Amide-Directed Rhodium-Catalyzed Chain-Walking Hydrothiolation of Internal Alkenes.

We developed a rhodium-catalyzed chain-walking hydrothiolation process for internal alkenes, which offers a novel and efficient alternative for C(sp)-H bond cleavage, while focusing on thiol incorporation. This method exclusively affords ,-acetals at 36-90% yields. Regioconvergent hydrothiolation significantly improved the effectiveness of this transformation.