Abstract
Visible-light photocatalysis and electrocatalysis are two powerful strategies for the promotion of chemical reactions. Here, these two modalities are combined in an electrophotocatalytic oxidation platform. This chemistry employs a trisaminocyclopropenium (TAC) ion catalyst, which is electrochemically oxidized to form a cyclopropenium radical dication intermediate. The radical dication undergoes photoexcitation with visible light to produce an excited-state species with oxidizing power (3.33 V vs. SCE) sufficient to oxidize benzene and halogenated benzenes via single-electron transfer (SET), resulting in C−H/N−H coupling with azoles. A rationale for the strongly oxidizing behavior of the photoexcited species is provided, while the stability of the catalyst is rationalized by a particular conformation of the cis-2,6-dimethylpiperidine moieties.
Original language | English |
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Pages (from-to) | 13318-13322 |
Number of pages | 5 |
Journal | Angewandte Chemie - International Edition |
Volume | 58 |
Issue number | 38 |
DOIs | |
Publication status | Published - 16 Sept 2019 |
Externally published | Yes |
Keywords
- C−H functionalization
- Electrophotocatalysis
- oxidation
- radical dication
- trisaminocyclopropenium ion