Palladium(I)-Iodide-Catalyzed Deoxygenative Heck Reaction of Vinyl Triflates: A Formate-Mediated Cross-Electrophile Reductive Coupling with cine-Substitution

The first deoxygenative Heck reactions are described, as illustrated by formate-mediated cine-substitutions of vinyl triflates with aryl iodides. The collective data corroborate a mechanism in which Pd(OAc)2 and Bu4NI form the dianionic iodide-bridged dimer [Pd2I6][NBu4]2, which, under reducing conditions, serves as a precursor to the palladium(I) complex [Pd2I4][NBu4]2. Dinculear oxidative addition of aryl iodide forms [Pd2I5(Ar)][NBu4]2, which dissociates to the monometallic complex [PdI2(Ar)][NBu4]. Vinyl triflate migratory insertion–sulfonate elimination delivers a palladium(IV) carbene, which upon β-hydride elimination/C–H reductive elimination gives the product of cine-substitution. These processes are the first efficient formate-mediated cross-electrophile reductive couplings beyond carbonyl addition.