We report a nickel-catalyzed cross-coupling between aryl (pseudo)halides and thiols under mechanochemical conditions. The reaction tolerated both alkyl and aryl thiols and required a lower catalyst lo...

We report a nickel-catalyzed cross-coupling between aryl (pseudo-)halides and thiols under mechanochemical conditions. The reaction tolerated both alkyl and aryl thiols and required lower catalyst loa...

We report a nickel-catalyzed stereoselective [2 + 2 + 2] cycloaddition between norbornadienes and benzocyclobutanones via C–C activation. This transformation generates four stereocenters, producing no...

A nickel-catalyzed and Lewis acid-assisted cross-electrophile coupling between thioesters and electron-rich benzylic alcohols is described. A series of investigations delivers insights into the mecha...

Complexes of the type LnNi(σ-aryl)Cl are known to be competitive precatalysts for various transformations, avoiding the use of expensive and sensitive Ni(0)-precursors, such as Ni(cod)2. The in situ activation requires a transmetalation step with a nucleophile, yielding the active Ni(0) catalyst after reductive elimination. Steric hindrance is usually implemented in the σ-aryl group (e.g., o-tolyl or 1-naphthyl) to enhance kinetic stability. Simultaneously, this steric hindrance can render the activation process slow, thus increasing the reaction time and possibly reducing the amount of active catalyst. To circumvent this issue, we envisaged substitution of the anionic chloride ligand of the precatalyst with more labile ligands that would facilitate transmetalation. In this work, a series of (Xantphos)Ni(o-tolyl)X complexes was successfully synthesized, and the effect of the counterion X on the reaction profile was investigated using C–S cross-coupling as the model reaction. (Xantphos)Ni(o-tolyl)OTf was identified as the most efficient precatalyst, probably due to the weak coordinating ability of the triflate anion that facilitated the activation step. Finally, this concept was also studied in Suzuki–Miyaura coupling and Buchwald–Hartwig amination reactions using (dppf)Ni(o-tolyl)X precatalysts.