The fluoride ion catalyzed oligomerization of F-vinylamines, such as F
-(N,N-dimethylvinylamine), F-(N-vinylmorpholine) and F-(N-vinylpyrroli
dine). was investigated. It was found that dimers were obtained in hig
h yields when the reaction was conducted in aprotic polar solvents, es
pecially in DMF using cesium fluoride as a fluoride ion source. Attemp
ts to obtain oligomers higher than dimers failed. The absence of highe
r oligomers is discussed in stereoelectronic and steric terms by compa
rison with the analogous oligomerization of hexafluoropropene. Unexpec
ted results obtained in the reaction of F-(N,N-dimethylvinylamine) wit
h the hexafluoropropene dimer F-2-methyl-2-propene are also included.