Radical-mediated thiodesulfonylation of the vinyl and (alpha-fluoro)vinyl sulfones, derived from aldehydes and ketones, with aryl thiols in organic or aqueous medium provided access to vinyl and (a-fluoro)vinyl sulfides. The vinyl sulfides were formed predominantly with E stereochemistry independent of the stereochemistry of the starting vinyl sulfones. (C) 2009 Elsevier Ltd. All rights reserved.