Higher‐Order Zincates as Transmetalators in Alkyl–Alkyl Negishi Cross‐Coupling

Negishi revisited: higher-order alkyl zincates have been subjected to Negishi coupling with alkyl bromides. For the first time, coupling takes place in straight THF, i.e., without a salt additive and a high dielectric co-solvent. This provides evidence that it is the higher-order zincate that undergoes transmetalation to Pd, and not mono-anionic zincates or any of the other species present in the Schlenk equilibrium.