Mechanistic Aspects of β-Bond-Cleavage Reactions of Aromatic Radical Cations
- 25 March 2000
- journal article
- review article
- Published by American Chemical Society (ACS) in Accounts of Chemical Research
- Vol. 33 (4) , 243-251
- https://doi.org/10.1021/ar980014y
Abstract
The mesolytic cleavage of a β-C−X bond (ArCR2−X•+ → ArCR2•/+ + X+/•) is one of the most important reactions of alkylaromatic radical cations. In this Account, our group's results concerning some fundamental aspects of this process (cleavage mode, structural and stereoelectronic effects, competitive breaking of different β-bonds, nucleophilic assistance, possible stereochemistry, carbon vs oxygen acidity in arylalkanol radical cations) are presented and critically discussed for reactions where X = H, CR3, SR, and SiR3. Several examples illustrating how this information was exploited as a tool to detect electron-transfer mechanisms in chemical and enzymatic oxidations are also reported.Keywords
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