Nickel‐Catalyzed Reductive Coupling of Carboxylic Acids with Disulfides to Access Thioesters

Abstract

A nickel‐catalyzed reductive cross coupling reaction of carboxylic acids with disulfides is described. The readily available and inexpensive carboxylic acid is activated in situ by the formation of a mixed anhydride. The transformation occurs at room temperature with wide functional group tolerance to efficiently generate structurally diverse thioesters. Moreover, the reaction tolerated a broad substrate scope, including sterically hindered of disulfides. Ultimately, this powerful method could be applied to the late‐stage functionalization for the construction of diverse thioesters, affording a convenient and practical tactic to construct carbon‐sulfur bonds.

Nickel-catalysed chelation-assisted reductive defluorinative sulfenylation of trifluoropropionic acid derivatives

“…On the other hand, Ni 0 complex undergoes oxidative addition with disulfides 2 to afford Ni II intermediate IV . 15 The resulting intermediate II interacted with Ni II intermediate IV to generate a migration insertion intermediate V , followed by β-F elimination to afford intermediate VI , which could undergo rapidly migration insertion by Ni–H intermediate III to afford Ni II intermediate VII . Subsequently, the β-F elimination of intermediate VII to provide the corresponding product thioacrylates 3 .…”