Photooxygenation of oxygen-substituted naphthalenes
- The reaction of oxygen-substituted naphthalenes with singlet oxygen (O-1(2)) has been investigated, and labile endoperoxides have been isolated and characterized at -78 degrees C for the first time. Low-temperature kinetics by UV spectroscopy revealed that alkoxy and silyloxy substituents remarkably increase the rate of photooxygenations compared to 1,4-dimethylnaphthalene, whereas acyloxy-substituted acenes are inert towards O-1(2). The reactivities nicely correlate with HOMO energies and free activation energies, which we determined by density functional theory calculations. The lability of the isolated endoperoxides is due to their very fast back reaction to the corresponding naphthalenes even at -20 degrees C under release of O-1(2), making them to superior sources of this reactive species under very mild conditions. Finally, a carbohydrate-substituted naphthalene has been synthesized, which reacts reversibly with O-1(2) and might be applied for enantioselective oxidations in future work.
Author details: | Marcel BauchORCiD, Angela Krtitschka, Torsten LinkerORCiDGND |
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DOI: | https://doi.org/10.1002/poc.3734 |
ISSN: | 0894-3230 |
ISSN: | 1099-1395 |
Title of parent work (English): | Journal of physical organic chemistry |
Publisher: | Wiley |
Place of publishing: | Hoboken |
Publication type: | Article |
Language: | English |
Year of first publication: | 2017 |
Publication year: | 2017 |
Release date: | 2020/04/20 |
Tag: | kinetics; labile peroxides; low-temperature experiments; naphthalenes; singlet oxygen |
Volume: | 30 |
Number of pages: | 11 |
First page: | 6803 |
Last Page: | 6813 |
Funding institution: | University of Potsdam |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
Peer review: | Referiert |