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Mechanistic Insight into the Photoredox Catalysis of Anti-Markovnikov Alkene Hydrofunctionalization Reactions
Open accessAbstract
We describe our efforts to understand the key mechanistic aspects of the previously reported alkene hydrofunctionalization reactions using 9-mesityl-10-methylacridinium (Mes-Acr(+)) as a photoredox catalyst. Importantly, we are able to detect alkene cation radical intermediates, and confirm that phenylthiyl radical is capable of oxidizing the persistent acridinyl radical in a fast process that unites the catalytic activity of the photoredox and hydrogen atom transfer (HAT) manifolds. Additionally, we present evidence that diphenyl disulfide ((PhS)2) operates on a common catalytic cycle with thiophenol (PhSH) by way of photolytic cleaveage of the disulfide bond. Transition structure analysis of the HAT step using DFT reveals that the activation barrier for H atom donation from PhSH is significantly lower than 2-phenylmalononitrile (PMN) due to structural reorganization. In the early stages of the reaction, Mes-Acr(+) is observed to engage in off-cycle adduct formation, presumably as buildup of PhS(-) becomes significant. The kinetic differences between PhSH and (PhS)2 as HAT catalysts indicate that the proton transfer step may have significant rate limiting influence.
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Metadata
- Authors
- Romero, N. A., & Nicewicz, D. A.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2014-11-24
- Volume
- 136
- Issue
- 49
- Pages
- 17024-17035
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2317194706
- Cited by
- 377
- References
- 51
- FWCI
- 10.70
- Type
- journal article
- Language
- en
- Open access
- hybrid
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