Pd(0)-Catalyzed Polycondensation of Aryl-Substituted Propargylic Carbonates with Bifunctional Nucleophiles Promoted by Aryl Group on the Acetylenic Terminal Carbon

A Pd(0)-catalyzed polycondensation of bifunctional nucleophiles and propargylic carbonates having an aryl group was investigated. The polycondensation was carried out for tetrahydrofuran at 60 degrees C for 3 h in the presence of Pd(0) catalyst. The Pd(0)-catalyzed polycondensation of phenyl-substituted propargylic carbonates and nucleophiles proceeded efficiently, when bis[(2-diphenylphosphino)phenyl]ether was used as the ligand. We found that the position of the phenyl group was crucial for the successful polycondensation. The introduction of a phenyl group on the acetylenic terminal carbon remarkably promoted the polycondensation and afforded high molecular weight polymers. On the other hand, a phenyl group at the propargylic position was not effective. Propargylic carbonates having a substituted phenyl group were also examined. Electron-withdrawing group-substituted phenyl groups on the acetylenic terminal carbon were found to be more effective for the polycondensation. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 642-649, 2011