chemistry , enzyme , computer science , molecule , ion , computer network
Substitution of a histidine, comprising part of the catalytic base group in the ent‐copalyl diphosphate synthases found in all seed plants for gibberellin phytohormone metabolism, by a larger aromatic residue leads to rearrangements. Through a series of 1,2‐hydride and methyl shifts of the initially formed bicycle predominant formation of (−)‐kolavenyl diphosphate is observed. Further mutational analysis and quantum chemical calculations provide mechanistic insight into the basis for this profound effect on product outcome.