Anomalous C−C Bond Cleavage in Sulfur-Centered Cation Radicals Containing a Vicinal Hydroxy Group
- 26 September 2003
- journal article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 68 (21) , 8236-8239
- https://doi.org/10.1021/jo035001z
Abstract
1,3-Dithianyl cation radicals having α-hydroxy-neopentyl or similar groups in position 2, which are generated via oxidative photoinduced electron transfer, undergo anomalous fragmentation necessitating refinement of the accepted mechanism. Experimental and computational data support a rationale in which proton abstraction from the hydroxy group in the initial cation radical does not cause a Grob-like fragmentation, but rather produces a neutral radical species, the alkoxy radical, that undergoes fragmentation in either direction, i.e., cleaving the C−C bond to dithiane or to the tertiary alkyl group.Keywords
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