Biomimetic Platinum-Promoted Polyene Polycyclizations: Influence of Alkene Substitution and Pre-cyclization Conformations
| Autor: | Dean J. Tantillo, Brandi M. Hudson, Michael J. Geier, Michel R. Gagné, Christina H. McCulley |
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| Rok vydání: | 2017 |
| Předmět: |
Models
Molecular Squalene Stereochemistry Quantum chemical computations Molecular Conformation chemistry.chemical_element Stereoisomerism Polyenes Alkenes 010402 general chemistry 01 natural sciences Biochemistry Article Catalysis chemistry.chemical_compound Colloid and Surface Chemistry Computational chemistry Biomimetics Models Reactivity (chemistry) Platinum chemistry.chemical_classification 010405 organic chemistry Chemistry Alkene Substitution (logic) Molecular General Chemistry Polyene 0104 chemical sciences Cyclization Chemical Sciences |
| Zdroj: | Journal of the American Chemical Society, vol 139, iss 32 |
| Popis: | Results of kinetic experiments and quantum chemical computations on a series of platinum-promoted polycyclization reactions are described. Analyses of these results reveal a reactivity model that reaches beyond the energetics of the cascade itself, incorporating an ensemble of pre-cyclization conformations of the platinum-alkene reactant complex, only a subset of which are productive for bi- (or larger) cyclization and lead to products. Similarities and differences between this scenario, including reaction coordinates for polycyclization, for platinum- and enzyme-promoted polycyclization reactions are highlighted. |
| Databáze: | OpenAIRE |
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