Blocking Deprotonation with Retention of Aromaticity in a Plant ent -Copalyl Diphosphate Synthase Leads to Product Rearrangement
| Autor: | Kevin C. Potter, Reuben J. Peters, Brandi Malchow, Jiachen Zi, Samuel Schulte, Dean J. Tantillo, Young J. Hong |
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| Rok vydání: | 2015 |
| Předmět: |
Reaction mechanism
Stereochemistry natural products 010402 general chemistry 01 natural sciences Catalysis Article Gas Chromatography-Mass Spectrometry Residue (chemistry) chemistry.chemical_compound Deprotonation Biosynthesis rearrangements Histidine Plant Proteins Alkyl and Aryl Transferases biology 010405 organic chemistry Chemistry cyclizations Organic Chemistry food and beverages Aromaticity General Chemistry Metabolism General Medicine Plants 0104 chemical sciences reaction mechanisms Chemical Sciences biology.protein ent-Copalyl diphosphate synthase Protons biosynthesis |
| Zdroj: | Angewandte Chemie (International ed. in English), vol 55, iss 2 |
| ISSN: | 0044-8249 |
| DOI: | 10.1002/ange.201509060 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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