Regioselective Alkyne Hydroarylation as an Atom-Economical Approach to Oligomerization

Nickel-catalyzed hydroarylation allows a completely atom-economical approach by the catalytic union of alkynes and polyfluorinated arenes through a ligand-to-ligand hydrogen transfer (LLHT) mechanism. To enable application of this process in oligomerizations and polymerizations, we studied the influence of catalyst, ligand, and substrate structure to control regioselectivity and optimize yields towards a single reaction outcome. These findings were applied in 2:1 alkyne:arene couplings to develop model conditions and were then further evaluated in preliminary applications of step-growth polymerizations.