β’-Thio-substituted-enones, assembled from the combination of β-tert-butylthio-substituted aldehydes and alkynes, using rhodium-catalysis, are shown to smoothly undergo in-situ intramolecular S-conjugate addition to deliver a range of S-heterocycles in a one-pot process. Aryl, alkenyl and alkyl aldehydes can all be employed, to provide thiochroman-4-ones, hexahydro-4H-thiochromen-4-ones and tetrahydrothiopyran-4-ones, respectively. A variety of in-situ oxidations are also performed, allowing access to S,S-dioxide derivatives, as well as unsaturated variants.
