ABSTRACT: Polycyclic, non enolizable cycloaliphatic thioketones 1a and 1b react smoothly with the lithium salt of diethyl methylphosphonate 7 in THF solution at –40°C to afford products of the carbophilic attack exclusively. Quenching of the obtained lithium thiolates with alkyl iodides yields sulfanes of type 9 or 11, respectively, in good yields. 1-Fluoro-2,4-dinitrobenzene was shown to act as an arylating agent. In the case of the ‘cage’ thioketone 1b, the carbanion of salt 7 approaches the C=S bond from the exo-side exclusively. In contrast to the parent carbonyl compounds, thioketones 1 show no tendency to undergo the conversion analogous to the Horner-Wadsworth-Emmons reaction, which would result in the formation of an olefinic product.