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 °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. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011