title: Anomalous C-C bond cleavage in sulfur-centered cation radicals containing a vicinal hydroxy group.
abstract: 1,3-dithianyl cation radicals having alpha-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.
authors.affiliation: Department of Chemistry and Biochemistry, University of Denver, Denver, Colorado 80208-2436, USA.
authors.forename: Zaiguo
authors.initials: Z
authors.lastname: Li
authors.forename: Andrei G
authors.initials: AG
authors.lastname: Kutateladze