Stepwise Mechanisms in the Ene Reaction of Alpha,Beta-Unsaturated Esters with N-Phenyl-1,2,4-Triazoline-3,5-Dione and Singlet Oxygen - Intermolecular Primary and Secondary Hydrogen Isotope Effects
| dc.contributor.author | Elemes, Y. | en |
| dc.contributor.author | Foote, C. S. | en |
| dc.date.accessioned | 2015-11-24T16:47:50Z | |
| dc.date.available | 2015-11-24T16:47:50Z | |
| dc.identifier.issn | 0002-7863 | - |
| dc.identifier.uri | https://olympias.lib.uoi.gr/jspui/handle/123456789/9241 | |
| dc.rights | Default Licence | - |
| dc.subject | diels-alder reaction | en |
| dc.subject | substituted tetramethylethylenes | en |
| dc.subject | stereochemical dependence | en |
| dc.subject | regioselective reaction | en |
| dc.subject | geminal selectivity | en |
| dc.subject | transition-state | en |
| dc.subject | cis-alkenes | en |
| dc.subject | triazolinediones | en |
| dc.subject | intermediate | en |
| dc.subject | aldimines | en |
| dc.title | Stepwise Mechanisms in the Ene Reaction of Alpha,Beta-Unsaturated Esters with N-Phenyl-1,2,4-Triazoline-3,5-Dione and Singlet Oxygen - Intermolecular Primary and Secondary Hydrogen Isotope Effects | en |
| heal.abstract | Intermolecular primary and secondary isotope effects on the ene reaction of N-phenyl-1,2,4-triazoline-3,5-dione (PTAD) and singlet oxygen (O-1(2)) with deuterium-substituted (E)-2-methylbuten-2-oic (tiglic) acid methyl esters have been determined. In the case Of O-1(2), the primary isotope effect is 1.30-1.49 and the alpha and beta-secondary isotope effects are near unity, consistent with a stepwise reaction path via a perepoxide intermediate, where the allylic hydrogen-abstraction step is rate determining. On the other hand, the existence of both primary (1.44) and inverse alpha and beta-secondary isotope effects (0.91 and 0.77, respectively) in the PTAD reaction is consistent with either a concerted or a stepwise mechanism. Experiments in which both intermolecular primary and secondary isotope effects were measured at the same time suggest that, like singlet oxygen, PTAD reacts in a stepwise manner with the formation of the aziridinium imide intermediate (AI) in the rate-determining-step. | en |
| heal.access | campus | - |
| heal.fullTextAvailability | TRUE | - |
| heal.identifier.primary | Doi 10.1021/Ja00041a023 | - |
| heal.identifier.secondary | <Go to ISI>://A1992JE22500023 | - |
| heal.identifier.secondary | http://pubs.acs.org/doi/pdf/10.1021/ja00041a023 | - |
| heal.journalName | J Am Chem Soc | en |
| heal.journalType | peer reviewed | - |
| heal.language | en | - |
| heal.publicationDate | 1992 | - |
| heal.publisher | American Chemical Society | en |
| heal.recordProvider | Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας | el |
| heal.type | journalArticle | - |
| heal.type.el | Άρθρο Περιοδικού | el |
| heal.type.en | Journal article | en |
Αρχεία
Φάκελος/Πακέτο αδειών
1 - 1 of 1
Φόρτωση...
- Ονομα:
- license.txt
- Μέγεθος:
- 1.74 KB
- Μορφότυπο:
- Item-specific license agreed upon to submission
- Περιγραφή: