Rational Ligand Design for the Arylation of Hindered Primary Amines Guided by Reaction Progress Kinetic Analysis

We
report the Pd-catalyzed arylation of very hindered α,α,α-trisubstituted
primary amines. Kinetics-based mechanistic analysis and rational design
have led to the development of two biarylphosphine ligands that allow
the transformation to proceed with excellent efficiency. The process
was effective in coupling a wide range of functionalized aryl and
heteroaryl halides under mild conditions.