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Direct (hetero)arylation polymerization exploits the palladium-catalyzed activation of aromatic CH bonds for the atom-economical synthesis of conjugated polymers for a wide range of applications. This account outlines how direct arylation methodologies overcome many of the limitations of contemporary polymerization techniques at both the research and production scale, and explains how monomer design and reaction conditions must be tailored to ensure high polymer molecular weight, yield, and structural integrity. Current research aims to improve further this reaction's profile as a sustainable methodology while at the same time making it competitive with the Migita-Stille and Miyaura-Suzuki polymerizations both in scope of accessible structures and synthetic efficiency. This feature article charts the recent developments and future directions of CH activation research as it moves toward becoming at once an industrially feasible, environmentally friendly, and synthetically powerful polymerization technique.
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