A novel p-toluenesulfonic acid-catalyzed solvent-controlled regioselective thiolation of 2-furylcarbinols for the efficient and chemoselective preparation of densely functionalized furan- and lactone-based sulfides under mild metal-free conditions has been developed. By using thiols as nucleophiles in DCE at 80 °C, a new reactivity involving a cascade C5-selective nucleophilic substitution/protonation-hydration/C-S bond cleavage/thia-Michael addition leads to lactone-based sulfides rather than the known Piancatelli-type rearrangement products was revealed for the first time. This tunable thiolation protocol enables ready access to both furan- and lactone-based sulfide derivatives with excellent yields by the judicious choice of the reaction solvent.

中文翻译：

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Brønsted 酸催化溶剂控制区域选择性硫醇化 2-呋喃基甲醇


已经开发了一种新型对甲苯磺酸催化的 2-呋喃基甲醇区域选择性硫醇化，用于在温和的无金属条件下高效和化学选择性制备密集官能化的呋喃和内酯基硫化物。通过在 80 °C 下使用 thiol 作为 DCE 中的亲核试剂，首次揭示了一种涉及级联 C5 选择性亲核取代/质子化-水合/C-S 键切割/thia-Michael 加成的新反应性导致基于内酯的硫化物，而不是已知的 Piancatelli 型重排产物。这种可调硫醇化方案可通过明智地选择反应溶剂，以优异的产率获得基于呋喃和内酯的硫化物衍生物。