| Autor: |
Ruth M. Gschwind, Christian Feldmeier, Hanna Bartling, Kathrin Magerl |
| Rok vydání: |
2014 |
| Předmět: |
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| Zdroj: |
Angewandte Chemie International Edition. 54:1347-1351 |
| ISSN: |
1433-7851 |
| DOI: |
10.1002/anie.201409146 |
| Popis: |
Mechanistic insights into chemical photocatalysis are mainly the domain of UV/Vis spectroscopy, because NMR spectroscopy has been limited by the type of illumination so far. An improved LED-based illumination device can be used to obtain NMR reaction profiles of photocatalytic reactions under synthetic conditions and perform both photo-CIDNP and intermediate studies. Flavin-catalyzed photooxidations of alcohols show the potential of this setup. After identical initial photoreaction steps the stabilization of a downstream intermediate is the key to the further reaction mechanism and the reactivity. As a chemical photocatalyst flavin can act either as a one- or a two-electron mediator when the stability of the zwitterionic radical pair is moldulated in different solvents. This demonstrates the importance of downstream intermediates and NMR-accessible complementary information in photocatalytic reactions and suggests the control of photoorganic reactions by solvent effects. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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