Electronic Effects on the Selectivity of Pd‐Catalyzed CN Bond‐Forming Reactions Using Biarylphosphine Ligands: The Competitive Roles of Amine Binding and Acidity

Electronic influence: Correlation between the relative binding constants of amines to isolated [SPhosPd(Ph)Cl] (SPhos=2-dicyclohexylphosphino-2′,6′-dimethoxy-1,1′-biphenyl) and the pKa of the amine complexes shows that the selectivity in the catalytic arylation of amines is influenced by the electronic properties of the amine. Selectivities observed in CN cross-coupling reactions using neutral amines can be reversed using lithium amides.