Synthesis of Poly(Arylene Alkenylene)s by Pd‐Catalyzed Three‐Component Coupling Polycondensation of Diiodoarenes, Non‐Conjugated Dienes, and Nucleophiles that Involves Chain Walking Isomerization

Abstract

ABSTRACTThe Pd‐catalyzed three‐component coupling polycondensation of diiodoarenes, nonconjugated dienes, and carbonucleophiles afforded poly(arylene alkenylene)s with moderate molecular weight in good yield. The reaction involves Mizoroki‐Heck coupling, olefin migration via chain walking, and addition of the carbonucleophile to the resulting π‐allylpalladium species. The polymerization with a slight excess of nucleophile with respect to diiodoarene also proceeded to give the polymer without significant decrease in molecular weight in spite of the nonstoichiometric mixture of the monomers. The Pd‐catalyzed three‐component coupling polycondensation of diiodoarenes, nonconjugated dienes, and diimide also proceeded. The base used in the reaction is critical for yield and molecular weight of the product. The reaction using NaHCO3 afforded the product with low solubility, which can be explained by the high molecular weight of the polymer and/or the strong interaction of the electron donating dimethoxyphenylene groups and electron accepting diimide groups in the polymer. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2535–2542