Both aromatic and aliphatic thiols were well tolerated in the alkylation with thietanol dioxide 2a, and the reaction proceeded smoothly at 40 ºC (5aa-5ae). Alkylation using the less electron-rich thietanol dioxide 2h was also successful (5hb, 5hd) but required higher thermal activation (110 ºC). Although the direct application of the reaction conditions to alcohol nucleophiles was unsuccessful, changing to Brønsted acid catalysis (Tf2NH, 10 mol%) in MeCN achieved the O-alkylation of primary and benzylic alcohols (6aa-6ac). Secondary alcohols were not tolerated due to a reversible C-O bond formation but irreversible elimination step funnelling the material to thiete dioxide 4a.