On the Mechanism of the ?-Alkynone Cyclization: A Theoretical Study
| Autor: | André S. Dreiding, Martin Karpf, José Kaneti |
|---|---|
| Rok vydání: | 1982 |
| Předmět: |
chemistry.chemical_classification
Chemistry Organic Chemistry Ab initio Substituent Biochemistry Propynal Catalysis Transition state Inorganic Chemistry chemistry.chemical_compound Acetylene Computational chemistry Drug Discovery Physics::Chemical Physics Physical and Theoretical Chemistry Carbene Alkyl Acyl group |
| Zdroj: | Helvetica Chimica Acta. 65:2517-2525 |
| ISSN: | 1522-2675 0018-019X |
| DOI: | 10.1002/hlca.19820650821 |
| Popis: | The acetylene carbene rearrangement of three model a-alkynones, namely propynal (1a), 2-butynal (1b) and butynone (1c) is studied by ab initio double-zeta, double-zeta plus polarization and double-zeta plus self-consistent electron pairs calculations. Transition states are located by force-gradient geometry optimization. Calculated minimum energy reaction paths reveal substituent effects on the activation parameters, which indicate that a H-atom or an alkyl group competes favorably with an acyl group in the [1,2]-shift from a-alkynones 1 to the corresponding acylvinylidenes 5. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Plný text