Radical polymerization of N tert butoxycarbonylacrylamide (NBocAAm) in toluene at low temperatures in the presence of the fluorinated alcohols 2 2 2 trifluoroethanol 111 3 3 3 hexafluoro 2 propanol and nonafluoro ten butanol afforded atactic heterotactic and syndiotactic polymers respectively NMR analysis revealed that the fluorinated alcohols formed hydrogen bonding assisted complexes with NBocAAm with different structures The difference in the structures of the complexes was responsible for the differences in the induced stereospecificities Based on the structures of the complexes between NBocAAm and the fluorinated alcohols mechanisms for the three kinds of stereospecific radical polymerizations are proposed (c) 2010 Wiley Periodicals Inc J Polym Sci Part A Polym Chem 48 5718-5726 2010