Exploring the Utility of Buchwald Ligands for C-H Oxidative Direct Arylation Polymerizations

Oxidative C-H/C-H cross-coupling polymerizations provide an opportunity to synthesize conjugated polymers with an increased ease of monomer preparation, reduced environmental impact, and increased sustainability. Considering these attributes, it is necessary to expand the diversity of monomers that readily and efficiently participate in this coupling strategy to enable the development of conjugated polymers with a wide range of properties. Herein, the oxidative direct arylation polymerization toolbox is expanded to include 3,4-propylenedioxythiophene being synthesized via C-H/C-H cross-coupling methodologies. In conjunction with these efforts, the utilization of Buchwald ligands in C-H/C-H cross coupling polymerizations also is reported, and variations in the ligand structure provide insight into the role ligand choice has on C-H cross-coupling polymerizations. Specifically, it is determined that the phosphine functionality affects the rate-determining, concerted metalation-deprotonation step of the catalytic cycle, while bulky isopropyl substituents on the ligand's lower aryl ring promote reductive elimination. By balancing these steric effects on the ancillary ligands, polymers are synthesized to exhibit molecular weights above the effective conjugation length, with recovered yields >90%. In addition to expanding the scope of conjugated polymers accessible via oxidative direct arylation polymerization, these results provide the foundational understanding for utilizing Buchwald-type ligands in C-H-activated polymerizations.