Synthesis of heterotactic and syndiotactic polyacrylamides via stereospecific radical polymerization of N-tert-butoxycarbonylacrylamide in the presence of fluorinated alcohols

Radical polymerization of a new protected monomer, N‐tert‐butoxycarbonylacrylamide, in toluene at −40 or 0 °C in the presence of fluorinated alcohols was investigated. The obtained polymers were successfully converted into polyacrylamide under acidic conditions. Further, it was revealed that atactic, heterotactic, and syndiotactic polymers were obtained with the addition of trifluoroethanol, 1,1,1,3,3,3‐hexafluoro‐2‐propanol, and nonafluoro‐tert‐butanol, respectively. To the best of our knowledge, these are the first syntheses of heterotactic and syndiotactic polyacrylamides.