Photoinduced Electron-Transfer Oxidation of Olefins with Molecular Oxygen Sensitized by Tetrasubstituted Dimethoxybenzenes: A Non-Singlet-Oxygen Mechanism
✍ Scribed by Tadashi Mori; Makoto Takamoto; Takehiko Wada; Yoshihisa Inoue
- Publisher
- John Wiley and Sons
- Year
- 2001
- Tongue
- German
- Weight
- 177 KB
- Volume
- 84
- Category
- Article
- ISSN
- 0018-019X
No coin nor oath required. For personal study only.
✦ Synopsis
Dedicated to Professor Andre M. Braun on the occasion of his 60th birthday a-Methylstyrene (1) was photo-oxidized in the presence of a series of alkylated dimethoxybenzenes as sensitizers in an oxygen-saturated MeCN solution to afford the cleaved ketone 2, epoxide 3, as well as a small amount of the ene product 4 in ca. 1 : 1 : 0.04 ratio. The relative rate of conversion was well-correlated with the fluorescence quantum yield of sensitizers. Thus, a non-singlet-oxygen mechanism is proposed, in which an excited sensitizer is quenched by (ground-state) molecular oxygen to produce a sensitizer radical cation and a superoxide ion (O À.
2 ), the former of which oxidizes the substrate, while the latter reacts with the resulting olefin radical cation (1 . ) to give the major oxidation products. Photodurability of such electron-donating sensitizers is dramatically improved by substituting four aromatic H-atoms in 1,4-dimethoxybenzene with Me or fused alkyl groups, which provides us with an environmentally friendly, clean method of photochemical functionalization with molecular oxygen, alternative to the ene reaction via singlet oxygenation.