Intermediates in the formation and thermolysis of peroxides from oxidations with singlet oxygen
- Herein we describe the recent mechanistic understandings of the singlet oxygen ene reaction to give hydroperoxides and the [4+2] cycloaddition affording endoperoxides. Both experimental findings and theoretical work conclude in the formation of intermediates structurally similar to perepoxides during the ene reaction. Such intermediates mainly control the regio- and stereoselectivities of this reaction class. For the [4+2] cycloaddition, both a synchronous concerted reaction (benzene, naphthalenes) and a stepwise reaction with a non-symmetric zwitterionic intermediate (larger acenes) have been found. The thermolysis of endoperoxides derived from acenes proceeds stepwise for anthracenes, but in a concerted manner for less stable adducts such as naphthalene.
| Author details: | Werner FudickarORCiDGND, Torsten LinkerORCiDGND |
|---|---|
| DOI: | https://doi.org/10.1071/CH13423 |
| ISSN: | 0004-9425 |
| ISSN: | 1445-0038 |
| Title of parent work (English): | Australian journal of chemistry |
| Publisher: | CSIRO |
| Place of publishing: | Clayton |
| Publication type: | Article |
| Language: | English |
| Year of first publication: | 2014 |
| Publication year: | 2014 |
| Release date: | 2017/03/27 |
| Volume: | 67 |
| Issue: | 3 |
| Number of pages: | 8 |
| First page: | 320 |
| Last Page: | 327 |
| Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
| Peer review: | Referiert |
