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Radical cation initiated cyclization reactions can be triggered by the one electron oxidation of an electron-rich olefin using either electrochemistry or visible light and a photoredox catalyst. In principle, the two methods can be used to give complimentary products with the electrolysis leading to products derived from a net two electron oxidation and the photoelectron transfer method being compatible with the formation of products from a redox neutral process. However, we are finding an increasing number of oxidative cyclization reactions that require the rapid removal of a second electron in order to form high yields of the desired product. In those cases, the electrochemical method can provide a superior approach to accessing the necessary two electron oxidation pathway. With that said, it is a combination of the two methods that provides the mechanistic insight needed to understand when a reaction has this requirement, and we are finding that the use of photoredox catalysis in combination with electrochemical methods is changing our understanding of even the most successful anodic cyclization reactions run to date.
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Anodic Olefin Coupling Reactions: Elucidating Radical Cation Mechanisms and the Interplay between Cyclization and Second Oxidation Steps
Abstract Anodic olefin coupling reactions generate new bonds and ring skeletons through a net two electron process that reverses the polarity of a known, electron‐rich functional group. While much of the early work on the mechanism of these reactions focused on the initial oxidation and cyclization steps of the process, the second oxidation step also plays a central role in determining the success of the reaction. Evidence supporting this observation is presented, along with evidence that optimization of this second oxidation step is not enough to pull a poor cyclization to the desired product. Successful cyclization reactions require optimization of both processes.
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- Award ID(s):
- 1764449
- PAR ID:
- 10249304
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- The Chemical Record
- Volume:
- 21
- Issue:
- 9
- ISSN:
- 1527-8999
- Page Range / eLocation ID:
- p. 2442-2452
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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