Blocking Deprotonation with Retention of Aromaticity in a Plant ent-Copalyl Diphosphate Synthase Leads to Product Rearrangement

Biblio

Publication Type:

Journal Article

Source:

Angew Chem Int Ed Eng, Volume 55, Issue 2, p.634-638 (2016)

ISBN:

1521-3773 (Electronic)<br/>1433-7851 (Linking)

Accession Number:

26603275

Keywords:

Biosynthesis, cyclizations, natural products, reaction mechanisms, rearrangements

Abstract:

<p>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.</p>

Notes:

Potter, Kevin C<br/>Zi, Jiachen<br/>Hong, Young J<br/>Schulte, Samuel<br/>Malchow, Brandi<br/>Tantillo, Dean J<br/>Peters, Reuben J<br/>ENG<br/>2015/11/26 06:00<br/>Angew Chem Int Ed Engl. 2015 Nov 25. doi: 10.1002/anie.201509060.