Palladium Catalyzed Oxidative Coupling of α‑Enolic Dithioesters: A New Entry to 3,4,5-Trisubstituted 1,2-Dithioles <i>via</i> a Double Activation Strategy

An operationally simple, facile, and convenient one-pot straightforward method for the construction of 3,4,5-trisubstituted 1,2-dithioles has been explored and developed via palladium catalyzed self-coupling of α-enolic dithioesters for the first time. Pd(0) efficiently catalyzes the activation and cleavage of S–H and C–S bonds to achieve cascade coupling, which results in the concomitant formation of new S–S and C–C bonds. Optimization data, substrate scope, and mechanistic insights are discussed.